Development of FEA-1100 - Chemours · Foam Expansion Agent with Desired Properties March 9-11, 2011 ... 1st Gen 2nd Gen 3rd Gen 4th Gen. 3 ... Low FEA le ve l High FEA le ve l

PUTECH 2011

Greater Noida, Delhi NCR, India

Development of FEADevelopment of FEA--1100 1100 –– a Zero ODP & Low GWP a Zero ODP & Low GWP

Foam Expansion Agent with Desired PropertiesFoam Expansion Agent with Desired Properties

March 9-11, 2011

Gary Loh

Joseph A Creazzo

Mark L Robin Ph.D

Helen A Walter-Terrinoni

Kapil Singhal

2

CFC-11 HCFC-141b

HCFCHCFC--141b Phase141b Phase--out Options out Options

HFC-245fa

HFC-365mfc

Pentane

Methyl Formate

Methylal

H2O(CO2)

Blends

HIGH ODP LOW ODP ZERO ODP Low GWP

FEA-1100

HBA-2

AFA-L1

1st Gen 2nd Gen 3rd Gen 4th Gen

3

HCFCHCFC--141b 141b vsvs Commercially Available Options (3Commercially Available Options (3rdrd Gen. Gen. FEAsFEAs))

Low10.733yesyesyesFEA-1100 a

Low - Medium

(Potential high vapor pressure)1015 - 30 yesyesno bAFA-L1 a

Low - Medium

(Potential high vapor pressure)15 - 32yesyesno bHBA-2 a

Low16.3-139yesyesyesCO2

High (Flammability)10.732noyesyesMethyl Formate

High (Flammability)42noyesyesMethylal

High (Flammability)1349noyesyesCyclopentane

Low-High (Flammability)10.5-11.224-40maybenoyesHFC-365mfc/Blends

Medium

(High vapor pressure)12.715yesnoyesHFC-245fa

NA9.732yesnonoHCFC-141b

Conversion Costλ@ 25 oC

(mW/mK)

Boiling

Point

(oC)

NonflammabilityLow

GWP

Zero

ODPFEAs

4

Zero ODP & Nonflammable (3rd Gen. Zero ODP & Nonflammable (3rd Gen. FEAsFEAs))


Low - Medium


Low - Medium







Medium




(mW/mK)

Boiling

Point

(oC)

NonflammabilityLow

GWP

Zero

ODPFEAs

5

Zero ODP & Nonflammable with Low Zero ODP & Nonflammable with Low λλ (3rd Gen. (3rd Gen. FEAsFEAs))


Low - Medium


Low - Medium







Medium




(mW/mK)

Boiling

Point

(oC)

NonflammabilityLow

GWP

Zero

ODPFEAs

6

Zero ODP, Low GWP, Nonflammable with Low Zero ODP, Low GWP, Nonflammable with Low λλ (3rd Gen. (3rd Gen. FEAsFEAs))


Low - Medium


Low - Medium







Medium




(mW/mK)

Boiling

Point

(oC)

NonflammabilityLow

GWP

Zero

ODPFEAs

7

Zero ODP, Low GWP & Nonflammable with Low Zero ODP, Low GWP & Nonflammable with Low λλ (3rd & 4th Gen. (3rd & 4th Gen. FEAsFEAs) )


Low - Medium


Low - Medium







Medium




(mW/mK)

Boiling

Point

(oC)

NonflammabilityLow

GWP

Zero

ODPFEAs

a: 4th generation low GWP FEAs

b: Indian Polyurethane Association, Alternative Blowing Agent Options for HCFC 141b, June 2010

8

FEAFEA--1100 1100 –– a Sustainable FEA with Desired Propertiesa Sustainable FEA with Desired Properties

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)

9

FEAFEA--1100 Vapor Pressure1100 Vapor Pressure

Vapor pressure is very close to HCFC-141b

Vapor Pressure

0

50

100

150

200

250

300

350

400

0 5 10 15 20 25 30 35 40 45 50 55

Temperature (oC)

Vap

or

pre

ssu

re (k

Pa)

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

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

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

Cyclopentane (b.p. = 49C)

