Further Development of FEA-1100: A Low GWP Foam · PDF filePolyurethane 2010 Technical...

Polyurethane 2010 Technical Conference

Houston Texas

Further Development of FEAFurther Development of FEA--1100: 1100:

a Low GWP Foam Expansion Agent a Low GWP Foam Expansion Agent

October 11, 2010

Gary Loh, Joseph A Creazzo & Mark L Robin Ph.D

2

Presentation OutlinePresentation Outline

• Background

• FEA-1100 Properties

• Program Status

• Recent study

• Summary

3

FEA-1100

Challenges to Develop Low GWP FEAs Challenges to Develop Low GWP FEAs

HCFC-22CHClF2 (-41°°°°C)

CFC-12CCl2F2 (-30°°°°C)

CFC-11CCl3F (+24°°°°C)

HFO-1234yfCF3CF=CH2 (-28°°°°C)

HFO-1234zeCF3CH=CHF (-19°°°°C)

HFO-1336mzzCF3-CH=CH-CF3 (+33°°°°C)

HFC-245faCF3-CH-CHF2 (+15°°°°C)

HCFO-1233xfCF3CCl=CH2 (+15°°°°C)

HCFO-1233zdCF3CH=CHCl (+19°°°°C)

HFC-134aCF3-CFH2 (-26°°°°C)

HCFC-142bCClF2-CH3 (-10°°°°C)

HCFC-141bCCl2F-CH3 (+32°°°°C)

HIG

H O

DP

SO

ME

O

DP

ZE

RO

O

DP

HIGH GWP SOME GWP LOW GWP

DEVELOPMENT PROGRESSION FOR FLUORINATED FOAMING AGENTS

Approximateboiling point shown to the

right of each formula

= FLAMMABLE

HFC-152aCH3-CHF2 (-25°°°°C)

HFC-365mfcCF3-CH2-CF2-CH3 (+40°°°°C)

HCFC-22CHClF2 (-41°°°°C)

CFC-12CCl2F2 (-30°°°°C)

CFC-11CCl3F (+24°°°°C)

HFO-1234yfCF3CF=CH2 (-28°°°°C)

HFO-1234zeCF3CH=CHF (-19°°°°C)

HFO-1336mzzCF3-CH=CH-CF3 (+33°°°°C)

HFC-245faCF3-CH-CHF2 (+15°°°°C)

HCFO-1233xfCF3CCl=CH2 (+15°°°°C)

HCFO-1233zdCF3CH=CHCl (+19°°°°C)

HFC-134aCF3-CFH2 (-26°°°°C)

HCFC-142bCClF2-CH3 (-10°°°°C)

HCFC-141bCCl2F-CH3 (+32°°°°C)

HIG

H O

DP

SO

ME

O

DP

ZE

RO

O

DP

HIGH GWP SOME GWP LOW GWP

DEVELOPMENT PROGRESSION FOR FLUORINATED FOAMING AGENTS

Approximateboiling point shown to the

right of each formula

= FLAMMABLE

HFC-152aCH3-CHF2 (-25°°°°C)

HFC-152aCH3-CHF2 (-25°°°°C)



Reduce GWP while maintaining other desired properties

4

Selected Low GWP FEAs Candidates (HFOs & HCFOs)Selected Low GWP FEAs Candidates (HFOs & HCFOs)

21419616414613113113211411496

Molecular

Weight

YesYesYesNoMarginalNoNoNoNoNo

Liquid at

Room

Temperature

29323251914-15-20-19-28-22

Boiling Point

(°C)

NoNoNoNoSlightYesFlammability

Acceptable

Disqualifie

d for

toxicity

Acceptabl

e

Acceptabl

eToxicity

NoneNoneNoneNone

Small;

disqualified

for ODP

Small;

disqualifie

d for ODPNoneNoneNoneNoneODP

LowLowLowLowLowLowLowLowLowLowGWP

CF3CH=CHCF2CF3CF3CF2CF2CH=CH2CF3CH=CHCF3CF3CF2CH=CH2CF3CH=CHClCF3CCl=CH2CF3CF=CHFCF3CH=CHFCF3CF=CH2CF3CH=CH2Formula

1438mzz-E1447fz1336mzz-Z1345zfc1233zd-Z1233xf1225ye-Z1234ze-E1234yf1243zf

HFOHFOHFOHFOHCFOHCFOHFOHFOHFOHFO

1400 Series1300 Series1200 Series

Property

5

21419616414613113113211411496

Molecular

Weight


Liquid at

Room

Temperature

29323251914-15-20-19-28-22

Boiling Point

(°C)


Acceptable

Disqualified

for toxicity

Acceptabl

e

Acceptabl

eToxicity

NoneNoneNoneNoneODP [1]ODP [1]NoneNoneNoneNoneODP






Property

Screening Low GWP FEAs Screening Low GWP FEAs -- ODPODP

1. Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, 2007.

[Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report No. 50, 572 pp., World

Meteorological Organization, Geneva, Switzerland, 2007.]

6

21419616414613113113211411496

Molecular

Weight


Liquid at

Room

Temperature

29323251914-15-20-19-28-22

Boiling Point

(°C)


AcceptableToxicityAcceptableAcceptableToxicity







Property




Screening Low GWP FEAs Screening Low GWP FEAs -- ToxicityToxicity

7

21419616414613113113211411496

Molecular

Weight


Liquid at

Room

Temperature

29323251914-15-20-19-28-22

Boiling Point

(°C)









Property

Screening Low GWP FEAs Screening Low GWP FEAs -- Flammability & Boiling PointFlammability & Boiling Point




8

21419616414613113113211411496

Molecular

Weight


Liquid at

Room

Temperature

29323251914-15-20-19-28-22

Boiling Point

(°C)






1438mzz-E1447fz

1336mzz-Z

(FEA-1100)1345zfc1233zd-Z1233xf1225ye-Z1234ze-E1234yf1243zf



Property

Screening Low GWP FEAs Screening Low GWP FEAs -- MWMW




9

FEAFEA--1100 1100 –– a Sustainable & Balanced Optiona Sustainable & Balanced Option

CF3CH=CHCF3

� Nonflammable (ASTM E 681 at 60oC & 100oC)

� b.p = 33 oC

� λλλλ= 10.7 mW/mK @ 25 oC

� MW = 164

FEA-1100 (HFO-1336mzz)

� ODP = 0

� GWP 100 yr ITH = 9.4 (NOAA)

� ATM lifetime = 24 days (NOAA)

10

FEAFEA--1100 Vapor Pressure1100 Vapor Pressure

Vapor Pressure

0

10

20

30

40

50

60

60 70 80 90 100 110 120 130

Temperature (oF)

Va

po

r p

ress

ure

(p

sia

)

FEA-1100 (b.p. =33C)

HCFC-141b (b.p. = 32C)

HFC-245fa (b.p. = 15C)

Cyclopentane (b.p. = 49C)

Drum pressure rating

Vapor pressure well below the drum pressure rating

11

FEAFEA--1100 Vapor Thermal Conductivity1100 Vapor Thermal Conductivity

• Low vapor thermal conductivity over broad temperature range

• Lowest thermal conductivity when temperature >150F

Vapor Thermal Conductivity vs Temperature

0.0030

0.0040

0.0050

0.0060

0.0070

0.0080

0.0090

0.0100

0.0110

0.0120

0.0130

0.0140

0.0150

0.0160

-50 0 50 100 150 200 250 300

Temperature (oF)

Vap

or

therm

al co

nd

ucti

vit

y

(Btu

/hr-

ft-F

)

FEA-1100

HFC-245fa

HCFC-141b

Cyclopentane

12

Candidate

Evaluation

Customer

Validation

Intermediate Scale

Commercial Sales

Full Scale

Commercial Sales

Screening

Candidates

Desired FEA

Properties

SNAP, PMN,

REACH & additional

tests as needed

Support customer

conversion

Intermediate scale

commercial plant

Support customer

testing &

optimization

2009 2010-2011 2012-2013 2014-2015

Small lot productionManufacturability Full scale

commercial plant

Support customer

conversion

Launch

FEA-1100Supply

FEA-1100

DuPont Low GWP FEA (Blowing Agent) ProgramDuPont Low GWP FEA (Blowing Agent) Program

ODP, GWP,

Flammability,

Toxicity..

Insulation

performance,

Stability,

Solubility…

Bench scale

production and

optimization

Safety &

Environmental

Properties

13

Previous Work Previous Work –– Demonstrating DropDemonstrating Drop--in Performancein Performance

• Superior initial and aged K-factors than HCFC-141b, HFCs (HFC-245fa &

HFC-365mfc) and pentanes (cyclopentane & isopentane) in generic

formulations containing major types of polyols

• FEA-1100 blends improves the performance of HFCs & pentanes

• Good material compatibility

� Metal, elastomers and plastics (including ABS and HIPS)

• Good polyol solubility

� Soluble in commonly used polyols

� Vapor pressure at 50C is well below the drum pressure rating

Reference: Proceedings of 12th International Conference: Blowing agents and foaming processes,

Cologne, Germany (2010), page 5

14

Recent Work Recent Work –– Providing Data for Customer TestingProviding Data for Customer Testing

