Post on 26-Mar-2018
1
Chunliang Li (TU Eindhoven) Rafaël J. Sablong (TU Eindhoven & PTG Group) Theo Veldhuis (DSM Coating Resins) Paul Buijsen (DSM Coating Resins) Cor Koning (TU/e & DSM Coating Resins)
Novel renewable coating resins based on
limoneneoxide and CO2
Global societal trends drive DSM’s markets
Population growth
Wealth
Resources constraints
Sustainability
Urbanization Healthcare costs Energy security
Food security
Ageing population
Materials Nutrition Health
Global shiftsHealth & WellnessHealth & Wellness Climate & Energy
BRIGHT SCIENCE, BRIGHTER LIVING
Sustainability Within DSM Coating Resins the focus on innovation includes sustainable coatings solutions. • Moving away from solvent-based technologies • Investing and innovating in waterborne technologies • Partnerships and acquisitions on sustainable technologies;
- Energy curable resins (AGI) - Bio-renewable resins
DSM Coating Resins conducts LCA* studies to maintain its high-level of commitment to Sustainability. • Conducting range of LCA studies for coatings industry As a result we contribute to the coatings industry as a whole
* LCA: life cycle assessment
‘Leading the Transformation to Sustainable Coatings’
Background
O
HO O
O
O O
O
O OH
R
m n
Rafaël J. Sablong, et al. Progress in Organic Coatings 76, 2013, 1704–1711
O OH
O
O
n
CO2
OH
NCO
NCO
OCNOHOH
Urethane linkage
O CO
NH
Prepolymer
‘S’
‘R’
LO/CO2 copolymerization
NNEt
Et Et
Et
NZn
NAr
Ar
RH
O
Cis (45
%)
R =
N(SiMe3)2
Trans- and cis-
(R)-limonene oxide
Trans (55
%)
O
+
Et-BDI-H
CO2
(Et-BDI)ZnR
O O
On
Htrans Hcis
HpHHH
Geoffrey W. Coates, et al. JACS, 2004, 126, 11404
1) Only trans reacts; 2) No ether groups
Entry [R-LO]/[Zn] PCO2 Bar
Conva
% Mn
b
kDa PDIb
1 125 40 55 14.4 1.19
2 250 40 54 16.9 1.21
3 250 10 52 16.0 1.19
Bulk synthesis of poly(limonene carbonate) Catalyzed by (Et-BDI)Zn[N(SiMe3)2]
Conditions: 25 °C, 12 h, bulk reaction. a: determined by 1H NMR; b: determined by SEC in THF. • Higher zinc concentration leads to lower Mw
• Reaction pressure has little effect on the polymerization results
• Conversion max of 55%: very low reactivity of cis isomer
• Polydispersities around 1.2
120-140 oC 80-100 oC 60-80 oC
The transcarbonation agents and catalysts
O
OSn
2
Sn(Oct)2
NN
O OAlO
(salen)AlEt
N
N
NH
Triazabicyclodecene (TBD)
O
OHO
OHH
H
Isosorbide
HO OH
n = 3, 10
n
Trimethanolethane (TMP)
OH
OH
OH
HO OH
HO OH
Pentaerythritol (PE)
P1 O
O
O P2 P1 O HO P2
HOR O
OR
OHOH
Entry Catalyst Polyol Temp
oC
Time
h
[Polyol]/
[Catalyst]
Mn
kDa PDI
1 Sn(Oct)2 Decanediol 120 4 10 5.9 2.7
2 (salen)AlEt Decanediol 120 4 10 6.6 2.5
3 TBD Decanediol 60 4 10 3.7 1.8
4 TBD Isosorbide 100 8 10 6.2 1.9
5 TBD Trimethanolethane 80 1 8 3.3 1.9
Transcarbonation experiments (TBD trials in toluene, others in bulk)
0 4 8 12 16
3
6
9
12
15
Mn (k
Da)
Time / h
[M]:[Cat.] = 100:11,10-decanediol
13.8 kDa, PDI~ 1.2
1.2
1.4
1.6
1.8PD
.I. Initial fast decrease in Mw induced by decanediol
Polymer with desired Mw obtained within 3 h
Marginal drop after 1 h
Maximum PDI after 3 h then constant
Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458
TBD . 60 oC
MALDI-ToF-MS characterization after alcoholysis reaction with 1,10-DCD.
