1

Department of Organic Chemical Technologies Prof As Zlatarov University of Burgas Bulgaria e-mail gkostovbtubg

Recent Advances in the Synthesis and Properties of Functionalized

Fluoropolymers as Engineering Materials

GKostov

VII National Conference on Chemistry 26-29 May 2011 Sofia Bulgaria

2

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

33

1 FEATURES BENEFITS ADVANTAGES of F POLYMERS

LOW REFRACTIVE INDEX

OPTICAL FIBRES AND COATINGS

LOW SURFACE ENERGY

LUBRICITY RELEASE

VERY LOW SURFACE TENSION

SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS

VERY STRONG ORGANIC ACIDS

CATALYSTS amp PROTON EXCHANGE MEMBRANES

4

HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY

PROTECTIVE COATINGS

INSULATION

WIRE AND CABLE INDUSTRIES

HIGH OIL WATER AND SOIL REPELLENCY

TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION

5

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

2

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

33

1 FEATURES BENEFITS ADVANTAGES of F POLYMERS

LOW REFRACTIVE INDEX

OPTICAL FIBRES AND COATINGS

LOW SURFACE ENERGY

LUBRICITY RELEASE

VERY LOW SURFACE TENSION

SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS

VERY STRONG ORGANIC ACIDS

CATALYSTS amp PROTON EXCHANGE MEMBRANES

4

HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY

PROTECTIVE COATINGS

INSULATION

WIRE AND CABLE INDUSTRIES

HIGH OIL WATER AND SOIL REPELLENCY

TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION

5

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

33

1 FEATURES BENEFITS ADVANTAGES of F POLYMERS

LOW REFRACTIVE INDEX

OPTICAL FIBRES AND COATINGS

LOW SURFACE ENERGY

LUBRICITY RELEASE

VERY LOW SURFACE TENSION

SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS

VERY STRONG ORGANIC ACIDS

CATALYSTS amp PROTON EXCHANGE MEMBRANES

4

HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY

PROTECTIVE COATINGS

INSULATION

WIRE AND CABLE INDUSTRIES

HIGH OIL WATER AND SOIL REPELLENCY

TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION

5

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

4

HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY

PROTECTIVE COATINGS

INSULATION

WIRE AND CABLE INDUSTRIES

HIGH OIL WATER AND SOIL REPELLENCY

TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION

5

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

5

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

6

21 Advantages of polymer opticalmaterials over conventional glasses

High optical transparency at transmission wavelengths

Potential to tune their optical properties by tailoringthe molecular structure

Lightweight

Flexibility even at large diameters

Good processability

Easy handling

Low cost

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

7

23Disadvantages of POWs

POWs reveal optical losses much higher than silica

PMMA (visible region) ndash 100 dBkm

Silica fibres ndash 03 dBkm

Transmission on short distances

Develop partial crystallinity and low Tg

Organic polymers are prone to oxidative degradation

22Applications of POWs

Short-haul communication links

Data systems in aircrafts automobiles

Local area networks

Inter- and intra- office network systems

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

8

SOLUTION

Substitution of F (or D) atoms for H atoms

- low overtone band strength

- less scattering

- low nD

Lower attenuation

Amorphous fluorinated polymers

Cytop trade(Asahi Glass)

Teflonreg AF(Du Pont)

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

9

24 OBJECTIVES

1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials

2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

10

25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS

Requirements for optical polymers

Optical transparency in the visible and NIR regions

amorphous with high Tg nD ndash14-15 Td gt150degC

Good processability to fibers films and tapes (Mn=2000-4000 gmol)

Photocrosslinkable (preferably acrylic and fluorinatedresins)

Homogenous network with good mechanical properties

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

11

Scheme 1 General scheme of fluoroacrylate synthesis

Fluoroolefin

-+ +

cyclicmonomer

termonomerX X OH

OH OH

OH

OCOCH=CH2

OCOCH=CH2

OCOCH=CH2

CF2=CFCl (CTFE)

