DuPont™ FEA-1100: Zero ODP, Low GWP, DuPont™ FEA-1100: Zero ODP, Low GWP, Non-Flammable Alternative for Non-Flammable Alternative for HCFC-141b

Helen Walter-Terrinoni

Nov 12, 2010

2Desired Properties for HCFC-141b Phase-out

• Environmentally sustainable

Zero ODP & Low GWP

• Safety & Handling

Low Toxicity

Chemical stable

Non-flammable

Suitable boiling point (25C - 35C)

• Good insulation performance

Low vapor thermal conductivity or Lambda

Flexibility to use high level of FEA

• Low conversion cost

Potential drop-in to existing process & equipment

Potential drop-in to existing formulations

3

CFC-11 HCFC-141b

HCFC-141b Phase-out Options

HFC-245faHFC-365mfc

PentanesMethyl Formate

MethylalH2O(CO2)Mixtures

HIGH ODP LOW ODP ZERO ODP

Next Generation Low GWP

FEA-1100

HBA-2AFA-L1

Next Generation Low GWPZero ODP

4

FEA-1100 – a Sustainable & Balanced OptionFEA-1100 – a Sustainable & Balanced Option

CF3CH=CHCF3

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

b.p = 33 oC

λ= 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)

5

FEA-1100

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-152a

CH3-CHF2 (-25°C)

HFC-365mfcCF3-CH2-CF2-CH3 (+40°C)

HFC-365mfcCF3-CH2-CF2-CH3 (+40°C)

Reduce GWP while maintaining other desired properties

6

Foam Expansion Agent Property Comparison

3-Carbon Series 4-Carbon Series 5-Carbon Series Property

HFO 1243zf

HFO 1234yf

HFO 1234ze-E

HFO 1225ye-Z

HCFO 1233xf

HCFO 1233zd-Z

HFO 1345zfc

HFO 1336mzz-Z

HFO 1447fz

HFO 1438mzz-E

Formula CF3CH=CH2 CF3CF=CH2 CF3CH=CHF CF3CF=CHF CF3CCl=CH2 CF3CH=CHCl CF3CF2CH=CH2 CF3CH=CHCF3 CF3CF2CF2CH=CH2 CF3CH=CHCF2CF3

ODP None None None None Small;

disqualified for ODP

Small; disqualified

for ODP None None None None

GWP Low Low Low Low Low Low Low Low Low Low

Boiling Point (°C)

-22 -28 -19 -20 14-15 19 5 32 32 29

Liquid at Room Temperature

No No No No No Marginal No Yes Yes Yes

Molecular Weight

96 114 114 132 131 131 146 164 196 214

Toxicity Acceptable Acceptable Disqualified for toxicity

Acceptable

Flammability Yes Slight No No No No

7

HCFC-141b Phase-out Option ComparisonsHCFC-141b Phase-out Option ComparisonsFEA-1100 – a zero ODP & low GWP FEA with desired properties

FEAs ODP GWP Flash Point(oC)Lambda @ 25 oC

(mW/mK)

Boiling Point

(oC)Conversion Cost

HCFC-141b 0.11 725 a none 9.7 32 NA

HFC-245fa 0 1030 a none 12.7 15Med ium

(High vapor pressure)HFC-365mfc 0 794 a -24 10.5 40 High (Flammability)Cyclopentane 0 11 b -7 13b 49 High (Flammability)CO2 0 0 none 16.3b -139 LowMethylal 0 0 -19 42 High (Flammability)Methyl Formate 0 0 -18 10.7b 32 High (Flammability)

HBA-2 Negligible b <15 d none 15 - 32 dLow - Medium

(Potential high vapor pressure)

AFA-L1 Negligible b <15 d none 10b 15 - 30 dLow - Medium

(Potential high vapor pressure)

FEA-1100 0 9.4c none 10.7 33 Low

a: IPCC/TEAP (2005)

b: UNDP, Phaseout Technologies for PU Foams, June 2010;

c: NOAA(2010)

d: Proceedings of Polyurethanes 2009 Technical Conference

8

Vapor Pressure

0

10

20

30

40

50

60

60 70 80 90 100 110 120 130

Temperature (oF)

Vap

or

pre

ssu

re (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 is very close to HCFC-141b