Nearly only α,ω-OH-end capped chains; No cyclic compounds observed
Presence of non-hydroxyl end group (not quantitative) due to rearrangement reaction LO Nearly 100 % carbonate linkage (no ether bonds observed, also not in NMR)
Polymers with 0, 1 or 2 DCD units
OOH O
O
OH
m n
Am,n
OOH O
O
OROH
m
Bm
Cm
OO O
O m
Dm
OO
O
O
mR
O
O
OROHH H
1500 1600 1700 1800 1900 2000 21000
10
20
30
40
50
60
70
80
90
100
C6,1
B7
A7,1
A8,0
% In
tens
ity
Mass (m/z)
A7,1
B7
D7,1
C6,1
Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458
Sample Polyol Mn
kDa PDI
OHV
[mgKOH/g]
Mn,titration
kDa
Tg
(oC)
1 isosorbide 3.3 1.9 28.1 3.9 96
2 1,10-DCD 3.0 2.0 29.2 3.7 71
3 1,3-PD 3.3 2.0 21.6 5.0 91
4 TMP 3.2 1.9 26.8 4.0 83
Properties of OH-ended PLCs used for toluene or tBuOAc casting and curing.
Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458
MWs calculated from titration results are higher Relevant for curing: 1) low reactivity of the tertiary OH end groups; 2) the presence of non-hydroxyl end group
PLC with 1,10-decanediol moieties has much lower Tg than others 1,10-DCD moieties act as flexible segments; isosorbide is rigid and 1,3-propanediol is stiffer than DCD
Catalyst: dibutyltin dilaurate (DBTDL)
Coating evaluation
N N
N
(CH2)6
(CH2)6 (CH2)6
NH
O O
oN N
N
(CH2)6
(CH2)6 (CH2)6
O O
o
O
NO
NHO
N
O
HN
O
N
O
I Desmodur N3600 II
Desmodur BL3272
(caprolactam
blocked)
Curing agents
OCN
NCOOCN
Curing T (oC)
Film thickness (μm)
Appearance Impact test (1 kg, 1 m)
Acetone rub test (50 acetone DR)
180 16 - 35 Transparent
Colorless- light yellow - * - *
Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458
* Irrespective of curing agent used
O O
O
n
HS R OH
O O
O
Op
O
O
n-p
S
R
OH
R= -CH2(CH2)4CH2- ,
-CH2CH2-
Post-modified PLCs with tunable thermal properties
HO *
3.7 ppm
H H
O
H
O
O
5.0 ppm
4.7 ppm
A typical NMR spectrum of the modified PLC (50 %). (Ratio C=C Hs/backbone H reduces by factor 2)
Before modification
After modification
Resins Mn
a
kDa Feeding ratio
[ene]:[OH] Target conv.
[=] % Conversionb
% Tg
c oC
Mnd
kDa PDI d
14k-E(50%)
14
2 50.0 47.5 103 19.5 1.96 14k-E(12.5%) 8 12.5 12.3 118 16.4 1.49 14k-E(6.3%) 16 6.3 6.2 117 15.3 1.41 8k-E(50%)
8 2 50.0 48.0 89 10.3 1.81
8k-E(12.5%) 8 12.5 12.3 97 9.2 1.59
Entry Mn
a kDa
Feeding ratio [ene]:[OH]
Target conv.[=] %
Conversionb %
Tgc
oC Mn
d kDa
PDId
14k-H(50%) 14
2 50.0 48.0 66 18.7 1.35
14k-H(12.5%) 8 12.5 12.3 94 17.6 1.32
8k-H(50%) 8
2 50.0 47.5 56 10.0 1.63
8k-H(12.5%) 8 12.5 12.3 84 9.6 1.69
Reactions with mercaptoEthanol
Reactions with mercaptoHexanol ( lower Tg than for ME modification)
a MW of polymers before modification. b Determined by NMR. c Determined by DSC. d Determined by GPC. Reactions conditions: 1,4-dioxane, 80 oC, [=]:[AIBN]=1:0.3
Post-modification of PLCs (8k DCD-alcoholyzed; 14k as synthesized)
Catalyst: Dibutyltin dilaurate (DBTDL)
Curing agents: Desmodur series I: N3600 II: BL3272 (ε-caprolactam blocked)
Conventional curing agents and catalyst
Transparent films after curing N N
N
(CH2)6
(CH2)6 (CH2)6
NH
O O
oN N
N
(CH2)6
(CH2)6 (CH2)6
O O
o
O
NO
NHO
N
O
HN
O
N
O
I Desmodur N3600 II
Desmodur BL3272
(caprolactam
blocked)
Curing agents
OCN
NCOOCN
2350 2300 2250 2200 2150 2100
0.00
0.02
0.04
0.06
Abs
orba
nce
Wavenumber (cm-1)
t = 0.5 min 1.5 min 3.5 min 7.5 min 12.5 min 20.5 min 30.5 min
0 5 10 15 20 25 300
20
40
60
80
100
Con
vers
ion
(%)
Time / min
IR spectra of the reaction mixture of resin 8k-E(12.5%) and N3600 ([OH]:NCO=1:1.1) and the NCO conversion over the time at 180 oC.
