DuPont™ FEA-1100: Zero ODP, Low GWP,
Non-Flammable Alternative for HCFC-141b
Helen Walter-Terrinoni
Nov 12, 2010
Desired 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
2
HCFC-141b Phase-out Options
HIGH ODP
CFC-11
LOW ODP
HCFC-141b
ZERO ODP
HFC-245fa
HFC-365mfc
Pentanes
Methyl Formate
Methylal
H2O(CO2)
Mixtures
3
Next Generation
Low GWP
Zero ODP
FEA-1100
Next Generation
Low GWP
HBA-2
AFA-L1
4
FEA-1100 – a Sustainable & Balanced Option
FEA-1100 (HFO-1336mzz)
 ODP = 0
 GWP 100 yr ITH = 9.4 (NOAA)
 ATM lifetime = 24 days (NOAA)
 Nonflammable (ASTM E 681 at 60oC & 100oC)
 b.p = 33 oC
CF3CH=CHCF3
 λ= 10.7 mW/mK @ 25 oC
 MW = 164
Challenges to Develop Low GWP FEAs
5
Reduce GWP while maintaining other desired properties
HIGH ODP
DEVELOPMENT PROGRESSION FOR FLUORINATED FOAMING AGENTS
Approximate
boiling point shown to the
right of each formula
CFC-12
CFC-11
= FLAMMABLE
CCl2F2 (-30°C) CCl3F (+24°C)
SOME ODP
HCFC-141b
CCl2F-CH3 (+32°C)
HCFC-142b
CClF2-CH3 (-10°C)
HCFC-22
HCFO-1233zd
CHClF2 (-41°C)
CF3CH=CHCl (+19°C)
HCFO-1233xf
CF3CCl=CH2 (+15°C)
HFC-365mfc
ZERO ODP
CF3-CH2-CF2-CH3 (+40°C)
HFO-1234ze
CF3CH=CHF (-19°C)
HFC-245fa
CF3-CH-CHF2 (+15°C)
HFO-1234yf
CF3CF=CH2 (-28°C)
HFC-134a
HFC-152a
CF3-CFH2 (-26°C)
CH3-CHF2 (-25°C)
HFO-1336mzz
CF3-CH=CH-CF3 (+33°C)
HIGH GWP
SOME GWP
LOW GWP
FEA-1100
6
Foam Expansion Agent Property Comparison
4-Carbon Series
3-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
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
Acceptable
Acceptable
Disqualified
for toxicity
Yes
Slight
No
Formula
Toxicity
Flammability
Acceptable
No
No
No
7
HCFC-141b Phase-out Option Comparisons
FEA-1100 – a zero ODP & low GWP FEA with desired properties
Lambda @ 25 oC Boiling Point
Flash Point( C)
(mW/mK)
(oC)
none
9.7
32
o
FEAs
ODP
GWP
HCFC-141b
0.11
725 a
HFC-245fa
0
1030 a
none
12.7
15
HFC-365mfc
Cyclopentane
CO2
Methylal
Methyl Formate
0
0
0
0
0
794 a
11 b
0
0
0
-24
-7
none
-19
-18
10.5
40
49
-139
42
32
HBA-2
Negligible b
<15 d
none
AFA-L1
Negligible b
<15 d
none
10b
15 - 30 d
0
9.4c
none
10.7
33
FEA-1100
a: IPCC/TEAP (2005)
b: UNDP, Phaseout Technologies for PU Foams, June 2010;
c: NOAA(2010)
d: Proceedings of Polyurethanes 2009 Technical Conference
b
13
16.3b
10.7b
15 - 32 d
Conversion Cost
NA
Med ium
(High vapor pressure)
High (Flammability)
High (Flammability)
Low
High (Flammability)
High (Flammability)
Low - Medium
(Potential high vapor
pressure)
Low - Medium
(Potential high vapor
pressure)
Low
Thermal Conductivity and Vapor Pressure Comparisons
8
•
Low vapor thermal
conductivity over broad
temperature range
•
Lowest thermal
conductivity when
temperature >150F
Vapor thermal conductivity
(Btu/hr-ft-F)
Vapor Thermal Conductivity vs Temperature
0.0160
0.0150
0.0140
0.0130
0.0120
0.0110
0.0100
0.0090
0.0080
0.0070
0.0060
0.0050
0.0040
0.0030
FEA-1100
HFC-245fa
HCFC-141b
Cyclopentane
-50
0
50
100
150
200
250
300
Temperature (oF)
Vapor Pressure
60
Vapor pressure (psia)
50
40
FEA-1100 (b.p. =33C)
HCFC-141b (b.p. = 32C)
30
HFC-245fa (b.p. = 15C)
Cyclopentane (b.p. = 49C)