• Further toxicity evaluation

• Chemical stability – shelf life

• Thermal stability – foaming process

• Heat of evaporation

• Foam expansion efficiency

15

Toxicity Assessment Toxicity Assessment

4-hr LC50: Very Low acute toxicity

Skin Irritation: Non - irritating

Ames Test: Non - mutagenic

Chromosomal Aberration: No genetic material damage

Cardiac Sensitization: Favorable cardiac sensitization potential profile

28-Day Repeat Inhalation: Favorable repeated inhalation profile

Clean data so far

90 Day/ developmental: Favorable repeated inhalation profile

consistent with 28-day test result

16

Shelf Life Stability Shelf Life Stability –– Polyether at 50 Polyether at 50 ooC for 6 MonthsC for 6 Months

Days at 50oC in

Oven

Cream time

(seconds)

Tack free

(seconds)

Ratio

(Tack free /Cream time)

Foam density

(pcf)

0 25 90 3.6 2.1

4 20 90 4.5 2.2

21 21 110 5.2 2.2

53 23 100 4.3 2.4

89 25 75 3.0 2.6

122 27 120 4.4 2.6

150 28 100 3.6 2.2

187 28 100 3.6 1.9

FEA-1100 is stable in a

generic polyether

formulation after 6

month storage at 50 oC

B-side ingredients Weight % (pbw)

Polyether (TDA) 100

Silicon Type Surfactant 2.0

Amine-based Catalyst 3.0

Co-catalyst 1.0

Water 1.0

FEA-1100 29.4

Foam index 1.2

17

FEA-1100 is stable in a

generic polyester

formulation after 6

month storage at 50 oC

Shelf Life Stability Shelf Life Stability –– Polyester at 50 Polyester at 50 ooC for 6 MonthsC for 6 Months

Days at 50oC in

Oven

Cream time

(seconds)

Tack free

(seconds)

Ratio

(Tack free /Cream time)

Foam density

(pcf)

0 25 90 3.6 2.5

15 30 110 3.7 2.4

47 20 130 6.5 2.3

83 25 135 5.4 2.6

116 27 120 4.4 2.2

144 30 100 3.3 2.4

181 30 100 3.3 2.2

B-side ingredients Weight% (pbw)

Aromatic Polyester 100

Silicon Type Surfactant 6.2

Potassium Catalyst 2.8

Amine-based Catalyst 0.7

FEA-1100 39.7

Foam index 2.5

18

Thermal Stability Test Thermal Stability Test -- Generic Spray Foam Formulation Generic Spray Foam Formulation

0 100 200101

102

103

FEA-1100 in spray foam formulation

Pressure vs. Temperature

Pres

sure

(psi

a)

Temperature (oC)[Plotted as -1/T]

• ARC test: ~90% full

• High FEA-1100 level

Spay Foam Formulation Weight % pbw

Polyether (Mannich-base) 50.00

Polyester 50.00

Silicone surfactant 0.25

Additive 3.00

Flame retardant (TCPP) 21.50

Tertiary amine catalyst 0.97

Potassium catalyst 0.25

Water 0.63

FEA-1100 47.69

• No sign of decomposition

FEA-1100 in Generic Spray Foam System

0

10

20

30

40

50

60

70

80

90

100

110

120

0 100 200 300 400 500 600

Time (minute)

Te

mp

era

ture

(C

)

0

10

20

30

40

50

60

70

80

90

100

110

120

Pre

ss

ure

(p

sia

)

Temperature

Pressure

• Heat – Wait – Search cycle to 100 oC

19

Thermal Stability Test Thermal Stability Test -- Generic Appliance Formulation Generic Appliance Formulation FEA-1100 in Generic Appliance System

0

10

20

30

40

50

60

70

80

90

100

110

120

0 50 100 150 200 250 300 350 400 450 500

Time(minute)

Te

mp

era

ture

(C

)

0

20

40

60

80

100

120

Pre

ss

ure

(p

sia

)

Temperature

Pressure

0 100 200101

102

103

FEA-1100 in appliance formulation

Pressure vs. Temperature

Pre

ssur

e (p

sia)

Temperature (oC)

[Plotted as -1/T]

• ARC test: ~90% full

• High FEA-1100 level

• Heat – Wait – Search cycle to 100 oC

• No sign of decomposition

Appliance Formulation Weight% (pbw)

Polyether (sucrose) 75.00

Polyether (TDA) 25.00

Silicone surfactant 6.00

Tertiaty amine catalyst 1 3.00

Tertiaty amine catalyst 2 0.38

Co-catalyst 0.50

Water 1.70

FEA-1100 42.05

20

Liquid Heat CapacityLiquid Heat Capacity

Liquid Heat Capacity vs. Temperature

0.25

0.30

0.35

0.40

0.45

0.50

30 40 50 60 70 80 90 100 110 120 130 140 150

Temperature (oF)