Curing kinetics
3900 3600 3300 3000 2700 2400 2100
0 min 30 min
Time / min0 5 10 15 20 25 30
0
20
40
60
80
100
Con
vers
ion
(%)
Time / min
IR spectra of the reaction mixture of 8k-H(50%) and BL-3272 ([OH]:NCO=4:1) and the conversion of the blocked isocyanate over the reaction time at 180 oC. NOTE: Faster than non-blocked system because of higher OH number of resin
Curing kinetics
R NH
CO
N R NCO R'OH RNH
CO
OR'deblocking
O
Coating tests after solvent casting (tol. or tBuOAc, 14k as synthesized; 8k alcoholyzed with DCD)
Resinsa Curing agentb
OHV (mg KOH/g)
Ratio (OH:NCO)
Acetone
resistancec
Av. film thickness
(μm)
Pencil Hardness
König Hardness
(S)
Curing T oC
8k-E(12.5%) I 45.6 1:1.1 + 28 2H 168
180 8k-H(12.5%) I 35.4 1:1.1 + 35 2H 182
14k-H(12.5%) I 31.6 1:1.1 + 38 2H 167
8k-H(50%) II 97.0 4:1 +/- 37 2H 167
180 8k-H(50%) II 97.0 2:1 + 45 2H 169
14k-H(50%) II 91.2 4:1 +/- 23 2H 168
14k-H(50%) II 91.2 2:1 + 30 2H 169 a E: mercaptoethanol used, H: mercaptohexanol used. b For curing reactions of polymer resins with low OHV, non-blocked isocyanate was used and the curing temperature was kept at 180 oC. c 50 Acetone ‘dubble rubs’ survived without visual damage
DMTA results alcoholyzed PLS (non-blocked curing agent I)
1. Higher [OH]/[NCO] ratio gives lower storage modulus in the rubbery plateau region. 2. The coatings with similar crosslink densities have comparable modulus in the rubbery plateau region. 3. Tgs of the coatings with higher concentration of mercaptohexanol moieties are much lower; Tan delta peaks are single and rather symmetric (‘single phase’ ?).
0 20 40 60 80 100 120 140 160 1800.1
1
10
100
1000
10000 8k-H(50%) [OH]:[NCO]=2:1 8k-H(50%) [OH]:[NCO]=4:1 8k-H(12.5%) [OH]:[NCO]=1:1.1
Sto
rage
Mod
ulus
/ M
Pa
Temperature / oC0 20 40 60 80 100 120 140 160 180
0.0
0.5
1.0
1.5
2.0 8k-H(50%) [OH]:[NCO]=2:1 8k-H(50%) [OH]:[NCO]=4:1 8k-H(12.5%) [OH]:[NCO]=1:1.1
Tan
Del
ta
Temperature / oC
DMTA results non-alcoholyzed PLC (non-blocked curing agent I)
20 40 60 80 100 120 140 160 180
0.0
0.2
0.4
0.6
0.8
1.0
1.2 14kE(50%) [OH]:[NCO]= 1:1 14kE(50%) [OH]:[NCO]= 2:1 14kE(50%) [OH]:[NCO]= 4:1
Tan
Del
ta
Temperature / oC20 40 60 80 100 120 140 160 180
0.1
1
10
100
1000 14kE(50%) [OH]:[NCO]= 1:1 14kE(50%) [OH]:[NCO]= 2:1 14kE(50%) [OH]:[NCO]= 4:1
Sto
rage
Mod
ulus
/ M
Pa
Temperature / oC
Less homogeneous than mercaptohexanol-modified coating system (different miscibilities of curing agent with polymer resins?; Mn may play a role in miscibility; systematic study required for explanation)
Storage modulus in the rubbery plateau region in accordance with the crosslink density
Mechanical failure observed above Tg for [OH]/[NCO] ratio of 4 (too low crosslink density/ weak network)
Crosslinking reactions using thiol-ene chemistry
SHHS
SH
SS
SS
S
S
S
S
S
or
HO O
O
O O
O
O OH
R
m n
R. Sablong et al. Progress in Organic Coatings (2013) 76, 1704–1711
Mats Johansson,et al. Polym. Chem., (2014), 5, 3245-3260
Properties of PLC resins
Sample Mn / kDa PDI Tg / oC
P1 6.0 2.2 83
P2 2.8 1.8 70
Photoinitiator: Irgacure@ 651
Curing agent: TMPMP (Thiocure®)
Thermal initiator: AIBN
