EPA-600/Ft-9 5-158
October 1995
IDENTIFICATION OF CFC AND HCFC SUBSTITUTES FOR
BLOWING POLYURETHANE FOAM INSULATION PRODUCTS
By:
Philip H. Howard
Jay L. Tunkel
Syracuse Research Corporation
Environmental Science Center
Merrill Lane
Syracuse, New York, 13210-4080
Sujit Baneijee
BRI
P.O. Box 7834
Atlanta, Georgia 30357
EPA Cooperative Agreement CR 821920-01-0
EPA Project Officer:
Robert V. Hendriks
Air Pollution Prevention and Control Division
Research Triangle Park, North Carolina 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, D.C. 20460
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before compli ||{ |||| || f|||| )| ||j| || |||
1, REPORT NO, 2,
EPA-600/R-95-158
3 in mi ii inn ii mi ii in
I PB96-113667 /
4. TITLE AND SUBTITLE
Identification of CFC and HCFC Substitutes for Blowing
Polyurethane Foam Insulation Products
S. REPORT DATE
October 1995
6. PERFORMING ORGANIZATION CODE
7, AUTHOfUSl
P. H, Howard and J. L, Tunkel (Syracuse), and
S. Banerjee (BRI)
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Syracuse Research Corporation, Merrill Lane, Syra-
cuse, NY 13210
BRI, P.O. Box 7834, Atlanta, GA 30357
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CR 821920-01-0
(Syracuse Rsrch Corp.)
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 9/93-11/94
14. SPONSORING AGENCY CODE
EPA/600/13
18. supplementary NOTES ^ppcD project officer is Robert V. Hendriks, Mail Drop 62B,
919/541-3928.
is. abstract rep0rj; gives results of a cooperative effort to identify ehlorofluorocar-
bon (CFC) and hydrochlorofluorocarbon (HCFC) substitutes for blowing polyurethane
foam insulation products. The substantial ongoing effort is identifying third-genera-
tion blowing agents for polyurethane foams to replace currently used stratospheric
ozone depleting ones. More than 100 chemicals have been identified and ranked as
polyurethane foam blowing agent candidates. The systematic investigation involved
the analysis of vapor thermal conductivity predictive models and utilizing this method-
ology to identify and screen potential new foam blowing agents. Collection of physical/
chemical properties of the new candidates enabled an overall evaluation. Based on the
vapor thermal conductivity, boiling point, and other important properties, the chemi-
cal compounds were ranked to identify the most promising new blowing agent candida-
tes. To efficiently evaluate new foam blowing agents, the compounds were placed and
evaluated in 14 groups based on chemical structure. Compounds ranked high in this
exercise included cyclopentane and cyclopentene, simple olefins consisting of hydro-
carbons with four to six carbons and at least one double bond, cyclobutane analogs,
and fluorinated propanes and butanes. Several novel chemical groups, such as fluoro-
iodoalkanes and silicon compounds, were also considered and ranked.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COsati Field/Group
Pollution Cyclopentane
Halohydrocarbons Cyclopentene
Polyurethane Resins
Blowing Agents
Thermal Conductivity
Boiling Points
Pollution Prevention
Stationary Sources
13 B
07C
111, 11J
L1G
20M
37 D
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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FOREWORD
The U. S. Environmental Protection Agency is charged by Congress with pro-
tecting the Nation's land, air, and water resources. Under a mandate of national
environmental laws, the Agency strives to formulate and implement actions lead-
ing to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental pro-
blems today and building a science knowledge base necessary to manage our eco-
logical resources wisely, understand how pollutants affect our health, and pre-
vent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for
investigation of technological and management approaches for reducing risks
from threats to human health and the environment. The focus of the Laboratory's
research program is on methods for the prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites and groundwater; and prevention and
control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental
technologies; develop scientific and engineering information needed by EPA to
support regulatory and policy decisions; and provide technical support and infor-
mation transfer to ensure effective implementation of environmental regulations
and strategies.
This publication has been produced as part of the Laboratory's strategic long-
term research plan. It is published and made available by EPA's Office of Re-
search and Development to assist the user community and to link researchers
with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
EPA REVIEW NOTICE
This report has been peer and administratively reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED.
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
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Abstract
Substantial effort is ongoing to identify and evaluate third-generation blowing agents for
polyurethane foams to replace currently used stratospheric ozone depleting ones. A cooperative
agreement between the Environmental Protection Agency and Syracuse Research Corporation
has identified and ranked over 100 chemicals as polyurethane foam blowing agent candidates.
The systematic investigation involved the analysis of vapor thermal conductivity predictive
models and utilizing this methodology to identify and screen potential new foam blowing agents.
Collection of physical/chemical properties of the new candidates enabled an overall evaluation.
Based on the vapor thermal conductivity, boiling point, and other important properties, the
chemical compounds were ranked in order to identify the most promising new.blowing agent
candidates. In order to efficiently evaluate new foam blowing agents, the compounds were
placed and evaluated in a series of fourteen groups based on chemical structure. Compounds
ranked high in this exercise included cyclopentane and cyclopentene, simple olefins consisting of
hydrocarbons with 4 to 6 carbons and at least one double bond, cyclobutane analogs, and
fluorinated propanes and butanes. Several novel chemical groups, such as fluoroiodoalkanes and
silicon compounds, were also considered and ranked in the exercise.
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Table of Contents
Abstract ,, Iff
List of Tables . v
of Figures v
Introduction 1
Task 1: Analysis of Vapor Thermal Conductivity Predictive Models 3
Thermal Conductivity 4
Critical Temperature and Pressure 45
Developing Estimation Methods for Silicon-Containing Compounds 47
Roy-Thodos Constant 47
Boiling Point 48
Critical Temperature 49
Critical Pressure 50
Overall Comparison 51
Task 2: Identification of Potential New Foam Blowing Agents. 51
Ranking the List 54
Task 3. Evaluation of Potential New Foam Blowing Agents 69
Group A - Cyclopentane and Cyclopentene 77
Group B - Simple Olefins 79
Group C - Cyclobutane Analogs 81
Group D - Fluorinated Propanes and Butanes 83
Group E - Pentanes and Hexanes 86
Group F - HFEs 88
Group G - Ethers 90
Group H - Carbonyl Compounds 92
Group I - Fluorinated Olefins 94
Group J - Cyclopropanes '. 96
Group K - Fluorinated Cyclopentanes 97
Group L - Fluoroiodoalkanes 98
Group M - Fluorinated Methane and Ethanes 101
Group N - Silicon Containing Compounds 103
Information Gaps 104
Appendix A. Commercial Availability of Blowing Agent Candidates 108
Appendix B. Boiling Points of Blowing Agent Candidates at 760 mm Hg 112
Appendix C. Physical Properties of Blowing Agent Candidates I - Environmental Fate 115
Appendix D. Physical Properties of Blowing Agent Candidates II - Environmental Fate .... 118
Appendix E. References for Experimental Physical Properties from Appendices C and D ... 121
References 124
iv
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List of Tables
1, Experimental and Estimated Vapor Thermal Conductivities 8
2, Properties of Silicon Compounds 48
3. Comparison of Estimated and Experimental Properties for Silicon Compounds 49
4, Final Ranking of Blowing Agent Candidates 57
5. Compounds with Artificial CAS Registry Numbers 69
6. Group Ranking of Blowing Agent Candidates 70
List of Figures
1. Estimated vs. Experimental Vapor Thermal Conductivity .... 6
2, Estimated vs. Experimental Vapor Thermal Conductivities in mW/(m K) 44
v
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Introduction
Chlorofluorocarbons (CFCs) are recognized as a major contributor to the depletion of
stratospheric ozone in the Earth's atmosphere. Stratospheric ozone helps to filter harmful
ultraviolet (UV) radiation and decreases the amount that reaches the Earth's surface. Because of
the potential for harm to health or the environment as a result of the increased incidence of UV
radiation, the phaseout of production of this class of chemicals was called for as of January 1,
1996, under the auspices of the Montreal Protocol and current U.S. law. CFCs were widely used
as blowing agents for rigid polyurethane foams for insulation products due to their unique
combination of desirable physical/chemical properties and safety in use.
Worldwide efforts to replace CFC blowing agents led to the development of the so-called
second-generation blowing agents, the hydrochlorofluorocarbons, HCFCs (Rnopeck, GM. et al.,
1993; Decaire, BR. et al., 1992). HCFCs have significantly lower ozone depletion potentials
compared to CFCs and many of these second-generation blowing agents could be used directly as
drop-in replacements for CFCs. HCFCs, however, also face phase-out under the Montreal
protocols and subsequent agreements due to their contribution to stratospheric ozone depletion
and thus, they represent only an interim replacement for CFCs.
There is a need to identify chemical compounds that are not stratospheric ozone depleters
that can be used as substitutes for CFC and HCFC blowing agents in rigid polyurethane foam
insulating materials. The search for these compounds is complicated by the physical/chemical
properties they must possess as well as their overall compatibility with foam feedstocks and
production methods. Subtle differences between the third-generation blowing agents and CFCs
or HCFCs may result in modification in production methods as well as differences in use and
utility of the foam product.
1
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Substantial effort has been expended by governmental, industrial, and private laboratories
to test and evaluate a small number of third-generation blowing agents. This project was
designed to identify additional polyurethane foam blowing agent candidates in order to improve
the chances of finding successful ones by conducting a systematic search to identify new
compounds that could replace the CFCs and HCFCs currently in use.
This final report represents the findings under Tasks 1, 2, and 3 of the project entitled
Identification of CFC and HCFC Substitutes for Blowing Polyurethane Foam Insulation
Products. Task 1 involved the analysis of vapor thermal conductivity predictive models. The
vapor thermal conductivity of the blowing agent is an important physical property for insulating
materials because the blowing agent becomes incorporated into the foam and, therefore, is
partially responsibility for hindering the movement of heat through the foam. Given that
experimental vapor thermal conductivity values are essentially limited to currently available
blowing agents and refrigerants (which are mostly CFCs and HCFCs) and that experimental
measurements on a large number of compounds would be economically prohibitive, a model to
rapidly screen a large number of compounds would be advantageous in identifying new blowing
agents. This task involved the evaluation of current models for estimating vapor thermal
conductivity, fine tuning the models to reflect the current body of knowledge in this area, and
utilizing this methodology to identify and screen potential new foam blowing agents.
Task 2 involved the identification of potential new foam blowing chemicals and their
properties and the collection of physical/chemical properties and other data on the new
candidates. Based on the vapor thermal conductivity, boiling point, and other important
properties of each candidate, the chemical compounds identified in this task were ranked in order
to identify the most promising new blowing agent candidates. Task 3 involved the evaluation of
2
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potential new foam blowing agents as groups of related candidates. By placing candidates in
chemical groups, similarities could be discussed collectively and trends that represent differences
could be identified.
Task 1: Analysis of Vapor Thermal Conductivity Predictive Models
The vapor thermal conductivity of a blowing agent for an insulating foam is an important
factor in its overall insulating ability. Because of this, the vapor thermal conductivity is an
important chemical property to consider when looking at potential blowing agent substitutes.
Experimental data on vapor thermal conductivities are lacking in the open literature, except for
established blowing agents and refrigerants. Therefore, a significant portion of this project was
to establish the reliability of vapor thermal conductivity predictive models.
Two attributes of a gas enter into its thermal conductivity; how much heat the gas can
absorb, and how fast the gas can transport the heat from one surface to another (its diffusivity).
Absorption is dependent upon the heat capacity of the gas. Since heat is stored in bond
vibrations, the greater the number of bonds, the greater the heat capacity, all else being equal.
Thermal conductivity decreases with increasing critical temperature, which is the highest
temperature at which the gas can exist as a liquid. This dependence is complex since critical
temperature is related to both the absorption of heat by the gas and its translational motion. In
contrast, thermal conductivity increases with increasing critical pressure, which is directly related
to diffusivity.
The best potential blowing agent, in terms of low thermal conductivity, is one which
provides the best compromise between high critical temperature and low critical pressure, and is
3
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relatively bulky, yet has a low enough boiling point. Heat capacity is most favorable for
halogens, carbonyls, and ethers, and not for saturated hydrocarbons, alcohols, or amines.
The calculation of thermal conductivity, X, requires a knowledge of the Roy Thodos
constant C, which is estimated from group contribution values. Unfortunately, rules for
calculating these contributions are not well developed as shown from the following examples.
Thermal Conductivity
Thermal conductivity was estimated by the Roy-Thodos method (Roy, D. and Thodos, G.,
1968; Roy, D. and Thodos, G., 1970). Four input parameters are required:
Te - the critical temperature, in K;
Pc- the critical pressure, in bars;
C - a compound-specific constant estimated by a group contribution scheme; and
M - the molecular weight in g/mol.
