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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))
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
5
Zero ODP & Nonflammable with Low Zero ODP & Nonflammable with Low λλ (3rd Gen. (3rd 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
6
Zero ODP, Low GWP, Nonflammable with Low Zero ODP, Low GWP, Nonflammable with Low λλ (3rd Gen. (3rd 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
7
Zero ODP, Low GWP & Nonflammable with Low Zero ODP, Low GWP & Nonflammable with Low λλ (3rd & 4th Gen. (3rd & 4th 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
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
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 f luoride detected **
Clear No f luoride detected **
Clear No f luoride detected **
Clear No f luoride detected **
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