CF2=CF(CF3) (HFP)

O O

O

Vinylenecarbonate

X=O(CH2)n

n=2 or n=4

Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)

Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

1212

261) Fluorooligomers CTFEVCA-basedcopolymers

Length limit of polymer

Chain-transfer agent or suitable solvent

Photocrosslinkable reactive functions

Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index

2) Photocrosslinking

UV

Reactive diluent(s) Amorphous crosslinked network

26 CTFEVCAhydroxy VE copolymers

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

13

Main characteristics of CTFEVCA copolymers

Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics

CTFE inmonommixture(mol )

CTFEa

incopolym

(mol )

Yield

(wt )

Mnd

(gmol-1)

PDIb Tg

(degC)

Td10

(degC)

NC-Hcm3

(10-3)

nD

(23degC)

8070605040

603518459398346

640641658706722

28002500225020001800

2220252520

7090

100110120

274295289246254

5484115148162

14379143581435714459

-

Polar organic solvents acetone THF EtOAc DMF DMSO

Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

14

262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION

Objective to improve the solubility in reactivediluents and fluorine content in copolymers

Reaction conditions

CTFEVCA = 067 = const

HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR

Characterization of CTFEVCAHFP terpolymers

- solubility in reactive diluents

- Tg ~ 120degCTd ~ 250degC

- NC-Hcm3 (nD resp)

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

15

n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z

O

(C H 2 )n

O H

OOCO

O(C H 2 )n

O H

4 0 0 0 g m o l-1M n lt o ligo m e riza tio n

n = 2 o r 4+C = CF

C l

F

F

C HH C

OC

O

O

+

Scheme 3 CTFE VCA hydroxy VE terpolymerization

263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

16

OCH2 =CH C

O(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

acrylation

O H

(CH2)n

O

R]nCH)z(CHCH)y(CH2CF2)x(CClFH[

OC

OO

OC

OO

Function polymerizableunder UV

Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers

27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS

CH2=CHCOCl

CH2=C(CH3)COCl

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

17

28 Characterization of UV-cured materialsDMA analysis

Tg of acrylated CTFEVCAHBVE compositions ~90degC

E ndash modulus 1 GPa at 20degC 50 MPa at 120degC

Taird10 ~ 200ndash220degC

DSC analysis

Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC

Taird10 ~ 230ndash240degC

1

2

2

3

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

18

29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber

291 Monomer synthesis

F3CCF2FC

O O

F F

CF3F3CCFFC

O O

F F

CF2

CF2F2C

CFFCO O

F F

F2C CF2

CF2CF2

CFFCO O

F F

A B DC

Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives

Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

1919

292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)

F 2C CXY +

FC CFO

CO

F2CCF2

CF2

CF2TBPPi 75oC

C4F5H5

FC CF

OC

O

F2CCF2

CF2

F2C

CXY

F 2C

n

n

m

m

zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)

Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

20

Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)

Run Monomer M2 Monomers in the feed(mol )

F-Ox M2

Copolym compsby microanal

(mol)F-Ox M2

Copolym compsby NMR(mol )

F-Ox M2

Conv(wt)

Tg(degC)

Td10(degC)

1 F2C=CFCl 20 80 35 65 374 626 63 105 322

2 F2C=CFCl 40 60 62 38 615 385 70 148 354

3 F2C=CFOC3F7

64 36 874 126 852 148 82 144 342

4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359

5 F2C=CH2 14 86 382 618 378 622 65 108 370

6 F2C=CH2 35 65 584 416 579 421 67 138 356

nR lt 135

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

21

210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP

CTFEVCAHVE) oligomers in good yield and high Tg were synthesized

2 Successful acrylation of hydroxy functionalized cooligomers

3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties

4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties

dArr

Suitable for waveguides applications

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

22

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

2323

31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to

hydrogenated analogues

Lower interfacial tension and CMC

Excellent chemical and thermal stability

Oleophobicity oil and fat repellants

Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc

Traditional commercial fluorosurfactants

Long fluorocarbon chain C6ltRFltC12

Perfluorooctane sulphonate (PFOS)