Tr is the reduced temperature, i.e., T/Tc, both in K.
The thermal conductivity (A) is expressed as
X = XJT
where Xr is the reduced thermal conductivity, and f represents the reduced inverse thermal
conductivity in units of [mW/'fm K)]'!. T is calculated from
r=210 (tcm3/pc4)"®
The reduced thermal conductivity, Xt, has a translational and an internal component, i.e.,
Xr = (Xr)tr + (AT)int
The translational component is computed according to
(Xr)tr = 8.757[exp(0.0464Tr) - exp(-Q.2412Tr)]
The internal part of the reduced thermal conductivity is calculated through
ar)int = cf(Tr)
4
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where f(T.) is chemical class specific, and is given by various equations containing terms in Tr.
For example, for halides, the following equation applies
f(Tr) = - 0.107 Tr +1,330 Tr2 - 0,223 Tr3
Other equations are available for saturated hydrocarbons; olefins; acetylenes; naphthalenes and
aromatics; alcohols, aldehydes, ethers, and esters; amines and nitrites; and cyclic compounds.
The term "C " is a group contribution parameter that is obtained from the nature and number of
functional groups and their regiochemistry.
There are two difficulties with the technique. One is that since f(Tr) is chemical class
specific, there is no obvious solution if the structure falls into more than one chemical class. For
example, several of the structures considered were haloethers, and technically, either t he equation
for halides or ethers could be used. We used the equation for halides, since the structures usually
contained several halo groups but usually only a single ether linkage. In a few cases, calculations
were made with both equations and the results were similar.
The other difficulty lies with the estimation of C. For example, one equation governs
cyclic compounds, whereas another deals with halides, but there is no explicit equation for cyclic
halogenated compounds. Also, an equation exists for bromine substitution on methane, but not
for bromine substitution on anything else. In these cases, a near-neighbor approach was used if
the missing fragment was closely related to a listed species; otherwise, the structure could not be
considered further as a potential blowing agent substitute for this project.
In order to evaluate the reliability of the Roy-Thodos method for estimating thermal
conductivity, estimated values were directly compared to available experimental values. Figure 1
provides a comparison between experimental vapor thermal conductivity values obtained from
Daubert and Banner's compilation (Daubert, TE., and Danner, RP., 1989) to our estimated
5
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o
o
t—H
x
U
H
*->
p)
C/2
W
I
U
H
-i—>
c
(D
a
• fH
!-h
-<
CI
'1 CI el I
) f F F~) (
cl
-F
Cl
F")—(
H
H
Cl
5.8 7.4 8.5 9.1 9.6 10 10.3 10.5 10.8 10.9 11.4 11.5 11.6 11.7 12.4 12.6 13.1 13.5 13.6 14.1 14.4 14.8 14.9
6.9 7.7 8.8 9.4 9.8 10.2 10.5 10.7 10.8 11 11.5 11.5 11.7 12.1 12.4 12.9 13.2 13.6 13.8 14.2 14.8 14.8
Experimental Thermal Conductivity in mW/(m K)
Figure 1. Estimated vs. Experimental Vapor Thermal Conductivity
-------
values. As can be seen in Figure 1, the estimated vapor thermal conductivities were generally
within 10% of the experimental values for the chemicals listed in Daubert and Danner that had
experimental values. In addition, the estimated values were typically lower than the
experimental ones (bars above the line in Figure 1). Figure 1 also demonstrates that no
generalization can be developed regarding the potential magnitude and direction for the
differences between experimental and estimated values based on structure, functionality, or
substitution patterns. From these results, the overall accuracy of the Roy-Thodos model for
predicting vapor thermal conductivity was good enough to use these estimated values where used
directly in the second phase of this project.
Table 1 contains a complete list of experimental and estimated vapor thermal
conductivity values in mW/(m K) collected during this phase of the project and are sorted by
CAS Registry numbers . There are 51 experimental vapor thermal conductivity values at or near
room temperature (25 °C) in Table 1 that were collected from the open literature during this
phase of the task, A statistical analysis of the experimental and estimated vapor thermal
conductivities for these 51 compounds reveals a correlation coefficient (r2) of 0.82, a standard
deviation of .00952x10 ' mW/(m K), and an absolute mean error of .00691x101 mW/(m K).
Figure 2 provides a graphical representation of these results. In Figure 2, there are clearly two
outliers in this data set corresponding to 1,1,1 -trichIoro-2,2,2-trifluoroethane and 1-chloro-
1,1,2,2,2-pentafluoroethane. When these outliers are removed from the statistical analysis, a
correlation coefficient of 0.89, a standard deviation of .00719x10 ' mW/(m K), and an absolute
mean error of .00588x10"' mW/(m K) is obtained. Further analysis of Figure 2 shows that the
estimated results for compounds with thermal conductivities ranging from 8 to 13
7
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K)
Name
CAS Registry
Number
000067641 Acetone
Estimated Daubertand Literature Temp
Danner (1989)
12.00 0.00 0.00
Reference
Structure
U
A
000074873 Methane, chloro-
11.30 10.70 10.50 20 Suh, KW. (1994)
H3C —CI
000075003 Ethane, chloro-
11.90 11.40 8.87 0 Missenard, FA. (1966) H3C. .Cl
oo
000075092 Methane, dichloro-
000075105 Methane, difluoro-
000075296 Propane, 2-chloro-
000075343 Ethane, 1,1-dichloro-
8.01 7.41 6.30 20 Suh, KW. (1994)
11.10 11.00 12.80 25 Suehla, RA. (1962)
11.70 11.50 0.00
9.68 9.40 0.00
CI
H^Cl
H
F
H
H
CI
A
h3c ch3
CI
X,
H,C CI
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp Reference
CAS Registry
Number
000075376 Ethane, 1,1-difluoro-
Estimated Daubertand Literature Temp
Danner (1989)
11.40 11.50 14.70 25 Creazzo, JA et al.,
(1993)
Structure
F
H,C'X^F
000075434 Methane, dichlorofluoro-
000075456 Methane, chlorodifluoro-
^ 000075616 Methane, dibromodifluoro-
9.43 8.50 11.20 20 Suh, KW. (1994)
F
I^C1
CI
10.70 10.50 10.90 23
7.07 6.90 0.00
Cecchini, C. et al. (1991) F
H^I^F
CI
F
Br I ^F
r
Br
000075638 Methane, bromotrifluoro-
9.59 9.80 10.20 27 Suehla, RA. (1962)
F
Br I^F
r
000075683 Ethane, 1-chloro-1,1-difluoro-
11.20 11.70 9.40 25
Wiederman, RE. etal. CI H
(1991)
-H
H
000075694 Methane, trichlorofluoro-
8.01 7.70 7.80 23 Cecchini, C. et al. (1991) Cl
CI ^.F
r
Cl
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference Structure
Number Danner(1989)
000075718 Methane, dichlorodifluoro- 9.88 9.60 9.90 30 Wiederman, RE. et al. CI
(1991)
000075763 Tetramethyl silane
000075832 Butane, 2,2-dimethyl-
000075887 Ethane, 2-chloro-1,1,1 -trifluoro-
15.50 0.00
14.00 13.20
9.00 0.00
0.00
0.00
0.00
CH,
CH3-Si-CH3
CH
3
CH„
h3c-
¦\
CH3 CH3
CI E
H
000076131 Ethane, 1,1,2-trichloro-1,2,2-trifluoro- 8.48 8.80 7.31 27 Krauss, R. and Stephan, CI Cl
K. (1969) cl^ ^_F
000076142 Ethane,
1,2-dichloro-1,1,2,2-tetrafIuoro-
9.93 10.20 10.25 27 Krauss, R. and Stephan,
K. (1969)
Cl Cl
•-) f F
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
CAS Registry
Number
000076153 Ethane, chloropentafluoro-
Reference
Danner (1989)
11.70 14.90 0.00
Structure
CI F
fA (r~ F
000076197 Propane, octafluoro-
000078784 Butane, 2-methyl-
11.70 11.60 0.00
15.00 14.80 13.00 20 Missenard, FA. (1966)
F I F
F F
CH,
H3C—' \
CH,
000078795 1,3-Butadiene, 2-methyl-
13.50 14.40 0.00
CH,
—L
H2C==-^
CH„
000079298 Butane, 2,3-dimethyl-
13.70 12.40 0.00
9h3 ch,
h3c-
<
CH,
000107017 2-Butene
14.50 13.50 0.00
,CH,
H3C
000107302 Methane, chloromethoxy-
8.84 0.00 0.00
O. ^C1
H»c' Yh
H
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
14.20 14.80 0.00
CAS Registry
Number
000109660 Pentane
Reference
h3c
Structure
CH,
000109671 1-Pentene
13.20 13.60 0.00
h2c
CH,
000109682 2-Pentene
12.70 0.00 0.00
h3c
CH,
000109875 Dimethoxymethane
K>
14.90 0.00 0.00
.0. .0,
CH,
CH,
000115253 Cyclobutane, octafluoro-
11.60 10.00 12.48 27
000124732 Ethane,
1,2-dibromo-1,1,2,2-tetrafluoro-
Krauss, R. and Stephan,
K. (1969)
F
F
000116154 1-Propene, 1,1,2,3,3,3-hexafluoro- 10.90 10.47 0.00
F
F
6.63 5.80 0.00
F
Br
Br
F
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
000142290 Cyclopentene
Estimated Daubertand Literature Temp
Danner (1989)
12.10 10.80 0.00
Reference
Structure
o
000287230 Cyclobutane
15.90 14.80 12.40 0 Missenard, FA. (1966)
~
000287923 Cyclopentane
14.00 12.10 11.00 20 Missenard, FA. (1966)
o
000306832 Ethane, 2,2-dichloro-1,1I1-trifluoro^ 8.74 0.00 9.30 23 Cecchini, C. et al. (1991) F
LO
>—<
ci
ci
H
000329293
11.90 0.00
0.00
.CHF,
000333368 Bis-2,2,2-trifluoroethyl ether
000335273 Cyclohexane,
1,1 ^^.S.S^.S.S.e-decafluoro^.e-bis
(trifluoromethyl)-
9.93 0.00
9.42 0.00
0.00
0.00
o
F F
K F _
CF
\^CF3
A value of 0.00 indicates that no data are available
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Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
000335364 Furan, 8.45 0.00 0.00
2,2,3,3,4,4,5-heptafluorotetrahydro-5-
(nonafluorobutyl)-
CAS Registry
Number
Reference
C4F9
Structure
F F
000353366 Ethane, fluoro-
13.90 13.80
0.00
H H
H H
000353617 Propane, 2-fluoro-2-methyl-
13.80 0.00
0.00
CH,
h3c-
CH,
000354336 Ethane, pentafluoro-
11.00 10.90
14.30 23 Cecchini, C. etal. (1991) F E
000354585 Ethane, 1,1,1-trichloro-2,2,2-trifluoro- 10.40 0.00 7.20 20 Suh, KW. (1994)
CI F
cl) fF
CI F
000354643 Ethane, pentafluoroiodo-
8.30 0.00
0.00
F F
i4
000354698 Propane,
1,1,1,2,2-pentafluoro-3-iodo-
5.80 0.00
0.00
F i I
F H
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference
Number Danner(1989)
000355022 Cyclohexane, 9.89 0.00 0.00
undecafluoro(trifluoromethyl)-
000355259 Butane, decafluoro- 10.40 10.30 0.00
000355420 Hexane, tetradecafluoro- 8.40 0.00 0.00
Ul
000355680 9.73 0.00 0.00
000355759 8.95 0.00 0.00
Structure
F
F
CF.
F
F.