Drum pressure rating
20
10
0
60
70
80
90
100
110
o
Temperature ( F)
120
130
Vapor pressure is very close to HCFC-141b
9
FEA-1100 vs Other Zero ODP FEAs
Ingredients
TDA-based polyol
Surfactant
FEAs
FEA-1100
HFC-245fa
HFC-365mfc
Cyclopentane
Isopentane
Methyl formate
Methylal
yl
al
M
et
h
M
et
h
yl
f
or
m
at
e
en
ta
ne
Is
op
yc
lo
p
C
H
FC
-3
65
m
fc
-2
45
fa
FC
H
FE
A
en
ta
ne
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
-1
10
0
R-value @ 75F
PUR Foam R-value Com parisons
(Equi-m olar FEA)
R-value
Density
(ft2.h.oF/Btu.in) @ 75oF (pcf)
7.2
2.1
6.9
2.2
6.9
2.2
6.6
2.4
6.3
2.5
6.1
2.2
5.9
2.3
Catalysts
FEAs (moles)
Water (moles)
Isocyanate
Foam index
pbw
100
2.13
2.00
0.18
0.06
132
1.2
FEA-1100 has the best
insulation performance
FEA-1100 Impact on FEA Mixtures
10
R-value
Effect of FEA-1100 on Other FEAs
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
HFC-245fa & its HFC-365m fc & Cyclopentane
FEA-1100
its FEA-1100 & its FEA-1100
m ixture
m ixture
m ixture
Other FEAs
Isopentane &
its FEA-1100
m ixture
Methyl
form ate & its
FEA-1100
m ixture
FEA-1100-other FEA mixtures
R-value
(ft2.h.oF/Btu.in) @ 75oF
Density
(pcf)
HFC-245fa
FEA-1100/HFC-245fa mixture
6.9
7.1
2.2
2.4
Improved GWP, b.p & R-value
HFC-365mfc
FEA-1100/HFC-365mfc mixture
6.9
7.4
2.2
2.2
Improved GWP, R-value & flammability
Cyclopentane
FEA-1100/cyclopentane mixture
6.6
7.3
2.4
2.3
Improved R-value & flammability
Isopentane
FEA-1100/isopentane mixture
6.3
6.9
2.5
2.4
Improved R-value & flammability
Methyl formate
FEA-1100/methyl formate mixture
6.1
7.3
2.2
2.3
Improved R-value & flammability
Methylal
FEA-1100/methylal mixture
5.9
6.8
2.3
2.0
Improved R-value & flammability
FEAs
Methylal & its
FEA-1100
m ixture
Benefits
•
Adding FEA-1100 to other
zero ODP FEAs
•
Same foam formulation &
equi-molar FEAs
•
FEA-1100 improves Rvalue
11
FEA-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 Foam s
(FEA-1100 vs 50/50 cyclopentane/isopentane)
7.6
7.4
R-value
7.2
7.0
6.8
6.6
6.4
6.2
0
20
40
60
80
100
Days
120
140
160
180
200
12
FEA-1100 vs HCFC-141b & HFCs
Superior insulation performance compared to HCFC-141b & HFCs
Ingredients (pbw)
Sucrose- based polyol
Surfactant
Catalysts
water (moles)
FEA (moles)
Isocyanate
Foam Index
Cream time(s)
Rise time(s)
Tack free time(s)
Foam density(pcf)
FEA-1100 HCFC-141b HFC-245fa HFC-365mfc
100
100
2.00
2.00
4.00
4.00
0.08
0.08
0.20
0.20
121
121
1.1
1.1
Reaction Profile
7
6
120
120
140
150
Foam Initial Properties
1.9
2.0
R-value (ft2.h.oF/Btu.in) @ 75oF
7.0
6.7
100
2.00
4.00
0.08
0.20
121
1.1
100
2.00
4.00
0.08
0.20
121
1.1
6
120
140
7
130
140
2.0
1.9
6.5
6.5
FEA Level & R-value (FEA-1100 vs HFC-245fa)
R-value Comparison (FEA-1100 vs HFC-245fa)
R-value
* High level of HFC-245fa may cause pressure exceed drum
pressure rating
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
Low FEA level
High FEA level (b.p >25C)
HFC-245fa vs FEA-1100
•
High level of FEA-1100 can
be used without vapor
pressure or flammability
limitation
•
High level of FEA-1100 can
potentially improve