Thermal Conductivity and Vapor Pressure Comparisons

Vapor Thermal Conductivity vs Temperature

0.00300.00400.00500.00600.00700.00800.0090

0.01000.01100.01200.01300.01400.01500.0160

-50 0 50 100 150 200 250 300

Temperature (oF)V

apo

r th

erm

al c

on

du

ctiv

ity

(Btu

/hr-

ft-F

)

FEA-1100

HFC-245fa

HCFC-141b

Cyclopentane

• Low vapor thermal

conductivity over broad

temperature range

• Lowest thermal

conductivity when

temperature >150F

9

FEA-1100 vs Other Zero ODP FEAsFEA-1100 vs Other Zero ODP FEAs

FEA-1100 has the best

insulation performance

Ingredients pbwTDA-based polyol 100Surfactant 2.13

Catalysts 2.00FEAs (moles) 0.18Water (moles) 0.06Isocyanate 132Foam index 1.2

FEAsR-value

(ft2.h.oF/Btu.in) @ 75oFDensity

(pcf)FEA-1100 7.2 2.1HFC-245fa 6.9 2.2HFC-365mfc 6.9 2.2Cyclopentane 6.6 2.4Isopentane 6.3 2.5Methyl formate 6.1 2.2Methylal 5.9 2.3

PUR Foam R-value Comparisons (Equi-molar FEA)

5.86.06.26.46.66.87.07.27.4

FEA-110

0

HFC-245f

a

HFC-365m

fc

Cyclo

penta

ne

Isopen

tane

Met

hyl fo

rmate

Met

hylal

R-v

alu

e @

75F

10FEA-1100 Impact on FEA Mixtures

• Adding FEA-1100 to other

zero ODP FEAs

• Same foam formulation &

equi-molar FEAs

• FEA-1100 improves R-

value

FEAsR-value

(ft2.h.oF/Btu.in) @ 75oFDensity

(pcf) Benefits

HFC-245fa 6.9 2.2FEA-1100/HFC-245fa mixture 7.1 2.4 Improved GWP, b.p & R-value

HFC-365mfc 6.9 2.2FEA-1100/HFC-365mfc mixture 7.4 2.2 Improved GWP, R-value & flammability

Cyclopentane 6.6 2.4FEA-1100/cyclopentane mixture 7.3 2.3 Improved R-value & flammability

Isopentane 6.3 2.5FEA-1100/isopentane mixture 6.9 2.4 Improved R-value & flammability

Methyl formate 6.1 2.2FEA-1100/methyl formate mixture 7.3 2.3 Improved R-value & flammability

Methylal 5.9 2.3FEA-1100/methylal mixture 6.8 2.0 Improved R-value & flammability

Effect of FEA-1100 on Other FEAs

5.86.06.26.46.66.87.07.27.4

HFC-245fa & itsFEA-1100mixture

HFC-365mfc &its FEA-1100

mixture

Cyclopentane& its FEA-1100

mixture

Isopentane &its FEA-1100

mixture

Methylformate & its

FEA-1100mixture

Methylal & itsFEA-1100mixture

R-v

alu

e

Other FEAs FEA-1100-other FEA mixtures

11

FEA-1100 Mixture – Polyester PolyolFEA-1100 Mixture – Polyester Polyol• Blend FEA-1100 to 50/50 cyclopentane(c-C5)-isopentane(i-C5) mixture

• Same foam formulation & equi-molar FEAs

• FEA-1100 improves performance

Aged R-value - PIR Foams(FEA-1100 vs 50/50 cyclopentane/isopentane)

6.2

6.4

6.6

6.8

7.0

7.2

7.4

7.6

0 20 40 60 80 100 120 140 160 180 200Days

R-v

alu

e

12

FEA-1100 vs HCFC-141b & HFCsFEA-1100 vs HCFC-141b & HFCs

Superior insulation performance compared to HCFC-141b & HFCs

Ingredients (pbw)FEA-1100 HCFC-141b HFC-245fa HFC-365mfc

Sucrose- based polyol 100 100 100 100Surfactant 2.00 2.00 2.00 2.00Catalysts 4.00 4.00 4.00 4.00water (moles) 0.08 0.08 0.08 0.08FEA (moles) 0.20 0.20 0.20 0.20Isocyanate 121 121 121 121Foam Index 1.1 1.1 1.1 1.1

Cream time(s) 7 6 6 7Rise time(s) 120 120 120 130Tack free time(s) 140 150 140 140