Liq

uid

heat

cap

acit

y

(Btu

/lb

-F)

FEA-1100 HFC-245fa HCFC-141b Cyclopentane

HFC-245fa HCFC-141b FEA-1100 Cyclopentane

bp (Fo) 60 91 90 121

21

Latent HeatLatent Heat

Latent Heat vs. Temperature

60

80

100

120

140

160

180

200

30 40 50 60 70 80 90 100 110 120 130 140 150

Temperature (oF)

La

ten

t h

ea

t(B

tu/lb

)

FEA-1100 HFC-245fa HCFC-141b Cyclopentane

HFC-245fa HCFC-141b FEA-1100 Cyclopentane

bp (Fo) 60 91 90 121

22

Heat Required to Evaporate FEAHeat Required to Evaporate FEA--11001100

166.683.997.171.0Latent heat (Btu/lb) at FEA boiling point

21.90.04.95.8Heat required to heat FEA from 22°C to its

boiling point, (Btu/lb)

70134117164Molecular Weight

49153233Boiling point (°C)

Mass Basis:

CyclopentaneHFC-245faHCFC-141bFEA-1100

Close to HCFC-141b, HFC-245fa & cyclopentane

1.050.890.951.00Relative heat requirement to vaporize FEAs

1321711,25011,93912,586Total heat to vaporize FEA from 22°C, Btu/mol

Molar basis:

2.461.091.331.00Relative heat requirement to vaporize FEAs

188.583.9102.076.8Total heat to vaporize FEA from 22°C, Btu/lb

23

Effect of FEAEffect of FEA--1100 Level in Appliance Formulation1100 Level in Appliance Formulation

Effect of FEA-1100

(Generic Appliance Formulation)

0.125

0.135

0.145

0.155

0.165

0.05 0.10 0.15 0.20 0.25

Moles of FEA-1100K

-fa

cto

r

K-factor (35F) K-factor (50F) K-factor (75F)

Optimize for best insulation & FEA efficiency

Initial foam properties

Density(pcf) 1.8 1.7 2.0

K-factor (Btu.in/ft2.h.oF) @ 35oF 0.135 0.130 0.145



FEA-1100 pbw change 0% -34% -67%

FEA-1100 (0.21 moles)

FEA-1100 (0.14 moles)

FEA-1100 (0.07 moles)

Ingredients pbw pbw pbw

Susrose polyol) 75 75 75

TDA 25 25 25

Surfactant 6.0 6.0 6.0

Catalyst 1 3.0 3.0 3.0

Catalyst 2 0.38 0.38 0.38

Co-catalyst 0.5 0.5 0.5

Moles of H2O 0.14 0.21 0.28

Moles of FEA-1100 0.21 0.14 0.07

Total moles of FEA-1100+H2O 0.35 0.35 0.35

Isocyanate 169 191 212

Foam index 1.1 1.1 1.1

24

Effect of FEAEffect of FEA--1100 Level in Cyclopentane 1100 Level in Cyclopentane

Effect of FEA-1100 Level

(Generic PIP Formulation)

0.1350

0.1400

0.1450

0.1500

0.1550

0% 20% 40% 60% 80% 100%

Weight% of FEA-1100 in cyclopentane

K-f

acto

r100 wt% FEA-1100 85 wt% FEA-1100 50 wt % FEA-1100 0 wt% FEA-1100

Incredients pbw pbw pbw pbw

TDA based polyol 100 100 100 100

Surfactant 2.0 2.0 2.0 2.0

Catalyst 1.5 1.5 1.5 1.5

Co-catalyst 0.5 0.5 0.5 0.5

FEA(moles) 0.18 0.18 0.18 0.18

Water(moles) 0.056 0.056 0.056 0.056

Isocyanate 132 132 132 132

foam index 1.2 1.2 1.2 1.2

Density (PCF) 2.1 2.3 2.4 2.4

K-factor (Btu.in/ft2.h.

oF) @ 75

oF 0.138 0.137 0.148 0.151

25

Summary Summary

• Zero ODP & low GWP

• Non-flammable FEA with boiling point close to HCFC-141b

[1] Proceedings of 12th International Conference: Blowing agents and foaming processes,

Cologne, Germany (2010), page 5

• Good chemical and thermal stability

• Heat of evaporation close to HCFC-141b, HFC- 245fa & cyclopentane

• Superior insulation performance compared to HCFC-141b, HFCs (245fa &

365mfc) & pentanes (cyclopentane & Isopentane) [1]

• Good material compatibility and polyol solubility [1]

• Potential drop-in replacement with improved performance

Further Development of FEA-1100: A Low GWP Foam · PDF filePolyurethane 2010 Technical...

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