Perfluooctanoic acid ( PFOA)

their derivatives

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

2424

32 DRAWBACKS OF FLUORINATED SURFACTANTS

Bioaccumulable

Toxic and persistent

Wide-spread in the environment

3M company suggested perfluorinated chain le C4

bull Low bioconcentration factor

bull Low toxicity

bull Still high product performance

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

2525

General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4

Hydrophobic

G G GF- blockRF

Hydrophobic Hydrophilic

a ) for RF (CF3)2CF

b) for fluorinated monomer CH2=CH (TFP)

CF3

nCH2=CH + (CF3)2CFI RF - hydrophobic - I

CF3 CF3CF3

G

CF3

CF3CF-CH2-CH-CH2-CH Hydrophilic

CF3 CF3

Degradation

33 Synthesis of different end products as fluorinated surfactants

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

26

CF I + n nCFI

CF3

CF3

O

O

nCFCF3 I

O

O

Rad

nCFCF3

Zn

HSOH

O

nCFCF3

SOH

O

HOO

p

nCFCF3

SO

OO p

H2C CH2

nCFCF3

I

NNEt3

nCFCF3

NEt3nCF

CF3

N

I I

Surfactant C Surfactant B

Surfactant A

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

CF3

Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants

Anionic surfactant

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

27

Surfactant Appearance Fluoroalkyl

10 decomp temperature a

(oC)

Tg and melting point b (oC)

(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC

(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145

(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175

Table 1 Properties of synthesized fluorinated surfactants

a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin

b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin

G Kostov et al USP 0027349 (2007)

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

28

Conditions Weight losses ()

Surfactant A Surfactant B Surfactant C

(1) Base-acid resistance

98 H2SO4 25 oC 7 days 00 lt12 00

60 HNO3 25 oC 7 days - gt400 lt20

37 HCl 25 oC 7 days 00 gt150 00

40 NaOH 25 oC 7 days 00 00 00

(2) Solubility in selected solvents Solubility (g100mL)

Water 25oC 72 hrs gt10 gt10 gt10

Methanol 25oC 72 hrs gt10 gt10 gt10

Diethyl ether 25oC 72 hrs lt1 lt1 lt1

Benzene 25oC 72 hrs lt2 lt2 lt2

Acetone 25oC 72 hrs lt10 lt10 lt10

Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-

Conclusions

The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

29

Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

30

Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis

34 Phosphorous containing TFP surfactants

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

31

3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate

Hydrolysis

Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

32

Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to

those of PFOA (white)

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

33

CONTENTS

1-Introduction Objectives

2-Functionalized fluoropolymers for plastic optical fibres

3-Original fluorinated Surfactants potentially non-bioaccumulable

4-Functional fluoropolymers for fuel cell membranes

5-Conclusions and perspectives

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

34

Main characteristics of themembrane

To separate oxygen from hydrogen

To insure a good protonic conductivity

To be chemically physically andmechanically stable in acid media andat high temperatures

Rеasonable cost applications

No electronic conductivity

41 FUEL CELL MEMBRANES

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

35

Poor thermostability

Low hydrolytic stability

Instability to Radiations

Non-negligible solubility in usedfuels

Good thermalstability

Stability to hydrolysis and to acids

Good durability

Properties of super acide (-CF2-SO3H)

Good resistance to oxidation

Hydrogenated membranes versus fluorinated membranes

Hydrogenated membranes Fluorinated membranes

4 2Fluorinated ionomers for IE membranes

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

36

Perfluorinated ionomers

bull Clemson-produced sulphonyl imide ionomer

bull Commercially available Nafion ionomer (DuPont)