Reaction Profile

Foam density(pcf) 1.9 2.0 2.0 1.9

R-value (ft2.h.oF/Btu.in) @ 75oF 7.0 6.7 6.5 6.5

Foam Initial Properties

13FEA Level & R-value (FEA-1100 vs HFC-245fa)

R-value Comparison (FEA-1100 vs HFC-245fa)

6.06.26.46.66.87.07.27.47.67.8

Low FEA level High FEA level (b.p >25C) HFC-245fa vs FEA-1100

R-va

lue

HFC-245fa FEA-1100

* High level of HFC-245fa may cause pressure exceed drum pressure rating

• High level of FEA-1100 can

be used without vapor

pressure or flammability

limitation

• High level of FEA-1100 can

potentially improve

insulation performance

Ingredients (pbw)

HFC-245fa (low FEA level)

FEA-1100 (low FEA level)

Mannich polyol 50 50Polyester polyol 50 50Surfactant 0.25 0.25Flame retardant and additives 24.50 24.50Catalysts 1.22 1.22FEA (moles) 0.045 0.045Water (moles) 0.169 0.169Isocyanate 138 138Foam index 1.1 1.1

HFC-245fa (high FEA level)*

FEA-1100 (high FEA level)

50 5050 50

0.25 0.2524.50 24.501.22 1.220.179 0.1790.035 0.035

97 971.1 1.1

Cream time(s) 8 8 7 7Rise time(s) 70 67 85 71Tack free time(s) 70 70 90 85

Reaction Profile

Sample density (pcf) 2.6 2.6 2.5 2.8R-value (ft2.h.oF/Btu.in) @ 75oF 6.1 6.2 7.2 7.7

Foam Initial properties

14

Chemical Stability – Polyether at 50 Chemical Stability – Polyether at 50 ooC for 6 monthsC for 6 months

FEA-1100 is stable in a generic polyether formulation after 6 months storage at 50 oC

B-side ingredients pbwPolyether (TDA) 100Silicon Type Surfactant 2.0Amine-based Catalyst 3.0Co-catalyst 1.0Water 1.0FEA-1100 29.4Foam index 1.2

Days at 50oC in Oven

Cream time (seconds)

Tack free (seconds)

Ratio (Tack free /Cream time)

Foam density (pcf)

0 25 90 3.6 2.14 20 90 4.5 2.221 21 110 5.2 2.253 23 100 4.3 2.489 25 75 3.0 2.6

122 27 120 4.4 2.6150 28 100 3.6 2.2187 28 100 3.6 1.9

15

FEA-1100 is stable in a generic polyester formulation after 6 months storage at 50 oC

Chemical Stability – Polyester at 50 Chemical Stability – Polyester at 50 ooC for 6 monthsC for 6 months

B-side ingredients pbw

Aromatic Polyester 100Silicon Type Surfactant 6.2Potassium Catalyst 2.8Amine-based Catalyst 0.7FEA-1100 39.7

Foam index 2.5

Days at 50oC in Oven

Cream time (seconds)

Tack free (seconds)

Ratio (Tack free /Cream time)

Foam density (pcf)

0 25 90 3.6 2.515 30 110 3.7 2.447 20 130 6.5 2.383 25 135 5.4 2.6116 27 120 4.4 2.2144 30 100 3.3 2.4181 30 100 3.3 2.2

16

FEA-1100 is soluble in commonly used polyols

Polyol SolubilityPolyol Solubility

Polyol TypeOH#

(mg KOH/g)

Weight% in Polyols for Single Phase

Mixture (21oC)

Weight% in Polyols for Single Phase

Mixture (50oC)

Polyethers

Amine 391-800 5-50+ 40-50+Sucrose/amine 400-499 50+ 50+Sucrose/glycol 440 50+ 50+Sucrose/glycerine 280-520 50+ 50+Sorbitol 490 50+ 50+Mannich-base 300-390 5-50+ 29-50+

