co2-based polycarbonate polyols as strength enhancers … in flex foams.pdf · -based polycarbonate...
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CATALYZING GREEN CHEMISTRY
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CATALYZING GREEN CHEMISTRY
CO2-based Polycarbonate Polyols as Strength Enhancers in Flexible Foams
CPI 2013September 2013
Phoenix, AZ
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Novomer’s technology: direct conversion of waste gases to useful products via synthetic chemistry
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Polycarbonate polyols from CO2
O CO2+
Unique characteristics of the new polyol technology
• Distinctive performance from the high density carbonate backbone
• Economically attractive due to the use of inexpensive & readily available CO2
• Strong sustainability story due to direct sequestering of CO2 in backbone
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A wide range of starting molecules can be used…
Examples of starters used to create PPC polyols
Fn=
2Fn
> 2
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… to create a wide range of finished polycarbonate polyol structures
Fn=
2Fn
> 2
PPC Polyols produced to date
Starter
PO-based PPC
EO-based PEC
Other Epoxides
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Novomer has granted composition of matter patent protection on CO2-based polycarbonate polyols
CN 102149746 US 8,247,520
Novomer and its partners are free to pursue this new polyol technology platform in a wide variety of polyurethane and other thermoset chemistry applications
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These precise polycarbonate polyols enhance the strength of polyurethane products
0
2
4
6
8
10
12
Psi
(th
ou
san
ds)
PPC Polyol
Exist. PCDs
Ester Polyol
• 100% polycarbonate backbone:perfectly alternating CO2 / epoxide units yielding 100% carbonate and zero ether linkages
• Perfect -OH functionality: diols are 2.0 functional & triols are 3.0 functional at any molecular weight; no unsaturation
• Precise control of molecular weight: any Mw from ~500 g/mol to 10,000+ g/mol, all with a polydispersity index (PDI) of ~1.1
Characteristics of Novomer polyolsTensile strength of TPUs based on Novomer and other polyols
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Novomer PPC Polyol in flexible foams
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Raw materials and testing approach
Polyols
Other components
Testing approach
• Novomer PPC diol Equivalent Weight ~500, OH ~112
• Novomer PPC-PPG diol Equivalent Weight ~1000, OH ~56
• Polyether triol Equivalent Weight ~2000, OH ~27
• SAN Graft polyol Equivalent Weight ~2400, OH ~23
• Isocyanate – 2,4 MDI, TDI
• Surfactants and cell openers – standard types
• Catalysts – standard amine-type catalysts
• Create reference foams of three types – MDI-based flex, TDI-based flex, and viscoelastic
• Create test foams with varying levels of PPC polyol in B-side
• Test physical properties, including CFD, tensile strength, tear strength
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Viscosity of polyol formulations containing PPC
0
500
1000
1500
2000
2500
3000
10% 15% 20% 25%
Vis
cosi
ty (
cp, 2
5 C
)
Concentration of PPC polyol in total polyol formulation
PolyetherPolyol
NovomerPPC Polyol
Viscosity of polyol formulation at various PPC concentrations, room temperature
Formulation Note: Novomer PPC diol, OH ~112 formulated with standard EO-capped PPG triol, OH ~27.
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Examples of formulations used
MDI Baseline MDIwith 15% PPC
TDI Baseline TDIwith 20% PPC
Viscoelastic Baseline
Viscoelasticwith 20% PPC
Polyol System
Poly-G 85-29 97 82.45 48.5 38.8
Poly-G 30-240 21 11
Poly-G 76-120 21 11
Poly-G 85-34 18 18
DVV 6340 48.5 38.8
PPC Diol, OH ~112 14.55 20
PPC/PPG Diol, OH~56 19.4
Water 3.6 3.6 3.6 3.6 2.3 2.3
Lumulse POE 26 3 3 3 3 40 40
DEG 2.25 2.25
Tegostab B 4690 1 1 1 1 1.5 1.5
Dabco 33LV 0.8 0.5 0.5 0.5 0.1 0.1
Diethanolamine 1 2 1 1
Niax A-1 0.1 0.1 0.05 0.05 0.2 0.2
Iso System
Mondur MRS-2 57.12 63.35 49.45 49.15
Lupranate TD80 38.83 39.68
Iso Index 90 90 90 90 70 70
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Examples of formulations used
MDI Baseline MDIwith 15% PPC
TDI Baseline TDIwith 20% PPC
Viscoelastic Baseline
Viscoelasticwith 20% PPC
Polyol System
Poly-G 85-29 97 82.45 48.5 38.8
Poly-G 30-240 21 11
Poly-G 76-120 21 11
Poly-G 85-34 18 18
DVV 6340 48.5 38.8
PPC Diol, OH ~112 14.55 20
PPC/PPG Diol, OH~56 19.4
Water 3.6 3.6 3.6 3.6 2.3 2.3
Lumulse POE 26 3 3 3 3 40 40
DEG 2.25 2.25
Tegostab B 4690 1 1 1 1 1.5 1.5
Dabco 33LV 0.8 0.5 0.5 0.5 0.1 0.1
Diethanolamine 1 2 1 1
Niax A-1 0.1 0.1 0.05 0.05 0.2 0.2
Iso System
Mondur MRS-2 57.12 63.35 49.45 49.15
Lupranate TD80 38.83 39.68
Iso Index 90 90 90 90 70 70
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Examples of formulations used
MDI Baseline MDIwith 15% PPC
TDI Baseline TDIwith 20% PPC
Viscoelastic Baseline
Viscoelasticwith 20% PPC
Polyol System
Poly-G 85-29 97 82.45 48.5 38.8
Poly-G 30-240 21 11
Poly-G 76-120 21 11
Poly-G 85-34 18 18
DVV 6340 48.5 38.8
PPC Diol, OH ~112 14.55 20
PPC/PPG Diol, OH~56 19.4
Water 3.6 3.6 3.6 3.6 2.3 2.3
Lumulse POE 26 3 3 3 3 40 40
