co2-based polycarbonate polyols as strength enhancers … in flex foams.pdf · -based polycarbonate...

CATALYZING GREEN CHEMISTRY

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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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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


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


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


Iso Index 90 90 90 90 70 70


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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


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


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


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


+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%



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Finished foam testing – Tensile Strength

0

5

10

15

20

psi


+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



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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



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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

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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]

co2-based polycarbonate polyols as strength enhancers … in flex foams.pdf · -based polycarbonate...

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