Solvay Fluor GmbH Hans-Böckler-Allee 20 D-30173...

Solkane® 365mfc based solutions as alternative to HCFC141b

economical, ecological and technical considerations

Solvay Fluor GmbHHans-Böckler-Allee 20D-30173 Hannover

Physical data - blowing agents in comparison

Blowing agents in foams

Co-Blowing

Safety and handling

Flammability in systems

Physical properties in comparison

Flammability limits[% by volume]

Structure

Mol.-Weight

Boiling Point [°C]

Vapour pressureat 20 °C [bar]

lambda [gas at 25 °C]

Flash point

HFC-245fa

none

CF3-CH2-CF2H

134

15,3

1,2

12,2

none

HFC-365mfc

3,6 - 13,3

CF3-CH2-CF2-CH3

148

40,2

0,4

10,6

-27

HCFC-141b

7,4 - 17,7

CCl2F-CH3

116,9

31,7

0,6

9,5

none

HFC-134a

none

CF3-CFH2

102

-26,1

5,7

13,4

none

none

HFC-227ea

CF3-CFH-CF3

170

-17,0

3,9

12,7

none



Mol.-Weight

Boiling Point [°C]


lambda at 25 °C[mW/m.K]

Structure

Flash point [°C]

n-pentane

1,4 - 7,8

72

36,1

0,6

15,2

CH3-(CH2)3-CH3

-49

HFC-365mfc

3,6 - 13,3

148

40,2

0,4

10,6

CF3-CH2-CF2-CH3

-27

HCFC-141b

7,4 - 17,7

116,9

31,7

0,6

9,5

CCl2F-CH3

none

c-pentane

1,4 - 8,3

70

49,5

0,35

12,0

-37

1,4 - 8,3

i-pentane

72

27,8

0,8

14,7

CH3-CH-CH2-CH3CH3

-57



Mol.-Weight

Boiling Point [°C]


lambda at 25 °C[mW/m.K]

Structure

Flash point [°C]

Dimethoxymethane(Methylal)

2,2 – 19,9

76

41

0,44

13,1

CH3–O–CH2–O–CH3

-18

HFC-365mfc

3,6 - 13,3

148

40,2

0,43

10,6

CF3-CH2-CF2-CH3

-27

HCFC-141b

7,4 - 17,7

116,9

31,7

0,65

9,5

CCl2F-CH3

none

5 - 23

Methylmethanoate(Methylformiate)

60

32

0,58

10,7

CH3OOCH

-32


HCFC-141b HFC-365mfc HFC-245fa n-Pentane c-Pentane Methylal Methylformiate

MW 116.95 148.08 134.05 72 70.14 76 60

Bp 31.7 40.2 15.3 36.1 49.5 41 32 [°C]

k-Factor 9.5 10.6 12.2 15.2 12 13.1 10.7 [mW/m.K]

GWP 725 890 950 3 - 7 11 negligible ~ 1

ODP 0.11 0 0 0 0 0 0

VOC no no no yes yes yes yes

Flammability none yes none yes yes yes yes

LEL 5.6 3.6 - 1.4 1.4 2.2 5 [% by volume]

UEL 17.7 13.3 - 7.8 8.3 19.9 23 [% by volume]

Toxicology / Notification

Acute Toxicity, LC 50 (rats)

NOAEC chronic

Card.sens. (Threshold)

Mutagenicity

HCFC-141b

62 000 ppm

7,3 g/m3 (2 y)

0,5 %

negative

404-080-1ELINCS – No.:

HFC-365mfc

> 100 000 ppm

90 g/m3 (90 d)

7,5 %

negative

430-250-1

Commercial available Blends

Flammability Recommendation

Solkane 365mfc flammable Additive for pentane boards

Solkane 365/227 93:7 non flammable Foaming agent for direct production

Solkane 365/227 87:13 non flammable Foaming agent for systems

Product

Compatibility with materials

After 7 days immersion : (% by weight)

Materials HCFC-141b Solkane 365mfc

PVC 0,77 -0,02PE-HD 7,1 0,37PMMA dissolved 57Polycarbonate 2,3 0,27PP 12,5 0,16Nylon 66 1,87 -0,33PS dissolved 0,19

Neoprene 87 1,02Viton A 46 90,5EPDM 44 1,6Natural rubber 185 7,2Nitril rubber 47 2,5Silicone 110 16,1