Polyesters 240-307 5-30 23-35

17

Material Compatibility - MetalMaterial Compatibility - Metal

Changes after 2 weeks at 100oC (212oF) in FEA-1100

FEA-1100 is compatible with commonly used metals

Metal Coupons

Stainless Steel

Carbon Steel

Copper

Brass

Aluminum

Metal Coupon Weight

Metal Coupon Appearance

No weight change No sign of corrosion

No weight change No sign of corrosion

No weight change No sign of corrosion

No weight change No sign of corrosion

No weight change No sign of corrosion

FEA Solution Appearance

FEA Solution Analysis

Clear No fluoride detected **

Clear No fluoride detected **

Clear No fluoride detected **

Clear No fluoride detected **

Clear No fluoride detected **

** Detection limit = 0.5 ppm

18

Material Compatibility - Elastomers Material Compatibility - Elastomers

FEA-1100 is compatible with commonly used elastomers

Changes after 2 weeks at room temperature in FEA-1100

Symbol Material Brand

NR Natural Rubber Natural RubberCR Polychloroprene Neoprene® WNBR Acrylonitrile Butadiene BUNA NCSM Chlorosulfonated Polyethylene Hypalon 40®FFKM Fluoroelastomer Kalrez®T Polysulfide THIOKOL FA ®IIR Isobutylene Isoprene Butyl Rubber

EPDMHydrocarbon (Ethylene-Propylene Terpolymer) Nordel®

% Weight Change

% Volume Change

% Hardness Change

4.4% 1.9% 0.0%0.8% 0.1% 0.0%

15.3% 2.6% -13.6%0.2% 0.8% -1.3%7.9% -3.4% -2.9%0.3% 6.7% -6.1%0.3% 13.1% -13.3%

1.4% 5.5% -7.1%

19

Material Compatibility - Plastics Material Compatibility - Plastics

Changes after 2 weeks at room temperature in FEA-1100

FEA-1100 is compatible with commonly used plastics

Symbol Material Brand% Weight Change

% Volume Change

% Hardness Change

ABS Acrylonitrile-butadiene-styrene Cycolac®EX58 -0.1% -0.6% 0.0%HIPS High Impact Polystyrene 0.3% -0.4% -2.9%PET Poly(ethylene terephthalate) Rynite® 0.0% 0.7% -1.2%PS Polystyrene Styron® -0.4% 0.9% 0.0%PVC Polyvinyl Choloride Bakelite® 0.0% 0.0% 0.0%CPVC Chlorinated Polyvinyl Choloride 0.0% -0.3% 0.0%PTFE Fluorocabon(PTFE) Teflon ® 1.1% 0.3% -17.2%ETFE Fluorocabon(ETFE) Tefzel® 0.7% 0.0% 12.9%

Ionomer Surlyn® 0.3% 0.0% 1.9%POM Acetal Delrin® 0.1% -1.2% -1.3%PC Polycarbonate Tuffak® 0.0% -0.6% 0.0%PEEK Polyetheretherketone Victrex® 0.0% 0.2% 0.0%

Polyarylate Arylon® 0.2% -0.2% -4.4%LCP Polyester Xydar ® 0.0% -0.4% -1.5%

Nylon 6/6 Zytel® 101 0.4% -0.5% 3.1%PEI Polyetherimide Ultem® -0.1% 0.0% 0.0%

Polyaryl sulfone Radel® -0.2% 0.3% 0.0%PVDF Poly(vinylidene fluoride) Kynar® 0.1% -0.3% 0.0%PP Polypropylene Tenite® 0.3% -0.5% 0.0%

LCP Zenite -0.1% -0.9% 0.0%HDPE High Density Polyethylene Alathon ® 0.0% 0.3% 3.3%

Phenolic Duzez® 0.0% -0.1% 1.2%

20

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

FEA-1100: Favorable Results

90 Day/ developmental: Favorable repeated inhalation profile consistent with 28-day test result

21

CandidateEvaluation

Customer ValidationIntermediate 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-1100

Supply 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

22

FEA-1100 Summary FEA-1100 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[2] Proceedings of Polyurethans 2010 Technicla Conference 2010, Houston, USA (2010)

• Good chemical and thermal stability [2]

• Heat of evaporation close to HCFC-141b, HFC- 245fa & cyclopentane [2]

• 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

23

Disclaimer:

The information set forth herein is furnished free of charge and based on technical data that DuPont believes to be reliable. It is intended for use by persons having technical skill, at their own risk. Since conditions of use are outside our control, we make no warranties, expressed or implied and assume no liability in connection with any use of this information. Nothing herein is to be taken as a license to operate under, or a recommendation to infringe any patents or patent applications.

2424