F
F
F
F F
F
F
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
000356707
Estimated Daubertand Literature Temp
Danner (1989)
8.99 0.00 0.00
Reference
Structure
F F
F F
F F
F F
000359580
o\
000360576
000371904
9.86 0.00 0.00
000360521 2-Propanone, 1,1,3,3-tetrafluoro 9.63 0.00 0.00
10.60 0.00 0.00
11.90 0.00 0.00
CI
H
H I F
F F
O
F
H
F F
CF, F
F
F CF3
F F
000372907 1,4-Difluorobutane
13.00 0.00 0.00
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
000373535 Methane, iodofluoro- 5.11 0.00 0.00
CAS Registry
Number
Reference
Structure
H
H\|/]
000374129 1,1,2,2-Tetrafluorocyclobutane 11.00 0.00 0.00
F
^-F
000374981 Butane,
1,1,1,2,2,3,3-heptafluoro-4-iodo-
6.50 0.00 0.00
p H
F v J I
F F
000375177
000377366
000382105 1-Propene,
3,3,3-trifluoro-2-(trifluoromethyl)-
9.98 0.00 0.00
8.60 0.00 0.00
17.00 0.00 0.00
H
F r, F
F \yF I^F
H
F
F F
F „ F
F \sF |^F
H
H F
CF,
F
F
H F
000382207
12.30 0.00 0.00
A value of 0.00 indicates that no data are available
F F
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference
Number Danner(1989)
000382343 1,1,2,3,3,3-Pentafluoropropyl methyl 9.43 0.00 0.00
ether
Structure
pf r
F F
CH,
000407590 1,1,1,4,4,4-Hexafluorobutane
000421078 Propane, 1,1,1 -trifluoro-
10.10 0.00 9.50 20 Ball, EE. and Lamberts,
WM. (1993)
11.00 0.00 0.00
oo
000421147 Trifluoromethyl methyl ether
13.70 0.00
0.00
h3c^ ^cf3
o
000421501 2-Propanone, 1,1,1 -trifluoro
12.00 0.00
0.00
CH,
000422026
000422855 Propane,
1-bromo-1,1,2,2,3,3,3-heptafluoro-
9.38 0.00
7.19 0.00
0.00
0.00
CI
Br
H
F I F
H F
F
F
F
F I F
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner(1989)
9.46 0.00 0.00
CAS Registry
Number
Reference
000423223
000425821 1,1,2,2,3,3-Hexafluorooxetane 13.70 0.00 0.00
000425887 1-Methoxy-1,1,2,2-tetrafluoroethane 12.00 0.00 0.00
Co 000431050 1,1-Difluoroacetone
14.80 0.00 0.00
000431312 1,1,1,2,3-Pentafluoropropane 8.92 0.00
19.20 44 Knopeck, GM. et al.
(1993)
Structure
F F
F O.
<*>?1
F
F
F F
F F
F F
CH,
O
v H F
FAX;"
F T?
000431470 Methyl trifluoroacetate
11.00 0.00 0.00
o
,CH,
000431630 1,1,1,2,3,3-Hexafluoropropane 10.20 0.00 0.00
H I F
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner(1989)
000431710 2-Propanone, 1,1,1,3,3-pentafluoro 9.56 0.00 0.00
CAS Registry
Number
000431867
000431878
8.77 0.00 0.00
10.00 0.00 0.00
to
o
000431890 1,1,1,2,3,3,3-Heptafluoropropane 19.10 0.00 0.00
000453145 1,3-Difluoroacetone
000460128 1,3-Butadiyne
12.00 0.00 0.00
14.20 0.00 0.00
Reference
Structure
-vV:
F F
CI
CI
H I F
F F
CI
F
F
H I F
F F
F
F
F
H I F
F F
O
F F
000460344 1,1,1-Trifluorobutane 12.00 0.00 0.00 F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
Estimated Daubertand Literature Temp Reference
Danner (1989)
000460435 1-Methoxy-2,2,2-trifluoroethane 12.50 0.00 11.84 25 Smith, ND. (1993)
Structure
CH,
000460731 1,1,1,3,3-Pentafluoropropane
9.39 0.00 0.00
000461632 Difluoromethyl fluoromethyl ether 10.30 0.00 0.00
to
000462555
000503173 2-Butyne
10.30 0.00 0.00
12.50 14.20 0.00
H
F F
+Y;
F H
CH,
CH,
CH,
»CF.
H,C—=—CH,
000503300 Trimethylene oxide
13.80 0.00 0.00
D
000504609 1,3-Pentadiene
12.10 0.00 0.00
h2c
CH,
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
000507200 Propane, 2-chloro-2-methyl- 11.70 11.50 0.00
CAS Registry
Number
Reference
Structure
ci
H,C>^ | ^CH,
'\|/(
CH,
000512516 1,1,2,2-Tetrafluoroethyl ethyl ether 12.20 0.00 0.00
000513359 2-Butene, 2-methyl-
F F
-O
F F
13.20 14.10 0.00
CH,
h3c
CH,
to
K>
000540545 Propane, 1-chloro-
9.79 10.80
8.50 0 Missenard, FA. (1966) H
CI
CH,
000542927 1,3-Cyclopentadiene
11.70 13.10 0.00
G
000558372 1-Butene, 3,3-dimethyl-
13.00 12.40 0.00
h2c
CH,
CH,
H,C 3
000558612
10.20 0.00 0.00
CI
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner(1989)
13.60 12.90 0.00
CAS Registry
Number
000563462 1-Butene, 2-methyl-
Reference
Structure
h2c
CH3
000591935 1,4-Pentadiene
12.60 12.60 0.00
h2c
'CH,
000594116 Cyclopropane, methyl-
13.50 0.00 0.00
H,C
000627190 1-Pentyne
13.40 13.60 0.00
HC^ v CH,
000662351
000665167
9.33 0.00 0.00
11.10 0.00 0.00
F H
F t F I H
F F
CF,
F3C"
CF,
000666160 Fluorocyclobutane
13.50 0.00 0.00
]
ri
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
000677214 1-Propene, 3,3,3-trifluoro- 10.90 0.00 0.00
CAS Registry
Number
Reference
Structure
h2c^^<
000677565 1,1,1,2,2,3-Hexafluoropropane 10.00 0.00 0.00
000677690 Propane,
1,1,1,2,3,3,3-heptafluoro-2-iodo-
8.54 0.00 0.00
,H
F I "H
F F
I
F
F
F I F
F F
to
.j^ 000678262 Pentane, dodecafluoro-
000679856
6.60 0.00 0.00
8.29 0.00 0.00
000679867 1,1,2,2,3-Pentafluoropropane 8.81 0.00
15.90 44 Knopeck, GM et al.
(1993)
F K F
CI
H,
F F F F F
F
H
F I H
H F
F
F
H
F I H
F F
000680002 1,1,2,2,3,3-Hexafluoropropane 9.27 0.00 0.00
,H
F I F
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference Structure
Number Danner(1989)
000680546 1,1,2,3,4,4-Hexafluoro-l-butene 11.00 0.00 0.00 F F
F F
000684162 2-Propanone, hexafluoro 13.70 0.00 0.00 O
F " -F
F' I PF
F F
000686657 1,2-Difluorobutane 13.00 0.00 0.00 F
F,
^ 000689974 1-Buten-3-yne 13.80 0.00 0.00 2
Ui HC
000690222 Trifluoromethyl ethyl ether 12.50 0.00 0.00
-O
CF,
000690391 1,1,1,3,3,3-Hexafluoropropane 10.10 0.00 0.00
000691372 1-Pentene, 4-methyl-
12.30 11.70 0.00
H I F
F F
CH,
H2C
CH0
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
000754347 Propane,
1,1,1,2,2,3,3-heptafluoro-3-iodo-
000755259
000755271
to
5* 000811972 Ethane, 1,1,1,2-tetrafluoro-
Estimated Daubertand Literature Temp Reference
Danner (1989)
8.06 0.00 0.00
Structure
9.70 9.10
9.86 0.00 0.00
8.68 0.00 0.00
F I I
F F
F F F F
F F F F
OFF
F II F
F F F F
14.50 20 Creazzo. JAetal. (1993) F H
F-^ (~F
H
000819498 1-Trifluoromethoxy-2-fluoroethane 12.10 0.00 0.00
•o
CF,
000931919 Hexafiuorocyclopropane
10.90 0.00 0.00
001115088 1,4-Pentadiene, 3-methyl-
12.70 0.00 0.00
h2c
•CH„
CH,
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
001120203 1,1 -Difluorocyclopentane
001191964 Cyclopropane, ethyl-
Estimated Daubertand Literature Temp Reference
Danner (1989)
12.60 0.00 0.00
15.60 0.00 0.00
Structure
F F
,CH,
001479498 Trifluoromethyl ether
12.70 0.00 0.00
ty:
F F
to
001481363 Fluorocyclopentane
001493034 Methane, iododifluoro-
13.30 0.00 0.00
6.25 0.00 0.00
F
Hvpl
001511622 Methane, bromodifluoro-
8.97 0.00 0.00
.Br
001522221
7.92 0.00 0.00
o o
F^ JL JL ^F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
001584005 9.86 0.00 0.00
CAS Registry
Number
001584027
9.86 0.00
0.00
Reference
Structure
F F F
F F F F F F
F F F F
F F F F F F
001584038
001584038
001584038
001584038
10.30 0.00
10.30 0.00
10.60 0.00
10.60 0.00
0.00
0.00
0.00
0.00
F
F
F F F
F F F
F\/F P
F
F
F I F
F F F
F
F
^Tr;
F F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner(1989)
001634044 t-Butyl methyl ether 14.40 0.00 0.00
CAS Registry
Number
Reference
Structure
CH,
h3c.
CH,
001649087 Ethane, 1,2-dichloro-1,1-difluoro- 16.90 0.00 0.00
CH,
H
¦-) fH
CI CI
001691174 Difluromethyl ether
12.50 0.00 0.00
ty;
001717006 Ethane, 1,1-dichloro-1-fluoro- 9.46 0.00 9.20 23
H H
Cecchini, C. et al. (1991) CI H
fJ>—f'
CI H
001765260
001805227 Cyclopentane,
nonafluoro(trifiuoromethyl)-
11.40 0.00 0.00
10.50 0.00 0.00
001814886 1,1,1,2,2-Pentafluoropropane 11.50 0.00 0.00
CF
CF
CF
F F
F
F
H
F I ~H
F H
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
002070704
002206771
Estimated Daubertand Literature Temp
Danner(1989)
10.30 0.00 0.00
10.40 0.00 0.00
002252848 1,1,1,2,2,3,3-Heptafluoropropane 11.00 0.00 0.00
u>
o
002314978 Methane, trifluoroiodo-
8.06 0.00 0.00
Reference
Structure
F CF,
F F F F
F F
A
I I
V
F F
F F
002356618
002356629
10.90 0.00 0.00
11.40 0.00 0.00
F^ ^\q/CF,
F
F
-O.
"CF,
002358385 1,1-Difluorobutane
13.00 0.00 0.00
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
002366521 Butane, 1-fluoro-
Estimated Daubertand Literature Temp
Danner (1989)
12.50 0.00 0.00
Reference
h3c
Structure
,CH^—F
002396658 1,8-Nonadiyne
15.60
002837890 Ethane, 2-chloro-1,1,1,2-tetrafluoro- 18.00
0.00
0.00
0.00
15.90 80 Creazzo, JA. and
Hammel, HS. (1991)
002994710 Cyclobutane,
1,1,2,2,3,4-hexafluoro-3,4-bis(trifluoro
methyl)-
11.40
0.00
0.00
CF,
F
CF,
003330152 Propane, 13.10
1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-te
trafluoroethoxy)-
0.00
0.00
C
C3F7 O F
003822682 Trifluoromethyl difluoromethyl ether 16.20 0.00 0.00 F
EV I
'rv;
F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference
Number Danner(1989)
003831490 Ethane, 1-iodo-1,1,2,2-tetrafluoro- 7.45 0.00 0.00
013221711 Cyclobutane, 11.70 0.00 0.00
1,1,2,3,3,4-hexafluoro-2,4-bis(trifluoro
methyl)-
014115481 12.60 0.00 0.00
017737223 11.40 0.00 0.00
019430934 1-Hexene, 9.78 0.00 0.00
3,3,4,4,5,5,6,6,6-nonafluoro-
021297654 18.90 0.00 0.00
Structure
F
fx
F
CF
CF
CF
CF
F
F,C
F
CF
F
h2c
F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
CAS Registry
Number
022669096 1,1-Difluorocyclobutane
Danner (1989)
12.80 0.00 0.00
Reference
Structure
024270664 1,1,2,3,3-Pentafluoropropane
026446593
8.19 0.00 0.00
19.30 0.00 0.00
t
'¦ttY
H H
o
026637683
9.42 0.00 0.00
¦ 10
(CFJ
3' 2
028523866
028677001
12.20 0.00 0.00
11.40 0.00 0.00
o
ch2f
\
j— (CF3)
032778113 1 -Difluoromethoxy-1,1,2,2-tetrafluoro
ethane
11.50
0.00
0.00
F F
F F
-o„
CHF„
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner{1989)
032778168 1-Difluoromethoxy-2,2-difluoroethane 12.00 0.00 0.00
CAS Registry
Number
Reference
Structure
CHF0
032981229
13.90 0.00 0.00
038706739
11.90 0.00 0.00
F F
XX
o
F F
F
-f^ 040723635 1,1,2,2-Tetrafluoropropane
10.70 0.00 0.00
040723806 Butane, 1,1,1,2,2-pentafluoro-4-iodo- 6.63 0.00 0.00
F H
050422769 1-Fluoro-2-ethylcyclopropane 14.50 0.00 0.00
CH,
054264992
12.80 0.00 0.00
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
056281926 1-Dif)uoromethoxy-1,2,2-trifluoroetha 11.70 0.00 0.00
ne
CAS Registry
Number
Reference
Structure
o
,cf2h
057041675
11.30 0.00 0.00
F F
-O
F F
CHF„
065601685
068217469
11.10 0.00 0.00
8.60 0.00 0.00
069750681 2-Fluoroethylcyclopropane 14.50 0.00 0.00
069948294 1-Difluoromethoxy-1,1-difluoroethane 12.00 0.00 0.00
-o
CHF,
072507858 1,2-Difluorocyclobutane
12.70 0.00 0.00
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp Reference
Number Danner(1989)
085720781 10.90 0.00 0.00
090278005 10.90 0.00 0.00
OJ
OS
l-Chloro^^.S.S.^-hexafluorocycIo 14.60 0.00 0.00
butane
111 8.74 0.00 0.00
113742908 1,2-Difluorocyclopentane 12.50 0.00 0.00
Structure
CF.