Thermoplast ics

Elastomers

-10

0

10

20

30

40

50

60

Cha

nge

[mas

s-%

]

PVC

PE-HD

PMMAPolyc

arbonate PP

Nylon 66 PS

HCFC-141bSolkane 365mfc

diss

olve

d

diss

olve

d

-10

0

10

20

30

40

50

60

Cha

nge

[mas

s-%

]

Neopren

e

Viton A

EPDMNatu

ral ru

bberNitr

il rubber

Silicone

HCFC-141bSolkane 365mfc



Co-Blowing

Safety and handling


Solubility of Solkane 365mfc in comparisonHCFC-141b Solkane 365mfc n-pentane c-pentane

PolyetherDaltolac 585-8 complete soluble 32 4,5 11IXOL B251 3 0,3 1,4 2,2IXOL M125 37 5,3 2,1 5,6Tercarol A 350 complete soluble complete soluble 36 complete solubleTercarol RF 55 complete soluble complete soluble 4,5 18Voranol RA 640 complete soluble complete soluble 20 complete soluble

PolyesterRepol 201-28 57 21 2,7 5,4Stepanpol PS 3152 34 31 6,5 6,6Terate 203 32 18 1,3 no dataTerate 2541 42 11 0,1 no data

MiscellaneousTCPP complete soluble complete soluble 10 complete solubleMDI 44 V20 complete soluble 12 4,1 6,6Dipropylene glycole complete soluble complete soluble 13 36

Strategies to phase out HCFC-141b

Step 1: exchange HCFC-141b with Solkane 365/227 inmolar ratio 117 : 148

Step 2: exchange Solkane 365/227 stepwise with waterto reduce density and adjust Comp. Strength in parallel

Screening of initial lambda values (free rised lab foams)

20

22

24

26

28

0 0.5 1 1.5 2 2.5 3 3.5 420

22

24

26

28

0 0.5 1 1.5 2 2.5 3 3.5 4Amount of Water [pbw in formulation]

lam

bda

[mW

/m.K

]

S 365/227 10 °C S 365/227 24 °C

Com

pres

sive

str

engt

h [k

Pa]

0

100

24 26 28 30 32 34 36Foam density [kg/m³]

Solkane 365mfc

HCFC-141b

Influence of blowing agent to comp. strength

Flammability in Foams in ComparisonEN ISO 11925-2 – Ignitability Test (B2)

100

110

120

130

140

150

160

170

Solkane 141b

Solkane 365mfcR 245fa

n-Pentane

Solkane 365mfc/n-C5

Flam

e he

ight

[mm

]

Ageing of foams in comparison(measuring temperature 24 °C)

18

19

20

21

22

23

24

25

26

0 20 40 60 80 100 120 140 160 180 200Ageing [days]

k-fa

ctor

[mW

/m.K

]

cyclo-pentaneSolkane 141bR 245faSolkane 365mfc

RT 70 °C

Solkane 365/227 (93:7)Typical performance in application

Density [kg/m3]

Construction

39

20

ElementsDiscont.

32

20,5

ElementsPour-In-Place

49

20,5

Spray

62

21

Application

Lambda initial[mW/m.K, 10 °C]

Lambda initial[mW/m.K, 10 °C]

HCFC-141b

18,6

HFC-365mfc

19,5

S 365mfc/i-pentane

19,8

n-pentane

22,5

LaminatesS 365mfc/R 245fa

19,1

Best results in practise:

Blowing Agent: Solkane 365/245 60:40

050

100150200

y

xz

[kPa]

250

Core Density: 30 kg/m³Cell Orientation: Lambda (10 °C; initial):

18.5 mW/m.K

Object: cont. PanelFacing: 50 µm Aluminium

Lambda Behaviour of Solkane 365mfc in ComparisonLong Term

20

21

22

23

24

25

26

27

28

29

30

n-pentane Solkane 365/227

initial42 d RT3 years 70 °C

Lam

bda

[mW

/m.K

; 10

°C]

R 11R 14

1bR 36

5mfc

n-pen

tane

i-pen

tane

c-pen

tane

CO2

Air

23 °C70 °C

100 900

30 20050 70

13000

30608

10 5 20 7 6

5000

500

0

2000

4000

6000

8000

10000

12000

14000

Relative diffusion coefficient

[x10-14 m²/s]