Drum pressure rating

10

FEAFEA--1100 Vapor Thermal Conductivity1100 Vapor Thermal Conductivity

• Low vapor thermal conductivity (λ or K-factor) over broad temperature range

• Lowest thermal conductivity when temperature >60C

Vapor Thermal Conductivity vs Temperature

0.0050

0.0070

0.0090

0.0110

0.0130

0.0150

0.0170

0.0190

0.0210

0.0230

0.0250

0.0270

-50 -25 0 25 50 75 100 125 150

Temperature (oC)

Vap

or

ther

mal

co

nd

uct

ivit

y (W

/mK

)

FEA-1100

HFC-245fa

HCFC-141b

Cyclopentane

11

FEAFEA--1100 1100 vsvs HCFCHCFC--141b & 141b & HFCsHFCs [1][1]

Superior insulation performance compared to HCFC & 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 (kg/m3) 31.1 32.7 32.0 29.6

K-factor (W/mK) @ 23.9oC 0.0205 0.0214 0.0223 0.0222

Foam Initial Properties

12

FEA Level Adjustment for Optimal Performance FEA Level Adjustment for Optimal Performance [1][1]

* Pressure may exceed drum rating

• Drop-in to a HFC-245fa formulation with low FEA level (6 pbw HFC-245fa)

• Increase to high FEA levels typically used in HCFC-141b formulation

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

Reaction Profile

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

Foam density (kg/m3) 41.97 42.13 40.69 44.21

K-factor (W/mK) @ 23.9oC 0.0237 0.0231 0.0200 0.0188

Foam Initial properties

13

FEA Level & KFEA Level & K--factor factor [1][1]

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

• High level of FEA-1100 can be used for optimal performance without any

concern of high vapor pressure or flammability

K-factor Comparison (FEA-1100 vs HFC-245fa)

0.0180.0190.0200.0210.0220.0230.024

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

k-fa

cto

r(W

/mK

)

HFC-245fa FEA-1100

K-factor Comparison (FEA-1100 v s HFC-245fa)

0.018

0.019

0.020

0.021

0.022

0.023

0.024

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

k-fa

ctor

(W/m

K)

HFC-245fa FEA-1100

K -fa c to r C o m p a ris o n (F E A -1 1 0 0 v s H F C -2 4 5 fa )

0.018

0.019

0.020

0.021

0.022

0.023

0.024

L o w F EA le ve l H ig h F EA le ve l (b .p > 25C ) H F C -245fa vs F EA -1100

k-fa

cto

r (W

/mK

)

H F C -2 4 5 fa F E A-1 1 0 0

14

KK--factor After Aging factor After Aging [1][1]

Superior insulation performance maintains with aging

Aged K-factor for PIR Foam

0.018

0.019

0.020

0.022

0.023

0.024

0 30 60 90 120 150 180 210 240 270 300

days

K-f

acto

r (W

/mK

)

FEA-1100 HFC-245faPower (FEA-1100) Power (HFC-245fa)

15

FEAFEA--1100 vs Other Zero ODP FEAs 1100 vs Other Zero ODP FEAs [1][1]

FEA-1100 has the best insulation performance

FEAsK-factor

(W/mK) @ 23.9oC

Density

(Kg/m3)

FEA-1100 0.0199 34.1HFC-245fa 0.0208 34.8HFC-365mfc 0.0209 35.6Cyclopentane 0.0218 38.8Isopentane 0.0228 40.0Methyl formate 0.0236 35.2Methylal 0.0243 36.2

Ingredients pbw

TDA-based polyol 100

Surfactant 2.13

Catalysts 2.00

FEA or FEA-1100 mixture (moles) 0.18

Water (moles) 0.06

Isocyanate 132

Foam index 1.2

Foam K-factor Comparisons (Equi-molar FEA)

0.0190.0200.0210.0220.0230.0240.025

FEA-110

0

HFC-245fa

HFC-365m

fcCyc

lopen

tane

Isopen

tane

Methyl

form

ate

Methyla

l

K-f

acto

r(W

/mK

)

16

FEAFEA--1100 Impact on FEA Mixtures 1100 Impact on FEA Mixtures [1][1]