F
F
CF.
F
F
CI
F
Fv A ^F
f y f
F
F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name
CAS Registry
Number
116199292
Estimated Daubertand Literature Temp
Danner (1989)
11.90 0:00 0.00
Reference
Structure
123
12.50 0.00 0.00
123768183 1,1,2,2,3,3-Hexafluorocyclopentane 11.20 0.00 0.00
u>
-j
123812806 3-Fluorocyclobutene
12.50 0.00 0.00
F
F
F. F p
129362976 1,2,3,4-Tetrafluorocyclobutane 11.40 0.00 0.00
133360006 2,3,4,5-Tetrafluorotetrahydrofuran 14.80 0.00 0.00
F
/ \
F F
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
11.00 0.00 0.00
CAS Registry
Number
134166497
135617435
10.80 0.00 0.00
Reference
Structure
F CH3
F v. ^.0 F
135617446
12.00 0.00 0.00
oo 135617457
135617468
135617479
135617480
10.50 0.00 0.00
10.50 0.00 0.00
10.10 0.00 0.00
10.30 0.00 0.00
H
•vyu
F F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner(1989)
10.00 0.00 0.00
CAS Registry
Number
135617491
135617504
135617571
& 135617640
10.00 0.00 0.00
12.10 0.00 0.00
12.50 0.00 0.00
Reference
Structure
CF.
CF.
-H
-H
135617662
12.50 0.00 0.00
-H
135617673
12.10 0.00 0.00
CF,
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
CAS Registry
Number
135947169
Danner (1989)
9.17 0.00
0.00
Reference
F
F
136975092 1-Trifluoromethyl-1,2,2-trifluorocyclob 12.10
utane
0.00 0.00
4^
O
144109035 1,1,2,2,3-Pentafluorooxetane
13.00 0.00
0.00
£
144963699
9.62 0.00
0.00
F-
145354887
11.90 0.00 0.00
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
13.70 0.00 0.00
CAS Registry
Number
145866235
146229289
146780203
147356670
11.70 0.00 0.00
9.77 0.00 0.00
13.10 0.00 0.00
Reference
Structure
CF
CF.
F F
,0,
cf,—r "1 F
CF, 7^ F
F ° F
F
O
•H
154330402 1,1,3,3-Tetrafluorooxetane
12.20 0.00 0.00
,3
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
CAS Registry Name Estimated Daubertand Literature Temp
Number
222
234
25
to
345
39
Bromodifluoromethyl trifluoromethyl
ether
Danner (1989)
9.51 0.00
12.30 0.00
1,1,1,2,2,3,3-Heptafluorobutane 10.30 0.00
14.60 0.00
0.00
0.00
0.00
11.00 0.00 0.00
0.00
Reference
Structure
F F
rr,'
F F
40
Bis(trifluoromethoxy)difluoromethane 15.20 0.00 0.00
F r
'xV-A
F
F F F
F F F
F
A value of 0.00 indicates that no data are available
-------
Table 1. Experimental and Estimated Vapor Thermal Conductivities in mW/(m K) (continued)
Name Estimated Daubertand Literature Temp
Danner (1989)
6104 1,2,3-Trifluorocyclobutane 12.20 0.00 0.00
CAS Registry
Number
6108 1,2,3-Trifluorocyclopentane 12.00 0.00 0.00
Reference
Structure
F F
F
F-. S^-F
6109 1,2,3,4-Tetrafluorocyclopentane 12.00 0.00 0.00
•U>
6112 1,1,1,3-Tetrafluoroacetone
11.00 0.00 0.00
6119 Trifluoromethoxymethoxymethane 12.80 0.00 0.00
F" F
O
F F
H3C'
,0^
CF-
6330
64
1,2-Dichloro-1,2,3,3,3-pentafIuoropro
pane
12.90 0.00 0.00
8.73 0.00 0.00
CH,
H
,CF„
CI
H
CI
F I F
H F
A value of 0.00 indicates that no data are available
-------
Experimental
16
14
12
10
8
6
4
6
Estimated
Figure 2. Estimated vs. Experimental Vapor Thermal Conductivities in mW/(m K)
44
-------
mW/(m K) were very close to the experimental values and that the greatest deviation occurred in
the high-range estimates. The majority of compounds considered in phase 2 of this task had
thermal conductivities in the 8 to 13 mW/(m K) range.
Critical Temperature and Pressure
To perform the vapor thermal conductivity estimates, critical temperature (Tc) and
pressure (Pc) needed to be estimated first if experimental values could not be found in the open
literature. These were obtained by Joback's method (Joback, KG., 1982; Rcid. RC. et al, 1987).
Estimation of these values also required a boiling point that could be obtained, as required, from
Joback's method (Jobaek, KG., 1982). This method was advantageous as the fragment groups
for the Joback method are the same for the normal boiling point (Tb), Tc, and Pc; however, ATC
and APC need to be summed for estimating the critical temperature and critical pressure,
respectively. The critical temperature (Te in K) and critical pressure (Pc in bars) are then obtained
from the equations
Tc = Tb [0.584 + 0.965 EATC - (SAT,)2]"1
and
Pc = (0.113 + 0.0032 nA - £APC)"2
where nA is the number of atoms in the molecule. Tb represents the normal boiling point.
For cyclic hydrocarbons, group contributions are available only for -CH,- (4.25) and
--CH= (3.50). Thus, there is no recommended way to estimate C for substituted cyclic
hydrocarbons. In this study, we have assigned the value for -CH2- (4.25) to both -C- and -CH-
groups in cyclic structures. However, this only makes a minor difference to the overall thermal
conductivity. For example, consider fluorocyclobutane. If a value of 4.25 is assigned to the
45
-------
-CH- group, then 1=13.5 mW/(m K). If the value for CH= of 3.50 (an extreme case) is used,
1=12.7 mW/(m K). For one or two substituents, the difference is not appreciable. On the other
hand, the difference between cyclohexane and perfluorocyclohexane would be very significant
since these differences would be cumulative. However, the high-priority compounds on our list
are relatively small, and large differences in 1 arising from uncertainty in C are expected to be
unlikely.
There were several other occasions where approximations were required. For example,
among ethers, a group value is only given for a primary ether group; secondary and tertiary
derivatives are excluded. In our study, all ethers were assigned the group value for a primary
ether.
Another source of uncertainty lies in the calculation of f(Tr) which takes the form
f(Tr) = aTr + bTr2 + cTr3
where Tr is the reduced temperature and a, b, and c are fitted coefficients. Different values of the
coefficients are available for (I) saturated hydrocarbons, (ii) olefins, (iii) acetylenes, (iv)
naphthalenes and aromatics, (v) alcohols, (vi) aldehydes, ketones, ethers and esters, (vii) amines
and nitriles, (viii) halides, and (ix) cyclic compounds. A problem arises if a compound fits into
more than one category. Consider difluoromethyl fluoromethyl ether (Chemical Abstract Service
(CAS) Registry number: 461-63-2). If the "halide equation" is used, then 1=13.9 mW/(m K). If
the equation for ethers is applied, then 1=13.3 mW/(m K). Again, the difference is quite small if
only one or two substituents are involved.
In sum, although there were many compounds that fell outside the Roy-Thodos
formalism, the errors incurred by assigning values for their structurally nearest neighbors are
46
-------
expected to be quite small, and are probably insignificant for our purpose of prioritizing
structures for more detailed consideration.
Developing Estimation Methods for Silicon-Containing Compounds
In the course of this investigation, it became evident that tetraalkyl silicon compounds
should be considered as a potential group of blowing agent substitutes. With the exception of
tetramethylsilane, however, little experimental data were available on these compounds.
Moreover, estimation techniques described previously did not have group constants for the
silicon atom. Therefore, we set out to develop methodology for estimating the vapor thermal
conductivity of tetraalkyl silicon compounds.
Roy-Thodos Constant
Thermal conductivities, critical properties, and boiling points were obtained from the
literature for the fourteen silicon compounds (Si) in Table 2. Since the data set is quite small and
covers a narrow range of thermal conductivity, it was impractical to derive formal equations for
silicon compounds. Instead, a "perturbation" method was used. Here, experimental partial C
values were first back calculated for compounds containing silicon which have known thermal
conductivity values from the literature Pc, Tc, Tb, and A values. Partial C values for the silicon
groups were then obtained by subtracting out the known partial values of C for the other groups.
Although there are five kinds of silicon groups (Si to SiII4 in Table 2), the values were too close
to be separated, and a single value of C of 3.23 was averaged for all the groups.
47
-------
Boiling Point
Using known boiling points of compounds containing silicon groups, estimates of the
contribution a silicon group makes to the normal boiling point of a compound were made using
Table 2. Properties of Silicon Compounds
CAS# X Pc Tc Tb MW
Silane, dichloromethyl
Silane, tetramethyl
Silane, chlorotrimethyl
Silane, dichlorodimethyl
Silane, trichloromethyl
Silane, methyl
Silane, chloromethyl
Silane, trimethyl
Silane, chlorodimethyl
Silane, dimethyl
Silane, dichloro
Silane
Silane, trichloro
Silane, tetrachloro
A - mW/(m K)
Pc - bars
Tc -K
Tb - K
the method of Stein and Brown (Stein, SE. and Brown, RL., 1994). This method attributes a
contribution from each chemical group in the compound. Since values for the non-silicon groups
were available, it was a simple matter to estimate and average group contribution values for the
various silicon groups is 20,13 and 22 for Si, SiH and SiH2. Unfortunately, these averages have
very high uncertainty. For example, the Si value of 20 is averaged from 8, 24,22, 64, and -20.
Only one compound with an SiH, value was available, and this value was -6. Given these
variations, the averages for Si, SiH, and SiH2 were re-averaged to give 18, and this figure was
75-54-7
10.27
39.5
483
315
115
75-76-3
15.51
28.1
450
300
88
75-77-4
12.2
32.0
498
331
109
75-78-5
9.8
34.9
520
343
129
75-79-6
8.52
35.3
517
400
149
992-94-9
17.9
48.4
353
216
46
993-00-0
12.56
41.7
442
282
81
993-07-7
15.23
31.9
432
280
74
1066-35-9
11.9
36.2
472
309
95
1111-74-6
16.6
35.6
402
254
60
4109-96-0
10.09
44.3
449
281
101
7803-62-5
22.8
48.4
270
161
32
10025-78-2
7.92
41.7
479
305
135
10026-04-7
8.49
35.9
507
330
170
48
-------
used for all silicon groups. Estimated values of 1 based on estimated boiling point contribution
and actual values are compared in Table 3. Except for silane, the comparison is reasonably good,
probably because the inclusion of a single silicon group has only a small impact on the overall
boiling point, and the variations within these group values are, therefore, of relatively minor
importance.