Diffusion of blowing agents in foams

Life Cycle Environmental Profile ofWater/CO2 vs HCFC-141b vs Solkane 365mfc

Partners:

Life Cycle Environmental Profile ofn-Pentane vs HCFC-141b vs Solkane 365mfc

Partners:

Economic Spray foamAdvantage compared to Water blown Foams

Water/CO2 Solkane 365/227Density [kg/m³] > 40 30-33

Lambda (initial) > 28 19-20

Fire behaviour B 2 B 2

Foam behaviour brittle good

Adhesion medium good

Estimated price/m³ 73 € 68 €

Better foam at lower price



Co-Blowing

Safety and handling


Reduction of Density

62,69 €/m³62,49 €/m³

100

110

120

130

140

150

160

170

180

190

30 31 32 33 34 35 36 37Density [kg/m³]

Com

pres

sive

Str

engt

h [k

Pa]

cyclo/iso-pentaneS 365mfc//c/i-pentane 30:70

Remark: each point = average of 10 Tests

Cost evaluation per m³PIR-system for continuous Steel Sandwich with n-Pentane

Standard Co-Blowing Standard Co-Blowing[pbw] [pbw] [EURO/m³] [EURO/m³]

Component A 82.5 69.3 29.92 28.08

Catalyst 1 3.0 2.5 1.63 1.52Catalyst 2 0.9 0.6 0.82 0.61

n-Pentane 6.5 1.30S 365mfc/n-Pentane (30:70) 6.2 2.85

MDI 124 104 44.90 42.15

Sum 216.7 182.6 78.57 75.21

Density [kg/m³] 39.3 37.0 39.3 37.0

Comp. Strength [kPa]: 120 129

Lambda [mW/m.K]: 21.8 20.9

Difference -3.36 €/m³

Formulation Costs



Co-Blowing

Safety and handling


Easy and save handlingSpraying in closed rooms (cellar)

Classification PUR, B 2

Core density [kg/m³] 32.3

Cell gases in foam [mass-%] after 6 days

Air CO2 R 227ea R 365mfc

2.4 21.2 7.5 68.9

Compressive Strength 213 [kPa]

Lambda, initial 19.8 [mW/m.K]

Emission of Solkane 365mfc during spraying

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0:00 0:28 0:57 1:26 1:55 2:24 2:52 3:21Time [hours]

Con

cent

ratio

n [V

ol.-%

]

Concentration S 365mfcLower Explosion Limit

Dimensions:Square area: ~60 m² Height: ~70 cmOpening (Top): ~70 x 70 cm Foam thickness: ~20 cm

Emissions during a disk. Panel trial

Lower explosion limit

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

4,5

5,0

0 20 40 60 80 100 120

Time until closing [%]

Con

cent

ratio

n S

365m

fc [V

ol.-%

]

Form closed



Co-Blowing

Safety and handling


Potential flammability suppressants for HFC-365mfc can be⇒ HFC-134a and HFC-227ea, HFC-245fa.

Flammability rating

0250500750

100012501500

72750730007325073500

Propan

eSolka

ne-152

aSolka

ne-365

mfc

HFC-245fa

Solkane-1

34a

Solkane-2

27ea

flammable non flammable

f(ΔG

com

b.,re

actio

n ra

te)

???????

Evaluation of flashpoint as function of concentration

-10

0

10

20

30

40

50

60

70

0 5 10 15 20 25Concentration Solkane 365/227 93:7 in Polyol [mass-%]

Flas

h Po

int [

°C]

Tercarol A 350 S 365mfc

Tercarol A 350 S 365/227

Evaluation of flashpoint as function of concentrationof Solkane 365/227 – “flammable window”

Method: EN ISO 13736

-10

10

20

30

40

50

60

70

0 5 10 15Concentration of Blowing Agent [mass-%]

Flas

hpoi

nt [°

C]

0

Advantages of Solkane 365mfc

working with a true liquid

flammability in raw materials is solved

best fire behaviour in foams of all physical foaming agents

best insulation value of physical foaming agents includingageing of foam and thus implements the highest effect insaving CO2 for the Environment

low density foams with high dimension stability are standard and save costs

Solvay Fluor GmbH Hans-Böckler-Allee 20 D-30173...

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Transcript of Solvay Fluor GmbH Hans-Böckler-Allee 20 D-30173...