insulation performance
HFC-245fa FEA-1100
Ingredients (pbw)
Mannich polyol
Polyester polyol
Surfactant
Flame retardant and additives
Catalysts
FEA (moles)
Water (moles)
Isocyanate
Foam index
Cream time(s)
Rise time(s)
Tack free time(s)
Sample density (pcf)
R-value (ft2.h.oF/Btu.in) @ 75oF
HFC-245fa
(low FEA level)
FEA-1100
(low FEA level)
50
50
50
50
0.25
0.25
24.50
24.50
1.22
1.22
0.045
0.045
0.169
0.169
138
138
1.1
1.1
Reaction Profile
8
8
70
67
70
70
Foam Initial properties
2.6
2.6
6.1
6.2
HFC-245fa
(high FEA level)*
FEA-1100
(high FEA level)
50
50
0.25
24.50
1.22
0.179
0.035
97
1.1
50
50
0.25
24.50
1.22
0.179
0.035
97
1.1
7
85
90
7
71
85
2.5
7.2
2.8
7.7
13
14
Chemical Stability – Polyether at 50 oC for 6 months
FEA-1100 is stable in a generic polyether formulation after 6 months storage at 50 oC
B-side ingredients
Polyether (TDA)
Silicon Type Surfactant
Amine-based Catalyst
Co-catalyst
Water
FEA-1100
Foam index
pbw
100
2.0
3.0
1.0
1.0
29.4
1.2
Days at 50oC in
Oven
Cream time
(seconds)
Tack free
(seconds)
Ratio
(Tack free /Cream time)
Foam density
(pcf)
0
4
21
53
89
122
150
187
25
20
21
23
25
27
28
28
90
90
110
100
75
120
100
100
3.6
4.5
5.2
4.3
3.0
4.4
3.6
3.6
2.1
2.2
2.2
2.4
2.6
2.6
2.2
1.9
15
Chemical Stability – Polyester at 50 oC for 6 months
FEA-1100 is stable in a generic polyester formulation after 6 months storage at 50 oC
B-side ingredients
Aromatic Polyester
Silicon Type Surfactant
Potassium Catalyst
Amine-based Catalyst
FEA-1100
Foam index
Days at 50oC in
Oven
0
15
47
83
116
144
181
Cream time
(seconds)
25
30
20
25
27
30
30
Tack free
(seconds)
90
110
130
135
120
100
100
pbw
100
6.2
2.8
0.7
39.7
2.5
Ratio
(Tack free /Cream time)
3.6
3.7
6.5
5.4
4.4
3.3
3.3
Foam density
(pcf)
2.5
2.4
2.3
2.6
2.2
2.4
2.2
16
Polyol Solubility
FEA-1100 is soluble in commonly used polyols
Polyol Type
Polyethers
Amine
Sucrose/amine
Sucrose/glycol
Sucrose/glycerine
Sorbitol
Mannich-base
Polyesters
OH#
(mg KOH/g)
Weight% in Polyols
for Single Phase
Mixture (21oC)
Weight% in Polyols
for Single Phase
Mixture (50oC)
391-800
400-499
440
280-520
490
300-390
240-307
5-50+
50+
50+
50+
50+
5-50+
5-30
40-50+
50+
50+
50+
50+
29-50+
23-35
17
Material Compatibility - Metal
FEA-1100 is compatible with commonly used metals
Changes after 2 weeks at 100oC (212oF) in FEA-1100
Metal Coupons
Metal Coupon
Weight
Metal Coupon
Appearance
FEA Solution
FEA Solution Analysis
Appearance
Stainless Steel
No weight change
No sign of corrosion
Clear
No fluoride detected **
Carbon Steel
No weight change
No sign of corrosion
Clear
No fluoride detected **
Copper
No weight change
No sign of corrosion
Clear
No fluoride detected **
Brass
No weight change
No sign of corrosion
Clear
No fluoride detected **
Aluminum
No weight change
No sign of corrosion
Clear
No fluoride detected **
** Detection limit = 0.5 ppm
18
Material Compatibility - Elastomers
FEA-1100 is compatible with commonly used elastomers
Changes after 2 weeks at room temperature in FEA-1100
Symbol
NR
CR
NBR
CSM
FFKM
T
IIR
EPDM
Material
Natural Rubber
Polychloroprene