Table 3. Comparison of Estimated and Experimental Properties for Silicon Compounds
X est
A exptl
Pc est
Pc exptl
Tc est
Tee
Silane, dichloromethyl
7,0
10.27
45.4
39,5
490
483
Silane, tetramethyl
15.4
15.51
28.8
28.1
451
450
Silane, chlorotrimcthyl
11.7
12.2
39.0
32.0
500
498
Silane, dichlorodimethyl
8.1
9.8
32.8
34.9
520
520
Silane, trichloromethyl
9,0
8,52
35.2
35.3
see text
517
Silane, methyl
13.7
17.9
42.2
48.4
354
353
Silane, chloromethyl
12,1
12.56
39.7
41.7
447
442
Silane, trimethyl
15.4
15.23
32.5
31.9
432
432
Silane, chlorodimethyl
114.0
11.9
34.8
36.2
see text
472
Silane, dimethyl
16.0
16.6
36.9
35.6
400
402
Silane, dichloro
12,0
10.09
42.8
44.3
447
449
Silane
28.3
22.8
48.8
48.4
270
270
Silane, trichloro
11.0
7.92
40.2
41.7
477
479
Silane, tetrachloro
7.6
8.49
37.8
35.9
505
507
X est - mW/(m K)
X exptl - mW/(m K)
Pc est - bars
Pc exptl - bars
Tc est - K
Te exptl - K
Critical Temperature
Calculation of group contribution values of Tc, called fragment constants for ATC was
based on Joback's method and was estimated from the equation
Tc = Tb[0.584 + 0.965 2ATC - (SAT,)2]"1
49
-------
There are two solutions for ATC; the higher value was well outside the typical range for ATC, and
the lower value was, therefore, taken. The AT,, value for the silicon groups was obtained after
subtracting out the known ATC values for all of the other groups. Values for two compounds
(trichloromethylsilane and chlorodimethylsilane) were clear outliers. With their exclusion, the
following fragment constants were derived:
SiII4 0.0120 n=l
SiH, 0.0129 n=l
SiH, 0.0274 n=3
SiH 0.0301 n=3
Si 0.0367 n=4
There is a consistent trend to the data, and the magnitude is within the range of similar
groups. For example, the value for SiH4 is very close to that of the fluorine group. Estimated
and actual values for Tc using these and known other fragment constants along with experimental
Tb values are compared in Table 3.
Critical Pressure
Critical pressures were estimated from the equation
Pc = (0.113 + 0.0032 nA - SAP,)"2
(which is based on Joback's method) and known values of Pc and nA. The APcs ranged from
-0.035 to -0.00394 and no statistical differences existed for values for the five types of groups
involved, i.e., SiH, - Si. Hence, they were averaged to give a APC value of -0.0141 for any of
these groups. Estimated and actual values for Pc using these and known other fragment constants
along with experimental Pc values are compared in Table 3.
50
-------
Overall Comparison
Thermal conductivities calculated with estimated values of Pc, Tc, and AC values for the
Si group are compared to experimental measures in Table 3. For trichloromethyl and chloro-
methylsilane, experimental values of Tc were used for reasons described above. The comparison
is good, suggesting that the estimated parameters are adequate for computing thermal
conductivities of other structurally related compounds.
Task 2: Identification of Potential New Foam Blowing Agents.
The first step in this task was to develop a master list of potential foam blowing agent
substitutes by developing an electronic database of chemical substances that could then be
manipulated to obtain those substances that possess the most desirable physical/chemical
properties. The list of potential blowing agents was obtained from the following sources:
• TSCA Inventory. Chemical compounds known to be produced commercially were
identified. Searching by either molecular formula (for hydrocarbons) or chemical name
(for ketones, ethers, halogen containing compounds, etc.), a master list containing
thousands of potential candidates was obtained. Unacceptable candidates (e.g.,
aromatics) or compounds that would react with polyurethane foam feedstocks (e.g.
amines, thiols, epoxides, or alcohols) were removed electronically by searching for those
that contained sub-strings such as "anthracene" or "amino" in the chemical name field.
• Literature Sources. Additional rigid foam blowing agent candidates were obtained from
periodicals such as Proceedings of the Polyurethane World Congress, patent literature,
and pertinent journal articles discussing blowing agents or blown foams. If a chemical
compound was identified in these sources as a possible blowing agent, it was included.
This process allowed the inclusion of chemical compounds not known to be produced
commercially as well as those being considered as blowing agents by commercial and
academic research groups.
51
-------
• Other Sources. A number of candidates were obtained from a wide variety of other
sources including various EPA documents, encyclopedic sources, and chemical company
literature.
• Reverse-Engineered Compounds. The results from Task 1 allowed us to develop some
generalized trends relating changes in structure and functionality to vapor thermal
conductivity. Starting with chemical compounds that possessed low vapor thermal
conductivities, new functional groups were added (or subtracted), structures were
modified, and substitution patterns were changed in order to obtain new blowing agent
candidates. Some blowing agent candidates obtained through this process had not yet
appeared in the chemical literature and, thus, were theoretical species.
The master list contained approximately 1,000 chemical substances when this process was
completed.
The master list was then linked electronically with SRC's CHEMBASE® database of
physical properties on 7,000 chemicals, PHYSPROP, and the Environmental Fate Data Bases
(EFDB) (Howard, PH. et al, 1982; Howard, PH. et al., 1986), as well as other PC-based
databases developed in-house to obtain basic physical/chemical properties on as many
compounds as possible. This electronic search for physical/chemical properties was
supplemented by obtaining melting points, boiling points, and vapor pressures, as well as other
pertinent properties using encyclopedic sources including the Aldrich Catalog (Aldrieh, 1994),
Merck Index (Budavari, S. et al, 1989), Techniques of Chemistry - Organic Solvents (Riddick,
JA. et al., 1986) and Daubert and Danner's compilation (Daubert, TE. and Danner, RP., 1989);
the latter source also contained an extensive set of experimental vapor thermal conductivity data.
Vapor phase thermal conductivity data were also collected from available sources with the 1991
and 1993 Proceedings of the Polyurcthancs World Congress providing highly reliable data.
52
-------
It was decided that it would be too resource intensive to calculate the vapor-phase thermal
conductivity for this many chemicals, so the master list was trimmed based on boiling point.
Boiling points are readily available and they provided a reliable method of removing undesirable
compounds from the master list. For example, high boiling liquids do not make suitable blowing
agents while low boiling liquids or gases may make effective blowing agents with proper
equipment modifications. Known or experimental polyurethane foam blowing agents have
boiling points ranging from approximately -50 °C (difluoromethane) to 50 °C (cyclopentane). If
experimental boiling points were not available, they were estimated for this portion of the task
using the Joback's method, as described in Task 1. The available data indicated that
approximately 125 compounds on the master list had boiling points in the -60 to 60 °C range.
This initial list was reviewed and compared to compounds in the master list for which
boiling points were not available. If any of these compounds in the master list had a reasonable
match for structure, molecular weight, and functionality with a compound on the initial list, then
it was added to the initial list. Compounds were also removed from the initial list as appropriate.
For example, those with high vapor phase thermal conductivities relative to currently used foam
blowing agents were removed as were those that, upon closer examination, were expected to
react chemically with the polyurethane foam feedstocks (e.g., two fluorinated vinyl ethers were
removed from further consideration at this time because they were expected to react with the
feedstocks used in polyurethane foam production).
Additions to the initial list were made to expand the universe of potential blowing agents
for consideration. Unlike the compounds considered previously, these new additions were not
known to be produced commercially. This list was obtained by searches of Chemical Abstracts,
the chemical literature, as well as other sources for compounds of an appropriate molecular
-------
formula and/or structure that may possess the requisite physical/chemical properties at room
temperature to act as blowing agents. Reverse-engineered compounds were also considered.
Most of the compounds added in this exercise were fluorinated although also included were some
interesting chemical classes including furans, dioxanes, silanes, pyrans, morpholines, and
perfluorinated tertiary amines.
The next step was to fill any remaining data gaps for the compounds in the initial list of
potential blowing agent candidates. Physical/chemical property estimations were completed. In
order to estimate boiling points and vapor thermal conductivities, a new methodology was
developed, as described earlier in this report. Unfortunately, vapor thermal conductivity and
boiling point estimations could not be performed for an interesting class of potential blowing
agents, the perfluorinated amines, because appropriate group fragments were not available for
Joback's vapor thermal conductivity estimation method and they could not be derived as
experimental values on similar compounds were not available.
To further limit the initial list of potential blowing agents before the ranking exercise was
performed, all chlorine containing compounds were removed from further consideration since
they were likely to have some ozone depletion potential. The initial presence of chlorine
containing compounds was important, however, in determining the reliability of the thermal
conductivity estimation methods.
Ranking the List
At a Society of the Plastics Industry (SPI) Polyurethane Division meeting on third
generation blowing agents held on March 24, 1994, at Miles Inc., round-table discussions
between representatives of industry, the EPA, and SRC were held to determine the most
54
-------
important criteria for determining if a chemical candidate would reasonably be expected to
perform as a blowing agent for polvurethane foams. The four most important criteria were
concluded to be molecular weight, boiling point, vapor thermal conductivity, and global warming
potential (GWP). With these criteria identified, the list of potential rigid foam blowing agent
substitutes was ordered to identify the most promising alternatives. This ordering process was
based on the following:
• Boiling point. According to industrial representatives present at the meeting, the best
substitute blowing agent would be one that has a boiling point as close as possible to that
of CFC 11 (23.8 °C), as this would reduce retro-fitting costs. For the ranking exercise,
the absolute value of the difference between 23.8 °C and the boiling point of the potential
blowing agent substitute was used. Thus, ABP = |BPcrcil - BPmbsti J. The compound
with the smallest ABP was ranked number 1 while that with the largest was ranked
number 90. For chemicals whose experimental boiling point could not be located, the
boiling point was initially estimated using the method of Joback, During the later stages
of this project, we had just completed work on a new product in our suite of estimation
programs that estimated boiling points based on recent work by Stein and Brown (Stein,
SE. and Brown, RL., 1994). Joback's method for estimating boiling point used a set of
41 groups while that of Stein and Brown used 85 groups. Based on 6,584 diverse organic
compounds with experimental boiling points, the Stein and Brown method has a 3.2%
average error that corresponds to an absolute error of 15.5 °C. SRC's computer
estimation program is based on Stein and Brown's method and it was used to estimate
boiling points for all blowing agent candidates that did not have experimental values
available for the ordering exercise. However, because of resource constraints, the
estimated vapor thermal conductivities were not recalculated with the more accurate
boiling points,
• Molecular weight. The molecular weight also addresses the economics of using a
substance as a blowing agent since the higher the value, the more costly the compound on
a price by weight basis. Allied-Signal researchers (Deeaire, BR. et al, 1992) used an
arbitrary molecular weight cut-off of 180 in their evaluation of new blowing agents, and
we removed all compounds with a molecular weight >182 from our ranking list, with the
exception of perfluoroalkyl iodides (which, as described below, have some interesting
55
-------
properties and, we believe, should not be eliminated solely because of their potential cost
of use). For the molecular weight ranking, the lowest molecular weight compound was
ranked number 1.
• GWP. A determination of a compound's GWP is important because it addresses the
issues associated with greenhouse gases. Rigorous estimations of global warming
potential are extremely complex and time consuming. The GWP is dependent, in part, on
a compound's atmospheric lifetime, and, in part, on the infra red (IR) absorption strength
in the 800-1200 cm4 region (Wuebbles, DJ., and Edmonds, J., 1991). For a first order
approximation, compounds which have a short atmospheric lifetime are the ones most
likely to have a low GWP. An organic compound's atmospheric lifetime can be estimated
from the rate of its vapor-phase reaction with hydroxyl radicals. The more rapid the rate
constant for this reaction, the less likely the compound will contribute to global warming.
Hydroxyl radical reaction rates are available experimentally or can be estimated using the
method of Atkinson (Meylan, WM. and Howard, PH., 1993). For ordering the list by
GWP, experimental rate constants for vapor-phase hydroxyl radical reactions were
obtained from SRC's EFDB (Howard, PH. et al., 1982; Howard, PH. et al., 1986),
literature reviews (Atkinson, R„ 1985; Atkinson, R., 1994) or estimated using our
Atmospheric Oxidation Potential (AOP) computer program which is based on Atkinson's
method. The compound with the highest hydroxyl radical reaction rate constant was
assigned number 1.
• Vapor thermal conductivity. Vapor thermal conductivity values were collected or
estimated as described earlier. For thermal conductivity, the compound with the lowest
value was ranked number 1.
After the ranks for each of the four areas were assigned, they were added together to
establish an overall score. This methodology weighs all four criteria equally. The results of this
ranking exercise are provided in Table 4 in order of overall rank (left column). The column
56
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Table 4. Final Ranking of Blowing Agent Candidates
000142290 Cyclopentene
1 BP: 44.00 exp GWP : 65.50 MW: 68.12 TC : 10.80 exp
Rank: 52
24
000591935 1,4-Pentadiene
2 BP: 26.00 exp GWP: 53.30 MW: 68.12 TC: 12.60 exp
Rank:
8
10
68
H2C
CH
CH,
000563462 1-Butene, 2-methyl- . j
3 BP: 31.00 exp GWP: 60.70 MW: 70.14 TC: 12.90 exp
CH,
Rank: 20
13
76
H,C
123812806 3-Fluorocyclobutene
a BP: 32.67
Rank: 25
GWP : 56.26 MW : 72.00 TC : 12.50
6 17 67
000109682 2-Pentene
c BP: 37.00 exp GWP: 57.27 MW: 70.14 TC: 12.70 exp
Rank: 34 4 12 70
h3c
CH
000109671 1-Pentene
g BP; 29.90 exp GWP: 31.40 MW: 70.14 TC: 13.60 exp
Rank: 18 10 14 86
h2c
CH
002366521 Butane, 1-fluoro-
7 BP: 32.50
Rank: 23
GWP: 2.29 MW: 76.11 TC : 12.50
28 22 65
h3c
,CH;
000513359 2-Butene, 2-methyl-
q BP: 35.00 exp GWP: 86.90 MW: 70.14 TC: 14.10 exp
Rank: 30 1 15 93
CH,
h3c
CH,
000679867 1,1,2,2,3-Pentafluoropropane
q BP: 25.10 exp GWP: 0.13 MW: 134.05 TC: 8.81 exp h,
3 Rank: 5 59 69 9
000558372 1-Butene, 3,3-dimethy!