• Adding FEA-1100 to other zero ODP FEAs

• Same foam formulation & equi-molar FEAs without optimization

• FEA-1100 improves performance

FEAsK-factor

(W/mK) @ 23.9oCDensity (kg/m3)

Benefits

HFC-245fa 0.0208 34.8FEA-1100/HFC-245fa mixture 0.0204 38.4 Improved GWP, b.p & k-factor

HFC-365mfc 0.0209 35.6FEA-1100/HFC-365mfc mixture 0.0195 34.6 Improved GWP, k-factor & flammability

Cyclopentane 0.0218 38.8FEA-1100/cyclopentane mixture 0.0197 37.2 Improved k-factor & flammability

Isopentane 0.0228 40.0FEA-1100/isopentane mixture 0.0209 37.6 Improved k-factor & flammability

Methyl formate 0.0236 35.2FEA-1100/methyl formate mixture 0.0197 36.8 Improved k-factor & flammability

Methylal 0.0243 36.2FEA-1100/methylal mixture 0.0211 32.4 Improved k-factor & flammability

17

Effect of FEAEffect of FEA--1100 on K1100 on K--factor factor

FEA-1100 improves K-factor

Effect of FEA-1100 on Other FEAs

0.019

0.020

0.021

0.022

0.023

0.024

0.025

HFC-245fa & itsFEA-1100 mixture

HFC-365mfc & itsFEA-1100 mixture

Cyclopentane &its FEA-1100

mixture

Isopentane & itsFEA-1100 mixture

Methyl formate& its FEA-1100

mixture

Methylal & itsFEA-1100 mixture

K-f

acto

r (W

/mK

)

Other FEAs FEA-1100-other FEA mixtures

18

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

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

Days at 50oC in Oven

Cream time (seconds)

Tack free (seconds)

Ratio (Tack free /Cream time)

Foam density

(kg/m3)0 25 90 3.6 34.14 20 90 4.5 35.421 21 110 5.2 35.453 23 100 4.3 38.689 25 75 3.0 41.3122 27 120 4.4 41.6150 28 100 3.6 35.1187 28 100 3.6 31.1

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

19

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

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

Days at 50oC in Oven

Cream time (seconds)

Tack free (seconds)

Ratio (Tack free /Cream time)

Foam density

(kg/m3)0 25 90 3.6 39.9

15 30 110 3.7 38.947 20 130 6.5 37.283 25 135 5.4 41.3116 27 120 4.4 34.9144 30 100 3.3 38.4181 30 100 3.3 34.9

B-side ingredients pbw

Aromatic Polyester 100

Silicon Type Surfactant 6.2Potassium Catalyst 2.8

Amine-based Catalyst 0.7FEA-1100 39.7

Foam index 2.5

20

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)

PolyethersAmine 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

21

Material Compatibility Material Compatibility -- MetalMetal

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





FEA Solution Appearance

FEA Solution Analysis

Clear No f luoride detected **





** Detection limit = 0.5 ppm

22

Material Compatibility Material Compatibility -- Elastomers 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%

23

Material Compatibility Material Compatibility -- Plastics 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 f luoride) 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%

24

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

25

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

26

Summary Summary

• FEA-1100 – environmentally sustainable FEA with desired properties

� Zero ODP & low GWP

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

� Good chemical stability and material compatibility

� Superior insulation performance compared to commercially available

FEAs (HFCs, pentanes, methyl formate & methylal)

� Potential drop-in replacement with improved performance

• HFCs - good transitional FEAs

� Zero ODP

� Nonflammable

� Low thermal conductivity (K-factor orλ)

27

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.

REFERENCES

1. Loh, G., Creazzo J., Robin, M., “Development Program Update for a low GWP Foam Expansion Agent”,

Proceedings of Polyurethanes 2009 Technical Conference, Washington DC, USA

Documents

Development of FEA-1100 - Chemours · Foam Expansion Agent with Desired Properties March 9-11, 2011 ... 1st Gen 2nd Gen 3rd Gen 4th Gen. 3 ... Low FEA le ve l High FEA le ve l