Themal initiator: dicumyl peroxide
t1/2 = 10 h, 70 oC in toluene
t1/2 = 10 h, 115 oC in toluene
1800 1600 1400 1200 1000 800
0 min
1 min
2 min
5 min
10 min
15 min
20 min
25 min
30 min
Wavenumber (cm-1)
900 890 880 870 Wavenumber (cm-1)
FTIR for kinetic study
1650 1640 1630 Wavenumber (cm-1)
FTIR spectra of curing reaction mixture using dicumylperoxide ([=]/[SH]=1) maintained isothermally for various times at 180°C
0 5 10 15 20 25 30
102030405060708090
100
[=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4
%
Time / min
180 oC
0 5 10 15 20 25 30
102030405060708090
100 [=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4
%
Time / min
160 oC
0 5 10 15 20 25 300
102030405060708090
100 [=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4
%
Time / min
140 oC
Curing kinetics (DCP) % indicates % C=C left
Conversion versus time plots for isopropenyl groups cured with various amounts of TMPMP at different temperatures More curing agent (lower [=]/[SH]) yields higher
conversion of double bonds as expected. The curing reaction at 180 oC finished in 5
minutes. Conversions dependent on temperature
Resins Stoichimetry [=]:SH
Acetone resistance
Av. film thickness
(μm)
Pencil Hardness
König Hardness
(s)
Curing conditions
P1 1:1 + 28 3H 96
Thermal curing
DCP/160 oC
P1 2:1 + 35 3H 116
P1 4:1 + 38 2H 148
P2 1:1 + 25 3H 118
P2 2:1 + 28 4H 132
P2 4:1 + 29 3H 147
P1 1:1 + 37 3H 153
UV curing 130 oC
P1 2:1 + 36 3H 158
P1 4:1 + 25 2H 167
P2 1:1 + 45 2H 109
P2 2:1 + 50 2H 146
P2 4:1 + 28 2H 158
Coating tests (solvent casting)
-60 -40 -20 0 20 40 60 80 100 120 140 160 180 200
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4
Tan
Del
ta
Temperature / oC-40 -20 0 20 40 60 80 100 120 140 160 180
10
100
1000
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4
Sto
rage
Mod
ulus
/ M
Pa
Temperature / oC
DMTA results from films after curing (160 ºC, Dicumyl peroxide)
1. Initiator type greatly affects the homogeneity of the curing system Initiator with higher T to reach t1/2 gives more homogeneous films (More time to homogenize (?))
2. Films obtained with lower [=]/[SH] ratio show more elastic behavior. Higher peak intensities of tan δ reflect great energy loss/ more viscous behavior
3. Storage modulus increases with lower [=]/[SH] ratio
Mn=2.8 kDa; PDI=1.8
-40 -20 0 20 40 60 80 100 120 140 160 180 200
0.0
0.2
0.4
0.6
0.8
1.0
Mn = 2.8 KDa, PDI=1.8
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4
Tan
Del
ta
Temperature / oC
-40 -20 0 20 40 60 80 100 120 140 160 180 200
10
100
1000
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4
Sto
rage
Mod
ulus
/ M
Pa
Temperature / oC
Mn = 2.8 KDa, PDI=1.8
-40 -20 0 20 40 60 80 100 120 140 160 180 2000.0
0.3
0.6
0.9
Mn = 6.0 KDa, PDI=1.7
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 8
Tan
Del
ta
Temperature / oC
-20 0 20 40 60 80 100 120 140 160 180
10
100
1000
Mn = 6.0 KDa, PDI=1.7
[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 8
Sto
rage
Mod
ulus
/ M
Pa
Temperature / oC
DMTA results from films after UV thiol-ene curing (130 ºC, Irgacure 819)
Phase-separation for higher amount of Thiocure® (curing too fast to homogenize?)