10
H
F I H
F F
BP: 41.00 exp GWP: 28.50 MW: 84,16 TC: 12.40 exp HjC T^ch
61 H,C 3
^X.ch3
Rank: 44
12
26
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/lm - K)
MW = Molecular weight
GWP m Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
57
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Table 4. Final Ranking of Blowing Agent Candidates (continued)
000078784 Butane, 2-methyl- ?H3
<1 -I BP : 28.00 exp GWP : 3,90 MW: 72.15 TC : 14.80 exp H C—
Rank: 11 21 18 97 3 NCH
000107017 2-Butene
-jo BP: 1.00 exp GWP: 56.39 MW: 56.11 TC: 13.50 3
Rank: 58 5 3 83
000287923 Cyclopentane
13 BP : 50.00 exp GWP : 5.16 MW: 70.14 TC : 12.10 exp
Rank: 68
18
11
54
O
000431312 1,1,1,2,3-Pentafluoropropane
14 BP: 22.70 GWP : 0.06 MW: 134.05 TC: 8.92
Rank:
70
70
10
F H F
F-V^s^h
F H F
000461632 Difluoromethyl fluoromethyl ether
15 BP: 29.90 GWP : 0.05 MW: 100.04 TC: 10.30
Rank: 17
73
43
21
Hs
,° F
I H
H
000691372 1-Pentene, 4-methyl-
10 BP: 53.00 exp GWP: 30.11 MW: 84.16 TC: 11.70 exp
Rank: 76
11
25
43
072507858 1,2-Difiuorocyclobutane
17 BP: 24.07 GWP: 0.33 MW: 92.00 TC: 12.70
Rank: 1
49
34
73
000372907 1,4-Difluorobutane
1 q BP : 28.82
Rank: 14
GWP : 2.05 MW: 94.11 TC : 13.00
30 38 77
000666160 Fluorocyclobutane
BP: 29.19 GWP: 0.64 MW: 74.00 TC: 13.50
Rank: 15 43 20 85
19
rf
000431050 1,1-Difluoroacetone
2Q BP: 34.13 GWP: 0.07 MW: 94.00 TC: 11.00
Rank: 28
68
36
32
O
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/'m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
58
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
000407590 1,1,1,4,4,4-Hexafluorobutane
21 BP; 24.90 exp GWP : 0.16 MW: 166.07 TC: 9.50
Rank:
56
92
14
000360521 2-Propanone, 1,1,3,3-tetrafIuoro
22 BP: 23.31 GWP: 0.01 MW: 130.04 TC: 9.63
Rank:
87
62
16
022669096 1,1 -Difluorocyclobutane
23 BP: 17.69 GWP: 0.92 MW: 92.00 TC: 12,80
Rank: 19
40
35
74
000109660 Pentane
24 BP: 36.10 exp GWP: 3.94 MW: 72.15 TC: 14.80 exp
Rank: 33
20
19
98
h3c"
000677214 1-Propene, 3,3,3-trifluoro-
oc BP: -18.00exp GWP: 26.30 MW: 96.05 TC: 10.90
Rank: 90 13 41 27
H,C
000287230 Cyclobutane
20 BP : 12.50 exp GWP : 1.20 MW: 56.11 TC: 14.80 exp
Rank: 31
36
99
6119
27
Trifluoromethoxymethoxymethane
BP: 29.52 GWP : 3.43 MW : 130.00 TC : 12.80
Rank: 16 24 61 75
H3C'
.0,
6104
28
1,2,3-Trifluorocyclobutane
BP: 18.92 GWP : 0.13 MW: 110.00 TC: 12.20
Rank: 12 58 48 59
000067641 Acetone
29 BP : 56.00 exp GWP; 0.23 MW; 58.08 TC : 11.25 exp
Rank: 81
53
38
H3c
u
001191964 Cyclopropane, ethyl-
3Q BP: 34.50 GWP : 1.38 MW: 70.14 TC: 15.60
Rank: 29
32
16
103
.ch3
A
BP ¦» Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/(m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
59
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
001115088 1,4-Pentadiene, 3-methyl-
31 BP: 55.00 exp GWP: 54,62 MW: 82.15 TC: 12.70
Rank: 79
24
71
H„C
000460731 1,1,1,3,3-Pentafluoropropane
32 BP: 15.30 exp GWP: 0.03 MW: 134.05TC : 9.39
Rank: 21
77
71
13
000109875 Dimethoxymethane
33 BP: 41.00 exp GWP: 6.87 MW: 76.00 TC: 14.90
Rank: 45
16
21
101
H
H I H
F F
CH,
CH,
9Ha CH,
000079298 Butane, 2,3-dimethyl- , j
oa BP: 58.00 exp GWP: 6.20 MW: 86.18 TC: 12.40 exp hc—' (
at en 3 \
Rank: 83
27
60
CH,
000594116 Cyclopropane, methyl-
35 BP: 4.00 GWP: 0.28 MW: 56.11 TC: 13.50
Rank: 51
50
84
h3c
123768183 1,1,2,2,3,3-HexafIuorocyclopentane
30 BP: 13.58 GWP: 2.23 MW: 178.00 TC : 11.20
Rank: 27
29
97
37
\7
002358385 1,1-Difluorobutane
37 BP: 8.56 GWP : 1.40 MW: 94.11 TC : 13.00
Rank: 40
31
40
79
000503300 Trimethylene oxide
3g BP: 50.00 exp GWP: 3.73 MW: 58.00 TC: 13.80
Rank; 70
22
92
°G
000421501 2-Propanone, 1,1,1-trifluoro
30 BP: 26.21 GWP: 0.02 MW: 112.05 TC: 12.00
Rank:
86
50
46
000460344 1,1,1-Trifluorobutane
4Q BP: 0.38 GWP: 1.35 MW: 112.00 TC : 12.00
Rank: 60
33
49
49
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/(m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
60
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
001120203 1,1 -Difluorocyclopentane
BP: 46.57 GWP : 4.46 MW: 106.00TC : 12.60
Rank: 57
19
47
69
F F
040723635 1,1,2,2-Tetrafluoropropane
42 BP: -1.60 exp GWP: 0.21 MW: 116.06 TC: 10.70
Rank: 65
54
53
23
129362976 1,2,3,4-Tetrafluorocyclobutane
43 BP: 13.74 GWP: 0.05 MW: 128.00 TC : 11.40
Rank: 26
72
58
39
000512516 1,1,2,2-Tetrafluoroethyl ethyl ether
44
BP: 14.95 GWP: 1.07 MW: 146.00 TC : 12.20
Rank: 24
38
76
57
001493034 Methane, iododifluoro-
45 BP: 21.60 exp GWP: 0.01 MW: 177.92 TC : 6.25
Rank:
93
96
F H
F F
F F
F F I
CH_
H„
000686657 1,2-Difluorobutane
4g BP: 8.56 GWP: 0.91 MW: 94.11 TC: 13.00
Rank: 39
41
39
78
CH,
024270664 1,1,2,3,3-Pentafluoroproparie
47 BP : 39.30 exp GWP : 0.02 MW : 134.05 TC : 8.19
Rank: 41
83
68
6112
48
1,1,1,3-T etrafluoroacetone
BP : 28.81 GWP : 0.01 MW: 130.00 TC : 11.00
Rank: 13 90
60
36
000431470 Methyl trifluoroacetate
49 BP : 43.00 exp GWP: 0.05 MW: 128.00 TC: 10.90
Rank: 49
71
57
26
F
H
H H
O
F%
F F
0
* 0*
F
,CH,
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/(m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-crn/molacule-sec
61
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
000680002 1,1,2,2,3,3-Hexafluoropropane
5Q BP: 10.00 exp GWP: 0.05 MW: 152.04 TC: 9.27
Hs
Rank: 35
75
82
12
000075832 Butane, 2,2-dimethyl-
51
F F
CH.
Rank:
BP: 50.00 exp GWP: 2.32 MW: 86.18 TC: 13.20 exp «c-
69 26 28 81
~\
CH, ch3
6108
52
1,2,3-T rifluorocyclopentane
BP: 47.75 GWP: 1.25 MW: 124.00 TC : 12.00
Rank: 62 35 56 52
000075763 Tetramethyl silane
53 BP: 26.00 exp GWP: 0.10 MW: 88.23 TC: 15.50
Rank: 8
63
33
102
CH,
i 3
CH. —Sl-CH..
j
CH,
000374129 1,1,2,2-Tetrafluorocyclobutane
54 BP: 0.76 GWP: 0.61 MW: 128.07 TC: 11.90
Rank:
59
44
59
45
000680546 1,1,2,3,4,4-Hexafluoro-1 -butene
gg BP: -3.77 GWP: 7.07 MW: 164.00 TC : 11.00
Rank: 72
14
88
34
000431710 2-Propanone, 1,1,1,3,3-pentafIuoro
gg BP: 15.28 GWP : 0.00 MW: 148.03 TC : 9.56
Rank: 22
96
77
15
000421078 Propane, 1,1,1-trifluoro-
57 BP: -13.00exp GWP : 0.25 MW: 98.07 TC: 11.00
Rank: 86
51
42
31
F
V
F
F F
F F
O
'rV.'
F F
F
CH,
000690222 Trifluoromethyl ethyl ether
gg BP: 1.45 GWP : 1.07 MW : 114.00 TC : 12.50
Rank: 56
39
52
63
K3C
*0
CF,
000453145 1,3-Difluoroacetone
rq BP: 49.87 GWP : 0.13 MW: 94.06 TC: 12.00
Rank: 67 60 37 48
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/!m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
62
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
154330402 1,1,3,3-Tetrafluorooxetane
gQ BP : 21.20 exp GWP : 0,02 MW: 130.04 TC : 12.20
Rank; 10
82
63
58
,3
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
000075105 Methane, difluoro
70 BP: -51,65exp GWP: 0.01 MW: 52.02 TC: 11.00 exp j[
Rank: 104 89 2 29 H » F
H
000677565 1,1,1,2,2,3-Hexafluoropropane
71 BP: -1.20 exp GWP: 0.11 MW: 152.04TC: 10.00
Rank:
63
83
18
001634044 t-Butyl methyl ether
72
Rank:
BP : 55.00 exp GWP : 2.82 MW : 88.00 TC : 14.40
80
25
30
94
000353617 Propane, 2-fluoro-2-methyl-
73 BP: -5.02 GWP : 0.56 MW: 76.11 TC : 13.80
Rank:
73
46
23
91
F JJ
F F
CH,
H3C,
-O,
CH,
CH,
ch3
H3C——F
CH,
136975092 1-Trifluoromethyl-1,2,2-trifIuorocyclobutane
74 BP: 9.73 GWP : 0.61 MW: 178.00 TC : 12.10
Rank:
36
45
98
56
d?