Acrylonitrile Butadiene
Chlorosulfonated Polyethylene
Fluoroelastomer
Polysulfide
Isobutylene Isoprene
Hydrocarbon (Ethylene-Propylene
Terpolymer)
Brand
% Weight % Volume
Change
Change
% Hardness
Change
Natural Rubber
Neoprene® W
BUNA N
Hypalon 40®
Kalrez®
THIOKOL FA ®
Butyl Rubber
4.4%
0.8%
15.3%
0.2%
7.9%
0.3%
0.3%
1.9%
0.1%
2.6%
0.8%
-3.4%
6.7%
13.1%
0.0%
0.0%
-13.6%
-1.3%
-2.9%
-6.1%
-13.3%
Nordel®
1.4%
5.5%
-7.1%
19
Material Compatibility - Plastics
FEA-1100 is compatible with commonly used plastics
Changes after 2 weeks at room temperature in FEA-1100
Symbol
ABS
HIPS
PET
PS
PVC
CPVC
PTFE
ETFE
POM
PC
PEEK
LCP
PEI
PVDF
PP
HDPE
Material
Acrylonitrile-butadiene-styrene
High Impact Polystyrene
Poly(ethylene terephthalate)
Polystyrene
Polyvinyl Choloride
Chlorinated Polyvinyl Choloride
Fluorocabon(PTFE)
Fluorocabon(ETFE)
Ionomer
Acetal
Polycarbonate
Polyetheretherketone
Polyarylate
Polyester
Nylon 6/6
Polyetherimide
Polyaryl sulfone
Poly(vinylidene fluoride)
Polypropylene
LCP
High Density Polyethylene
Phenolic
Brand
Cycolac®EX58
Rynite®
Styron®
Bakelite®
Teflon ®
Tefzel®
Surlyn®
Delrin®
Tuffak®
Victrex®
Arylon®
Xydar ®
Zytel® 101
Ultem®
Radel®
Kynar®
Tenite®
Zenite
Alathon ®
Duzez®
% Weight % Volume
Change
Change
-0.1%
0.3%
0.0%
-0.4%
0.0%
0.0%
1.1%
0.7%
0.3%
0.1%
0.0%
0.0%
0.2%
0.0%
0.4%
-0.1%
-0.2%
0.1%
0.3%
-0.1%
0.0%
0.0%
-0.6%
-0.4%
0.7%
0.9%
0.0%
-0.3%
0.3%
0.0%
0.0%
-1.2%
-0.6%
0.2%
-0.2%
-0.4%
-0.5%
0.0%
0.3%
-0.3%
-0.5%
-0.9%
0.3%
-0.1%
% Hardness
Change
0.0%
-2.9%
-1.2%
0.0%
0.0%
0.0%
-17.2%
12.9%
1.9%
-1.3%
0.0%
0.0%
-4.4%
-1.5%
3.1%
0.0%
0.0%
0.0%
0.0%
0.0%
3.3%
1.2%
20
Toxicity Assessment
FEA-1100: Favorable Results
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
90 Day/ developmental:
Favorable repeated inhalation profile
consistent with 28-day test result
21
DuPont Low GWP FEA (Blowing Agent) Program
2009
2010-2011
2012-2013
2014-2015
Customer
Validation
Intermediate
Scale
Commercial
Sales
ODP, GWP,
Flammability,
Toxicity..
SNAP, PMN,
REACH & additional
tests as needed
Launch
FEA-1100
Supply
FEA-1100
Desired FEA
Properties
Insulation
performance,
Stability,
Solubility…
Support customer
testing &
optimization
Support customer
conversion
Support customer
conversion
Manufacturability
Bench scale
production and
optimization
Small lot production
Intermediate scale
commercial plant
Full scale
commercial plant
Screening
Candidate
s
Candidate
Evaluation
Safety &
Environmental
Properties
Full Scale
Commercial
Sales
22
FEA-1100 Summary
•
Zero ODP & low GWP
•
Non-flammable FEA with boiling point close to HCFC-141b
•
Superior insulation performance compared to HCFC-141b, HFCs (245fa &
365mfc) & pentanes (cyclopentane & Isopentane) [1]
•
Good material compatibility and polyol solubility [1]
•
Good chemical and thermal stability [2]
•
Heat of evaporation close to HCFC-141b, HFC- 245fa & cyclopentane [2]
•
Potential drop-in replacement with improved performance
[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)
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.
24