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO3 H

CF3

acidic proton

(CF2CF2)n (CF2CF)

OCF2CFOCF2CF2 SO2NSO2CF3

CF3

H

acidic proton

EW=1100 n = 66

EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau

421 SULFONYLFLUORIDE COPOLYMERS

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

37

PEM fuel cells mdash Nafionreg

A - fluorocarbonbackbone

B - interfacial zoneC - ionic clusters

Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

38

bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash

bull Du Pont technology

bullCo-polymerization

nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F

R(CF2CF2)n-(CF2CF)-x

CF2O(CF2)2SO2F

rTFE=1002 plusmn 063

r2=03 plusmn 09

R˙

G Kostov et al J Appl Polym Sci 1993 47 735

422 OUR SULFOFLUORINATED MEMBRANES

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

39

28732823ndashMelting temperature (ordmC)

30803140ndashThermal stability (ordmC)

313343408Copolymer yield (wt)

936863428

077072039

(-SO2F) content in the copolymer

IEC (meqg)

m2 (mol)

050077295TFEPPOTESF mol ration in the feed

Samples1 2 3

Parameters

Table 423 Copolymerization of TFE with PPOTESF in bulk

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

40

x F 2C =C FC l + y H2C =CC H2 F

[(C F 2C F)n (C H2 C )m

C H2F]p

C l

R

CTFE FMS

1-(fluoromethyl)styrene

Synthesis of poly(CTFE-co-FMS) copolymers

SULPHONATION

PEMFC

Collaboration with Prof Gouverneur Oxford Univ

43 CTFE-based copolymers for electrolytemembranes

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

41

44 CARBOXYL CONTAINING MEMBRANES

bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash

bullAsahi glass technology

bull Co-polymerization

CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer

40 10 30 20 mol

AR meqg ndash 12-29

R ohmcm2 ndash 12-158

αhydr - 73-99

Tg lt 250C

TdOCO ordmC gt 360

TfOCO ordmC ndash 180ndash190

σ MPa ndash 35ndash40

ε - 150ndash200

Application chloro ndash alkaline electrolysis PEMFC

J Membrane Sci 1992 68 133

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

42

Fuel cell challenges high temp operationFuel cell challenges high temp operation

bull DOE fuel cell cost target of $30kW ndash Incremental advances are

not adequatendash High riskhigh payoff basic

research coupled with applied programs

ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo

Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

4343

MeOH crossover

Cost ($ 400-500 m2)

Drying from 80degC including poor performances

Search for intermediate and high temperaturemembranes

To replace H2O by immobilized amphotericsolvents

Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245

Drawbacks of sulphonated membranes

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

4444

N

N

O

O

Ph

+

F

F

Cl

F

N

NH

O

O

F F

F Cl

n

Rad H2Pd(OH)2

(A)

(A) + PEEK-S

100 degCIEC 08 to 04Conductivity ~ 10 mScm-1

(at 100 degC 30 RH)

45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes

Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

45

CH2 CF2 CH2 C

CF3

CO2H

CF2 CF

CF3

x y z

1) A lL iH 4

E aton C ataly stNH2

NH22)

OH S O 3N a

S O 3N aN aO 3S

CH2 CF2 CH2 C

CF3

CH2

CF2 CF

CF3

x y z

O S O 3 N a

S O 3N aN aO 3S

H +

CH2 CF2 CH2 C

CF3

CF2 CF

CF3

x y z

NHN

PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

46

Remaining challenges

bull Find a useful balance between mechanical properties and glass transition temperature

bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

47

Membranes combining 2 conduction mechanisms

bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

48

Conclusions and perspectives

bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity

bull Efficient methods to mechanically stabilize the conductive films have to be developed

bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

49

COMPANIES

Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)

ACKNOWLEDGEMENTS

ACADEMICS

Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION

50

THANK YOU FOR YOUR KIND ATTENTION

THANK YOU FOR YOUR KIND ATTENTION