F
000431630 1,1,1,2,3,3-Hexafluoropropane
7g BP: 6.00 exp GWP: 0.01 MW: 152.04 TC: 10.20 exp
Rank:
46
88
85
20
069750681 2-Fluoroethylcyclopropane
7g BP: 52.94 GWP: 1.14 MW: 88.00 TC: 14.50
Rank:
75
37
32
96
000354643 Ethane, pentafluoroiodo-
77 BP: 12.00 exp GWP: 0.00 MW: 245.92 TC: 8.30
Rank:
32
100
103
H
H I F
F F
e £
000373535 Methane, iodofluoro-
7g BP: 53.40 exp GWP: 0.02 MW: 159.93 TC: 5.11
Rank: 77
79
87
1
H,
H
000811972 Ethane, 1,1,1,2-tetrafiuoro- F. .H
7g BP: -26.50exp GWP: 0.01 MW : 102.03 TC : 9.10 exp F —y F
Rank:
96
92
45
11
H
BP = Boiling point in degrees C exp »= experimental value
TC = Vapor thermal conductivity in mW/lm - K)
MW - Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
64
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
000353366 Ethane, fluoro- H.
qa BP: -37.70 exp GWP : 0.23 MW: 48.06 TC : 13.80 exp H-V
Rank: 101 1
52
1
90
r
H
H
003831490 Ethane, 1-iodo-1,1,2,2-tetrafluoro-
g-j BP : 41.00 exp GWP : 0.00 MW: 227.93 TC : 7.45
Rank:
43
97
102
Z £
¦H
000754347 Propane, 1,1,1,2,2,3,3-heptafIuoro-3-iodo-
Q2 BP: 40.00 exp GWP: 0.00 MW: 295.93TC: 8.06
Rank:
42
104
001691174 Difluromethyl ether
33 BP: 4.70 exp GWP: 0.02 MW: 118.03 TC: 12.50
Rank:
48
84
54
64
F F
Yr
H H
000677690 Propane, 1,1,1,2,3,3,3-heptafluoro-2-iodo-
BP : 38.00 exp GWP : 0.00 MW : 295.93 TC : 8.54
Rank:
37
101
105
8
Rank:
61
94
84
19
002314978 Methane, trifluoroiodo-
g y BP: -22.50exp GWP : 0.12 MW : 195.91 TC : 8.06
Rank:
92
61
101
000425887 1 -Methoxy-1,1,2,2-tetrafluoroethane
gg BP: -12.54 GWP: 0.08 MW: 132.00 TC: 12.00
Rank:
84
65
64
47
032778168 1 -Difluoromethoxy-2,2-difluoroethane
gg BP: -1.54 GWP: 0.02 MW: 132.00 TC: 12.00
Rank: 64
85
65
50
F I F
F F
001814886 1,1,1,2,2-Pentafluoropropane
oc BP: -17.60exp GWP: 0.19 MW: 134.05 TC: 11.50 exp F>
Rank: 88 55 72 41
000690391 1,1,1,3,3,3-HexafIuoropropane
gg BP: -0.07 exp GWP: 0.00 MW: 152.04 TC : 10.10
F I H
H
H
H
F
I
FJ,
F
F F
F
-0
F F
F
CH,
•o
CHF,
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/(m - K)
MW = Molecular weight
GWP = Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
65
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
069948294 1-Difluoromethoxy-1,1-difluoroethane
qq BP; -12.54 GWP: 0.06 MW: 132.00 TC: 12.00
Rank:
85
69
66
51
-O
CHF,
000382343 1,1,2,3,3,3-PentafIuoropropyl methyl ether
g *j BP; -7.07 GWP: 0.08 MW: 182.00 TC: 11.00
Rank:
78
66
100
30
92
Rank;
103
95
55
25
CH,
000354336 Ethane, pentafluoro- . .
BP: -48.50exp GWP: 0.00 MW : 120.02 TC: 10.90 exp H—^ ^-F
032778113 1 -Difluoromethoxy-1,1,2,2-tetrafluoroethane
Q0 BP: -3.10 exp GWP: 0.05 MW: 168.00 TC: 11.50
Rank:
71
74
93
42
F F
F F
-o
CHF,
144109035 1,1,2,2,3-Pentafluorooxetane
04 BP; 3.40 exp GWP; 0.03 MW: 148.03 TC: 13.00
Rank:
53
78
78
80
F .0
-Vr
F F
056281926 1-Difluoromethoxy-1,2,2-trifluorocthane
gg BP: -15.58 GWP: 0.02 MW: 150.00 TC: 11.70
Rank: 87
80
80
44
- ^0^CF,H
000421147 Trifluoromethyl methyl ether
96 BP:-24.10exp GWP: 0.07 MW: 100.04 TC : 13.70 exp
Rank: 93
67
44
87
H,C^ ^CF3
o
133360006 2,3,4,5-Tetrafluorotetrahydrofuran
gy BP: 49.77 GWP: 0.14 MW: 144.00 TC : 14.80
Rank;
66
57
75
100
002252848 1,1,1,2,2,3,3-HeptafIuoropropane
gg BP: -17.70exp GWP: 0.02 MW; 170.03 TC : 11.00
Rank:
89
81
95
35
F
ti
F F
F
.F
F I H
F F
BP = Boiling point in degrees C exp » experimental value
TC * Vapor thermal conductivity in mW/lm - K)
MW = Molecular weight
GWP — Atmospheric hydoxyl radical reaction rate in cu-cm/rnolecule-sec
66
-------
Table 4. Final Ranking of Blowing Agent Candidates (continued)
000382105 1-Propene, 3,3,3-trifluoro-2-{trifluoromethyl)-
gg BP: -29.10 GWP: 51.40 MW: 164.05 TC: 17.00
Rank:
99
89
105
000931919 Hexafluorocyclopropane
100 BP : -47,70 GWP: 0.00 MW : 150.00 TC: 10.90
Rank: 102
102
79
28
000431890 1,1,1,2,3,3,3-Heptafluoropropane
1Q1 BP: -18.70exp GWP: 0.00 MW: 170.03 TC: 11.00
Rank: 91
98
94
33
001479498 Trifluoromethyl ether
102 BP: -58.70exp GWP: 0.00 MW: 154.01 TC: 12.70
Rank: 105
103
86
72
H I F
F F
k. /J
Yr
003822682 Trifluoromethyl difluoromethyl ether
103 BP : -34.60exp GWP: 0.01 MW : 136.02 TC : 16.20 exp
Rank: 100
91
73
104
E
000425821 1,1,2,2,3,3-Hexafluorooxetane
104 BP : -28.20 exp GWP: 0.00 MW : 166.02 TC : 13.70
Rank: 98
104
90
88
F
F
O
F
F
000684162 2-Propanone, hexafluoro
BP: -26.00exp GWP: 0.00 MW: 166.02 TC: 13.70 exp
Rank: 95 105 91 89 F-
BP = Boiling point in degrees C exp = experimental value
TC = Vapor thermal conductivity in mW/(m - K)
MW = Molecular weight
GWP - Atmospheric hydoxyl radical reaction rate in cu-cm/molecule-sec
67
-------
heading BP refers to ABP (in °C), GWP refers to the hydroxyl radical rate constant (in
em3/molecuIe-sec X1012), MW refers to the molecular weight, and TC refers to vapor thermal
conductivity in mW/(m K).
This ranking exercise produced other interesting results which will be discussed in the
following section. For example, unsaturated compounds in the ranking list may also undergo
atmospheric reactions with ozone and/or nitrate radicals which would shorten their atmospheric
lifetime and, thus, they should be moved to a higher rank in the GWP ranking criteria.
Perfluoroalkyl iodides do not react with hydroxyl radicals and, for this exercise, were ranked very
low for GWP; however, this class of compounds is known to directly photodegrade in the
atmosphere upon exposure to UV radiation. Therefore, the global warming potential would be
considerably lower than indicated in the ranking exercise and these compounds should not be
removed from further consideration based solely on this criteria.
A wide range of chemical compounds were considered for this project. Some of these
compounds have not been previously discussed in the chemistry literature and, therefore, do not
possess CAS Registry numbers. To facilitate the extensive electronic data manipulation
operations utilized in this project, these compounds were provided with an artificial number, or a
CAS Registry numbers for a closely related, generic species, or for one of two possible geometric
isomers. These compounds are listed in Table 5.
68
-------
Table 5, Compounds with Artificial CAS Registry Numbers
CAS No.
Name
Notes
129362-97-6 1,2,3,4-Tetrafluorocyclobutane
6104
1,2,3-Trifluorocyclobutane
113742-90-8 1,2-Difluorocyclobutane
6108
6109
6119
1,2,3-Trifluorocyclopentane
1,2,3.4-Tetrafluorocyclopentane
50422-76-9 1 -Fluoro-2-ethylcyclopropane
Trifluoromethoxy-
methoxymethane
CAS Registry number is for generic
compound, tctrafluorocyclobutane
Compound does not exist in chemical
literature
CAS Registry number is for the trans
isomer
Compound does not exist in chemical
literature
Compound does not exist in chemical
literature
CAS Registry number is for the trans
isomer
Compound does not exist in chemical
literature
Task 3. Evaluation of Potential New Foam Blowing Agents
In order to efficiently evaluate potential new foam blowing agents, the compounds were
placed in a series of fourteen groups based on chemical structure. The chemical structure of a
compound ultimately determines the physical/chemical properties it will possess. By placing
compounds in chemical groups, similarities can be discussed collectively and trends that
represent differences can be identified. A complete listing of the chemicals compounds used in
our scoring exercise sorted by chemical group is provided in Table 6. In addition to the overall
rank, Table 6 also contains the order rank of each compound in each of the four criteria areas.
In the following, there are three areas of discussion on each group. A general section
identifies the members of the groups along with a potentially wide-ranging discussion of areas
that directly relate to their potential use as blowing agents. This may include a brief discussion
69
-------
Table 6. Group Ranking of Blowing Agent Candidates
A. Cyclopentane and cyclopentene
O
o
13
BP : 52 MW :9
GWP ; 2 TC ; 24
BP : 68 MW :11
GWP : 18 TC : 54
B. Simple olefins
BP: 7 MW :10
GWP : 8 TC : 68
H„C
3
ch3
3
BP : 20 MW :13
GWP : 3 TC : 76
BP : 34 MW :12
GWP : 4 TC : 70
BP: 18 MW :14
GWP : 10 TC : 86
CH,
h3c
8
CH,
BP: 30 MW :15
GWP : 1 TC : 93
H.C
H ,C
CH,
CH,
10
BP : 44 MW :26
GWP : 12 TC : 61
h3c
12
BP : 58 MW :3
GWP : 5 TC : 83
BP ; 76 MW ;25
GWP : 11 TC : 43
H,C
CH0
CH,
31
BP : 79 MW :24
GWP : 7 TC : 71
C. Cyclobutane analogues
P F
_/
F
BP: 25 MW :17 I7 BP : 1 MW :34
GWP : 6 TC : 67 GWP : 49 TC : 73
1
rf
19
BP: 15 MW :20
GWP : 43 TC : 85
iC
23
BP : 13 MW :35
GWP : 40 TC : 74
26
F
/-Y
BP: 31 MW :S
GWP : 36 TC : 99
28 BP : 12 MW :48 4-3 BP: 26 MW :58 54 BP : 59 MW 59
GWP : 58 TC ; 59
GWP : 72 TC : 39
GWP : 44 TC : 45
70
-------
Table 6. Group Ranking of Blowing Agent Candidates (continued)
C. Cyclobutane analogues
F
74 BP: 36 MW :98
GWP : 45 TO : 56
D, Fluoririated propanes and butanes
h3c
7
BP : 23 MW :22
GWP : 28 TC : 65
Hs
H
H
• F F
9 BP: 5 MW :69
GWP : 59 TC : 9
H F
'-V^Sc
14
H
H
F
BP: 4 MW :70
GWP: 70 TC : 10
18
BP: 14 MW :38
GWP : 30 TC : 77
H
H
F
H
21 BP : 3 MW ;92 32 BP : 21 MW :71
GWP : 56 TC : 14
GWP : 77 TC : 13
BP : 40 MW :40
GWP : 31 TC : 79
BP: 60 MW :49
GWP : 33 TC : 49
F H
42 BP : 65 MW :53
GWP : 54 TC : 23
H I F
H
H
H>
*F
BP : 39 MW :39 47 BP : 41 MW :68 50 BP: 35 MW :S2
GWP : 41 TC ; 78
GWP : 83 TC : 6
GWP : 75 TC : 12
BP: 86 MW :42 71 BP: 63 MW :83
GWP : 51 TC : 31
GWP : 62 TC : 18
CH,
h3c-
CH,
73
H
BP : 73 MW :23 75 BP: 46 MW :85
GWP : 46 TC : 91
GWP : 88 TC : 20
F
H
H
H
F
H
85 BP: 88 MW :72 86 BP: 61 MW :84 98 BP: 89 MW :95 101 BP: 91 MW :94
GWP : 55 TC : 41
GWP : 94 TC : 19
GWP : 81 TC : 35
GWP : 98 TC : 33
71
-------
Table 6. Group Ranking of Blowing Agent Candidates (continued)
E, Pentanes and hexanes
CH,
h3c-
A
CH,
11
BP: 11 MW :18
GWP : 21 TC : 97
BP : 33 MW :19
GWP : 20 TC : 98
CH
3 CH,
h3c-
CH,
BP: 83 MW :27
GWP ; 17 TC : 60
CH,
h3c-
51
ch3 ch3
BP : 69 MW :28
GWP ; 26 TC ; 81
F. HFEs
H.