Thermoset UV powder coating
Advantage: 1. Environmentally friendly; No solvent nor water needed. 2. Energy consideration: low curing temperature (180 ºC is standard) 3. High efficiency: no drying process, powder waste recyclable
Film Mn (kDa) a PDI a Curing agent Stoichimetry [=]:[SH]
Curing T (oC)
F1 6.0 2.2 TMPMP 4:1 130
F2 2.8 1.8 TMPMP
4:1 130
F3 3.1 1.8 TMPMP
2:1 130
Polymer resin properties and formulation
Compounds Weight %
Function
TMPMP - Curing agent
Irgacure @651 2 Photo-initiator
Resiflow PV 5 1.5 Flow agent
Benzoin 0.754 Degassing agent
Coatings on Al plates
a Determined by GPC. The polymer resins used in the powder coating were obtained after breaking down the high molecular weight PLCs with 1,10-decanediol.
Films F1 F2 F3 Av. film thickness (micrometer) 64 75 84
PCI powder smoothness rating (1-10) 5-6 5-7 5-7 Adhesion to metal (ASTM D3359) 5B (100%) 5B (100%) 5B (100%)
Pencil hardness (ASTM D3363) 2H 3H 3H Falling dart impact (ASTM D2794) - - -
König hardness (ASTM D4366) 199 s 190 s 174 s Cupping test (ISO 1502) 1.8 mm 0.8 mm 1.8 mm
Acetone resistance (ASTM D4752) + + +
Higher application temperature helps to achieve good leveling
Low toughness. as indicated by the fast impact test and slow deformation cupping test
Good adhesion and acetone resistance
Hard coating
Powder Coating Tests of film F1 (Mn=6 kDa; 130 ºC. [=]:[SH] = 4:1)
NOTE: Collaboration with Paul Buijsen / Gert Dijkstra at DSM CR, Zwolle, NL
1. The curing reaction of α,ω-dihydroxyl PLCs with multifunctional non-blocked and blocked isocyanates after solvent casting is not complete because of the low reactivity of the secondary and tertiary OH end groups. 2. Post-modification of PLCs with primary hydroxyl functionality by thiol-ene chemistry enhances the reactivity with multifunctional isocyanates and improves the performance of the resulting cured coatings, which have tunable thermal properties. 3. Direct thiol-ene chemistry curing of PLCs using a trifunctional thiol compound is both possible using thermal and UV initiators and both curing methods seem to give sufficiently cross-linked films exhibiting good properties.
4. The UV curable powder coatings from PLCs with Mn ranging from ca. 3 to 6 kDa show promising properties like good metal adhesion, acetone resistance and high hardness. As for the solvent-casted coatings the toughness is poor.
Summary
15-10-2015 32
Eindhoven University of Technology Department of Chemical Engineering and Chemistry Laboratory of Polymer Materials T +31 40247 2175 / 5197 F +31 40246 3966 c.li@tue.nl / rafael.sablong@ptgeindhoven.nl c.e.koning@tue.nl / cor.koning@dsm.com www.fp7-refine.eu
Contact
Acknowledgement
Chunliang Li
Dr. Rafaël Sablong
Martin Fijten
Carin Dietz
Liliana Gustini
Other SPM group members
Susana Torron Timhagen (KTH, Sweden)
Prof. Mats Johansson (KTH, Sweden)
Dr. Paul Buijsen (DSM, Zwolle)
Dr. Gert Dijkstra (DSM, Zwolle)
REFINE (network, funds)
Elham Hosseini Nejad, et al. Macromolecules, 2013, 46 (3), pp 631–637
Rearrangement reaction of limonene oxide and MPVO reaction.
OO O
O mH
The structure was introduced after the copolymerization of LO and CO2 because of the rearrangement reaction and thus appeared as an unexpected structure after the transcarbonation reactions.