Development of Novel Blowing Agents for

Polyurethane Foams

John McMenaminMark L. Robin, Ph.D.Gary LohJoseph A. Creazzo

Presented at:UTECH Europe 2009Maastricht, NetherlandsMarch 31-April 2, 2009

2

Development of a Novel Blowing Agent for Polyurethane Foams

OUTLINE

• Introduction

• Blowing Agents for Polyurethane

• Novel Blowing Agent FEA-1100Polyurethane foams (PUR)

Polyisocyanurate foams (PIR)

• Conclusion

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• Largest family of rigid thermoset foams

• Primary Markets• Construction insulation • Appliance insulation

• Use as insulation materials based on low thermal conductivity ( ), or high thermal resistivity (R-value) of foams

• Insulating characteristics of foam • Largely dependent upon the composition of the gas (Blowing agent) trapped in the cells

Rigid Polyurethane Foams

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Thermal Conductivity of Foam

λ = λsolid + λgas + λconvective + λradiative

λgas : gas in cells responsible for most of heat transfer

- foam usually over 90% gas or more by volume

λsolid : small

- 2 pcf PU foam, consists of 3% of solid polymer

λconvective, λradiative : small

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Blowing Agents for PU foams: Historical

Generation Main Characteristics Examples

First Generation

Low thermal conductivity

High ODP, GWP CFC-11

Second Generation

Low thermal conductivity

Low ODP, Moderate GWP

Moderate thermal conductivity

Zero ODP, Moderate GWP

Low thermal conductivity

Zero ODP, Low GWP

HCFC-141b

Third Generation

HFC-245fa, HFC-365mfc

Pentane, Isopentane

Fourth Generation FEA-1100

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Comparison of Blowing Agents

1st

Generation

2nd

Generation

3rd

Generation

CFC-11 HCFC-141b HFC-245fa HFC-365mfc Isopentane

ODP 1 0.12 0 0 0GWP 4750 725 1020 782 11bp oC 23.9 32.1 15.3 40.0 27.9

λ gas 25 oC

mW/mK 8.4 9.7 12.7 10.5 13.3Flash Point None None None - 25 oC - 51 oC

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Insulation Performance (measured by vapor thermal conductivity) among top three most important customer concerns … and a significant “pain point” because each previous conversion resulted in decreased performance.

0

2

4

6

8

10

12

14

CFC-11HCFC

-141b

HFC-245fa

HFC-365m

fcIso

pentan

e

Pentan

e

mW

/mK

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Boiling Point among top three most important customer concerns …and a significant “pain point” among existing users of HFC-245fa.

0

10

20

30

40

50

CFC-11HCFC-14

1bHFC-245

faHFC-365

mfcCyclo

pentaneIso

pentane

Pentan

e

Tem

pera

ture

- °C

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Ideal Blowing Agent• Zero ODP• Low GWP• Low vapor thermal conductivity• Nonflammable• Liquid at room temperature ( bp > 25 oC)• Low toxicity• Chemically/thermally stable• Soluble in formulation• Low rate of diffusion• Economically feasible

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FEA-1100: A Novel “4th Generation” Blowing Agent for Polyurethane Foams

ODP = 0

GWP = 5

Low vapor thermal conductivity10.7 mW/mK @ 25 oC

NonflammableASTM E 681; 60 oC, 100 oC

Boiling point > 25 oC

LC50 (4h, rat) > 106,000 ppm

Ames test negative

Chromosomal aberration negative

28 day inhalation NOEL = 2,500 ppm

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Insulation Performance (measured by vapor thermal conductivity) among top three most important customer concerns … and a significant “pain point” because each previous conversion resulted in decreased performance.

0

2

4

6

8

10

12

14

CFC-11HCFC

-141b

HFC-245fa

HFC-365m

fcIso

pentan

e

Pentan

eFEA-11

00

mW

/mK bp > 25 oC

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PUR Foams: FEA-1100 and HFC-245faBlowing Agent

Ingredients (pbw) FEA-1100 HFC-245fa

water 1.5 1.5

Rise time (s) 100

B-side 106.0 106.0

FEA-1100 32.2 0.0

HFC-245fa 0.0 26.3

120

Isocyanate 155.0 155.0

PROCESS DATA

Cream time (s) 7 6

Tack free time (s) 110 140

INITIAL PROPERTIES

Foam Index 1.1 1.1

Foam density (pcf) 2.2 2.1

R-value, BTU-in/ft2 h oF @ 75 oF 7.1 6.6

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Polyurethane Foams (PUR)

Polyurethane Foam HFC-245fa

Polyurethane Foam FEA-1100

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FEA-1100 and HFC-365mfc (PUR Foams)

Blowing Agent

Ingredients (pbw) FEA-1100 HFC-365mfc

water 1.5 1.5

Rise time (s) 120

B-side 106.0 106.0

FEA-1100 32.2 0.0

HFC-365mfc 0.0 29.1

110

Isocyanate 120.6 120.6

PROCESS DATA

Cream time (s) 7 7

Tack free time (s) 140 135

INITIAL PROPERTIES

Foam Index 1.1 1.1

Foam density (pcf) 1.9 1.8

R-value, BTU-in/ft2 h oF @ 75 oF 7.0 6.5

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FEA-1100 and Cyclopentane (PUR Foams)Blowing Agent

Ingredients (pbw) FEA-1100 cyclopentane

water 1.0 1.0

Rise time (s) 105

B-side 104.0 104.0

FEA-1100 29.4

cyclopentane 0.0 12.6

90

Isocyanate 132.0 132.0

PROCESS DATA

Cream time (s) 9 10

Tack free time (s) 105 100

INITIAL PROPERTIES

Foam Index 1.2 1.2

Foam density (pcf) 2.1 2.4

R-value, BTU-in/ft2 h oF @ 75 oF 7.2 6.6

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PIR Foams: FEA-1100 & HFC-245faBlowing Agent

Ingredients (pbw) FEA-1100 HFC-245fa

B-side 109.7 109.7

FEA-1100 39.7 0.0

HFC-245fa 0.0 32.4

Isocyanate 158.2 158.2

PROCESS DATA

Cream time (s) 15 12

Rise time (s) 110 110

Tack free time (s) 120 120

INITIAL PROPERTIES

Foam Index 2.5 2.5

Foam density (pcf) 2.1 2.2

R-value, BTU-in/ft2 h oF @ 75 oF 7.7 7.2

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Polyisocyanurate Foams (PIR)

PolyisocyanurateFoam HFC245fa

PolyisocyanurateFoam FEA-1100

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R-Value Comparisons

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Conclusion

Development of FEA-1100, a Novel Foam Expansion Agent for Polyurethane Foams

Zero ODPLow GWPLow vapor thermal conductivity NonflammableLow ToxicityPUR and PIR foamsGood dimensional stabilityUniform cell sizeR values exceed those obtained with HFC-245fa,HFC-365mfc and cyclopentane