DEG 2.25 2.25
Tegostab B 4690 1 1 1 1 1.5 1.5
Dabco 33LV 0.8 0.5 0.5 0.5 0.1 0.1
Diethanolamine 1 2 1 1
Niax A-1 0.1 0.1 0.05 0.05 0.2 0.2
Iso System
Mondur MRS-2 57.12 63.35 49.45 49.15
Lupranate TD80 38.83 39.68
Iso Index 90 90 90 90 70 70
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PPC Polyols can greatly increase CFD
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Ref 10% PPC,OH 112
15% PPC,OH 112
psi
TDI-based Flex MDI-based Flex Viscoelastic
Impact of PPC Polyol on Foam tensile strength vs. standard polyether-based foams
25%
50%
65%
+ 2X with 15% PPC
~2.5 pcf foams, Tables 5&6 in report
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Ref 10% PPC,OH 112
20% PPC,OH 112
psi
25%
50%
65%+ 2X with 20% PPC
~3.3 pcf foams, Table 3 in report
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Ref 18% PPC,OH 112
30% PPCs,mixed
psi
+75% w/ 30% PPC
25%
50%
65%
~3 pcf foams, Table 3 in report
Note: All reported values are absolute & not adjusted for density; all densities are +/- 10% for each data set
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Impact of PPC Polyols on CFD is greater than graft polyols at a similar concentration
0.0
1.0
2.0
3.0
4.0
Reference 10% Strength EnhancingPolyol
25% Strength EnhancingPolyol
Novomer
Graft
Graft = 50% CFD increase at 10%
PPC = 75% CFD increase at 10%
Compression Force Deflection @ 50% with increasing PPC / Graft polyol
Reference foam CFD indexed to 1.0
Formulation Note: MDI-based flex foam formulations
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PPC polyols impart consistent strength to foams as measured by support factor
0.0
1.0
2.0
3.0
4.0
Reference
Support Factor (CFD)
Note: Support factor based on CFD results, not adjusted for density. All densities within +/- 10% for each data set. Density values available in full report.
TDI Foams, 50/25 CFD
TDI Foams, 65/25 CFD
MDI Foams, 65/25 CFD
MDI Foams, 50/25 CFD
Various formulations containing PPC at 10-20% concentrations
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Finished foam testing – Tear Strength
0
250
500
750
1,000
n/m
TDI-based Flex MDI-based Flex Viscoelastic
+10-25%
Impact of PPC Polyol on Foam tear strength vs. standard polyether-based foams
0
1
2
3
4
5
Lbf-
in
+5-40%
0
1
2
3
Lbf-
in
+5-25%
Note: All reported values are absolute & not adjusted for density; all densities are +/- 10% for each data set
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Finished foam testing – Tensile Strength
0
5
10
15
20
psi
TDI-based Flex MDI-based Flex Viscoelastic
+25% v Ref
Impact of PPC Polyol on Foam tensile strength vs. standard polyether-based foams
0
5
10
15
20
psi
+10-15%
0
5
10
15
20
psi
TBD
Note: All reported values are absolute & not adjusted for density; all densities are +/- 10% for each data set
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PPC Polyol can decrease resilience;the extent to which it does depends on formulation
0
20
40
60
80
Reference 5% PPC 10% PPC 15% PPC
TDI-basedFlex
Resilience vs. PPC backbone concentration in polyol formulation
Res
ilien
ce (
%)
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PPC Polyol can be used to create highly energy absorbing, slow recovery viscoelastic foams
0
1
2
3
4
CFD, 25% CFD, 65% Hysteresis Loss Recovery Time
Ch
ange
(b
ase
line
ind
exe
d t
o 1
)
Viscoelastic formulations with increasing PPC polyol concentration
2.2x
1.7x
2.1x
22x
PPC-based VE foams
Note: All reported values are absolute & not adjusted for density; all densities are +/- 10% for each data set
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PPC Polyols can be formulated into HR foams meeting automotive seating specifications
TDI-Based HR Foams Study, 4Q 2012
Core Density, pcf
CFD at 50%, psi
Tear Resis-tance, N/m2
Hysteresis Loss, % loss (max)
Wet Comp. Set, % (max)
2.362.39
2.5
0.540.42
829650
450
2720
30
1612
20
Value of PPC in HR Seating Foams
• Increased load bearing properties
• Increased tear and tensile strength
• Can be formulated with TDI to meet all automotive seating specs
Chrysler Spec
Baseline Foam
Foam w/ 10% PPC
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Additional testing currently underway
• PPC / PPG block copolymer backbone vs. foam properties• Viscosity & compatibility
• Finished foam properties
• “Equivalent structure” studies – 3000 Mw triol• Example compression set vs. backbone without changing x-link density
• Machine trials – flexible and rigid foams
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Summary
New family of CO2-based polyols can be used to increase the strength of flexible polyurethane foams
• Increased CFD – very significant increase with a small addition of PPC polyol; more pronounced than with graft polyols
• Increased tensile & tear strength – PPC backbone imparts high strength to urethane foams
• Increased energy absorbance – extent depends on formulation; can be formulated around or leveraged
Formulation testing & applications development is ongoing
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Thank You – Questions?
Novomer would like to thank Aisa and Vahid Sendijarevic of Troy Polymers, Inc., for designing and executing the experiments herein
Jason Anderson – [email protected]