15
Y
F H
BP : 17 MW :43
GWP : 73 TC : 21
h3c*
27
-0,
.0,
CF,
BP; 16 MW :61
GWP : 24 TC : 75
F F
F F
44
CH,
BP : 24 MW #6
GWP : 33 TC ; 57
h3c
CF,
58
BP : 56 MW :52
GWP : 39 TC : 63
F
60
30<
F
0 F
BP : 10 MW :63
GWP : 82 TC : 58
BP : 50 MW :67
GWP : 42 TC ; 55
BP : 55 MW :51
GWP ; 48 TC ; 62
67
BP : 38 MW :99
GWP: 64 TC: 17
F^O
83
y
H H
BP : 48 MW :54
GWP : 84 TC : 64
F F
CH,
F F 3
88
BP : 84 MW :64
GWP : 65 TC : 47
CHF,
BP : 64 MW :65
GWP : 85 TC : 50
-o.
CHF,
90
BP : 85 MW :66
GWP : 69 TC : 51
F F
-o
CHF,
F F
91 BP: 78 MW:100
GWP : 66 TC : 30
F F
93
BP : 71 MW 33
GWP ; 74 TC : 42
Je O
•-Vr
94
,CF2H
BP : 53 MW :78 95 BP : 87 MW SO
GWP : 78 TC : 80
GWP : 80 TC : 44
h3c^cf3
96
BP : 93 MW :44
GWP : 67 TC : 87
n
I
Y
F F
Q7
M/ BP : 66 MW :75
GWP : 57 TC ; 100
102
BP : 105 MW £6
GWP : 103 TC : 72
Y Y
103
BP : 100 MW :73
GWP : 91 TC : 104
72
-------
Table 6, Group Ranking of Blowing Agent Candidates (continued)
F. HFEs
o
>9<;
104
BP : 98 MW :90
GWP : 104 TC : 88
G. Ethers
-CV >0.
3
33
CH,
0—|
~
38
h3c.
CH,
CH,
CH,
BP : 45 MW :21
GWP : 16 TC : 101
BP : 70 MW :6 72 BP; 80 MW :30
GWP : 22 TC : 92
GWP ; 25 TC : 94
H. Carbonyl compounds
o
20 BP : 28 MW :36
GWP ; 68 TC : 32
0
H
F
22 BP:
F
H
MW :62
GWP : 87 TC : 16
0
h3c
29
CH,
BP ;
GWP : S3 TC : 38
O
CH,
81 MW :7 39 BP : 9 MW :50
GWP : 86 TC : 46
O
F
F F
48 BP ; 13 MW :60
GWP : 90 TC ; 36
-CH,
O
F
49 BP : 49 MW :57
GWP ; 71 TC : 26
O
F
H
F F
56 BP : 22 MW :77
GWP : 96 TC : 15
F F
59 BP: 67 MW :37
GWP : 60 TC : 48
F
F
F F
105 BP: 95 MW:91
GWP : 105 TC : 89
I, Fluorinated olefins
,F
HX
'!srs*yC
25
BP : 90 MW ;41
GWP ; 13 TC : 27
F-v ^
F
F F
55 BP: 72 MW :88
GWP : 14 TC : 34
F
64 BP:
F
97 MW :81
GWP : 15 TC : 22
99 BP
F
99 MW :89
GWP :9 TC : 105
73
-------
Table 6. Group Ranking of Blowing Agent Candidates (continued)
J. Cyclopropanes
CH,
h3c
35
A
BP : 29 MW :16
GWP : 32 TC : 103
BP: 51 MW :4
GWP : 50 TC : 84
V
CH,
J
63
BP: 54 MW;31
GWP : 34 TC : 95
A
76
BP; 75 MW :32
GWP : 37 TC : 96
F.
F
100
F
F
BP : 102 MW :79
GWP : 102 TC : 28
K. Fluorinated cyelopentanes
F F
36
BP : 27 MW :97
GWP : 29 TC : 37
41
BP : 57 MW ;47
GWP : 19 TC : 69
52
BP : 62 MW :56
GWP : 35 TC : 52
61 BP ; 74 MW :46
GWP : 27 TC : 66
66 BP : 82 MW :29
GWP : 23 TC : 82
69
BP : 47 MW :74
GWP : 47 TC : 53
L. Fluoroiodoalkanes
F
45
BP : 6 MW :96
GWP : 93 TC ; 2
f F
F F
77
BP: 32 MW :103
GWP : 100 TC : 7
H
F
78
BP : 77 MW :87
GWP : 79 TC : 1
i-) fH
F F
81
BP: 43 MW :102
GWP : 97 TC : 3
F I I
F
F
82 BP: 42 MW :104 84 BP: 37 MW :105
GWP : 99 TC : 4 GWP : 101 TC : 8
BP: 92 MW :101
GWP : 61 TC : 5
74
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Table 6. Group Ranking of Blowing Agent Candidates (continued)
M. Fluorinated methane and ethanes
F F F H
J. F-) (~F
H3<= F "TF F/ \
68 ?0 H 79
BP: 94 MW :8 BP: 104 MW :2 BP: 86 MW :45
GWP : 76 TC : 40 GWP : 83 TC : 29 GWP : 92 TC : 11
H~) fF
F F
92
BP : 103 MW :55
GWP : 95 TC : 25
N. Silicon containing compounds
CH,
I 3
CH3-Si-CH3
ch3
53
BP : 8 MW ;33
GWP : 63 TC : 102
H H
H-^ ^-F
H H
80
BP: 101 MW:1
GWP : 52 TC : 90
75
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of physical/chemical properties. For a complete listing of physical/chemical properties, please
refer to Appendices B, C, D, and E. The second section, manufacture, briefly indicates the
commercial availability of the members of the group. The commercial availability of all
compounds considered in the ranking exercise is provided in Appendix A. The determination of
commercial availability was obtained by searching chemical company catalogues, articles from
trade journals collected for this project, and on-line searches (using STN) of the CSCHEM
database (for a limited number of compounds), as well as the chemical intuition of the authors of
this report. Appendix A cannot be considered a comprehensive compilation of commercial
availability, but rather an indication of the likelihood that a compound would need to be
synthesized before experimental data could be obtained. The final section, toxicity, provides an
indication of the potential health and ecological effects of the group members. Toxicity
information was obtained by searching the Registry of Toxic Effects for Chemical Susbstances
(RTECS) current awareness file, the Toxic Substances Control Act Test Submission (TSCATS)
database (Santodonato, J. et ah, 1987), and the Integrated Risk Information System (IRIS).
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Group A - Cyclopentane and Cyclopentene
O
o
General
The commercialization of cyclopentane as a blowing agent for refrigerator and
construction foams has been demonstrated by European manufacturers (Volkert, O., 1993;
Walker, G. et al., 1993; Kuhn, E. and Schindler, P., 1993), The physical/chemical properties for
cyclopentane, its cyclic geometry, and its commercialization as a blowing agent led to the
investigation of closely related analogues. Cyclopentene was chosen for investigation as it would
be expected to react more rapidly with photochemically produced hydroxyl radicals and, thus,
would be expected to have a shorter atmospheric lifetime and corresponding lower GWP,
Moreover, cyclic hydrocarbons tend to have lower vapor thermal conductivities than their
straight-chain analogues and its physical/chemical properties would be expected to be similar to
cyclopentane.
Using our ordering scheme, cyclopentene is the highest ranked alternative blowing agent
for rigid polyurethane foams and cyclopentane ranked number 13. Given the commercial success
of cyclopentane as a blowing agent, the relatively close ranking of cyclopentane and
cyclopentene, and their comparable physical/chemical properties, these two compounds were
combined into a single group.
The higher ranking of cyclopentene over cyclopentane is consistent with the overall
premise of the ordering exercise. Cyclopentene has a slightly lower molecular weight than
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cyclopentane, a lower vapor thermal conductivity, a boiling point closer to CFC 12, and a lower
expected GWP. These differences in the four ordering criteria are all in a direction that would be
expected to produce a better foam blowing agent.
Manufacture
Both cyclopentene and cyclopentane are commercially available and relatively
inexpensive. They are produced by the hydrogenation of cyclopentadiene which is obtained from
the steam cracking of naphtha feedstocks (Griesbaum, K. et al., 1987; Griesbaum, K. et al.,
1989).
Toxicity
Cyclopentene has an oral LD50 in rats of 1656 mg/kg and a LD50 in rabbits of 1231 mg/kg
by dermal application as reported in RTECS.
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Group B - Simple Olefins
CH.
'CH3 H2C
-------
expected atmospheric lifetime, is an important contributor to the high ranking of 1,4-pentadiene
(ranked second overall). It is also important to note that this higher chemical reactivity of the
dienes (and to some extent, all members of this group) is expected to be of consequence in the
available purity of the blowing agent feedstock, stability in storage, and stability in the foam. No
problems are expected to arise during the actual blowing of the foam.
Manufacture
All members of this group are commercially available and are readily obtained from the
thermal cracking of wet natural gas and petroleum fractions (Gricsbaum, K. et al., 1989).
Toxicity
According to abstracted studies in TSCATS, concern for inhalation genotoxicity in mice
for 2-methyl-2-butene and 2-methyl-l-butene exists. In RTECS, an LC50 of 425 ppm by
inhalation in mice is reported for both compounds.
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Group C - Cyclobutane Analogs
~
¦CF,
General
Group C is a novel group of compounds that have not previously been considered as foam
blowing agents. Indeed, some members of this group have not been discussed in the chemical
literature (that is, no CAS number has been assigned). The first member of this group,
3-fluorocyclobutene ranked as one of the top five candidates in the overall rank while the mono-,
di-, trifluoroeyclobutanes all ranked relatively closely to one another (17, 19, 23, and 28) as did
the two tetrafluorocyclobutanes (43 and 54).
The reasons that members of this group ranked relatively well are due to their boiling
point, relatively low molecular weight, and relatively rapid rate of atmospheric destruction.
Their vapor thermal conductivity values are all pretty close together. Although not outstanding,
their thermal conductivities are in the middle of the range [11-12 mW/(m K)] of chemicals
considered during this project.
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Cyclobutane itself was placed in this group because of its similar structural backbone.
However, cyclobutane does not appear to offer any advantages over the use of cyclopentane as a
blowing agent and is hampered by the expected higher cost relative to cyclopentane.
Manufacture
Cyclobutane is the only member of this group known to be commercially available. Of
the fluorinated isomers, 1,1,2,2-tetrafluorocyclobutane used to be commercially available but it is
not known if it is currently available. One of the interesting aspects of this group is that the
mono-, di-, and trifluorocyclobutanes are ranked relatively close together. For this reason, it is
not unreasonable to expect that a mixture of these compounds would also make a suitable
blowing agent. This may offer some manufacturing benefits as a commercial synthesis of one
isomer is likely to produce (or have as impurities) the others. If the final product was intended to
be a mixture of the isomers, the synthetic process and the purification step would be simplified
and the associated production costs would be lower.
Toxicity
No data were located.
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Group D - Fluorinated Propanes and Butanes
General
This group is comprised of three and four carbon HFCs, Industrial concerns have
expended significant effort looking at this group of compounds because they are expected to have
similar physical/chemical properties to current blowing agents and refrigerants but do not contain
chlorine like HCFCs. A complete discussion of HFC research is outside the scope of this
document; however, industrial experiments often include foaming trials that provide an
indication of the compound's usefulness as a blowing agent as well as the properties of the
resulting foam. According to the literature, HFCs of this group with potential as blowing agent
substitutes include HFC 356 (1,1,1,4,4,4-hcxafluorobutane) and 227 (1,1,1,2,3,3,3-
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heptafluoropropane) (Ball, EE. and Lamberts, WM„ 1993; Yu-Halada, LC, and Reichel, CJ., 1993).
An interesting result from the ranking exercise on this group of compounds was that both
the number and the position of the fluorine substituents strongly affected the overall score.
For example, 1-fluorobutane ranked 7 and 1,1,1,2,3,3,3-heptafluoropropane ranked 101; there
was not a linear correlation based on the number and position of fluorine atoms between these
two extremes.
There is some evidence that some of the HFCs, particularly those with a CF, group, may
not be as environmentally benign as originally believed. Although these experiments were
performed on lluorinatcd ethanes (Ravishankara, AR. et al., 1994; Wallington, TJ. and
Schneider, WF., 1994), the authors found that trifluoromethyloxy radicals could be formed which
could participate in the catalyzed destruction of stratospheric ozone. The authors have stated that
their kinetic models indicate that the ozone depletion potential from these compounds is expected
to be negligible.
In the atmosphere, HFCs containing a CF3 group may also react with photochemically
produced hydroxyl radicals producing trifluoroacetate. Trifluoroacetate can then undergo
atmospheric removal, most likely by a wet deposition process. It has recently been shown
(Visscher, PT. et al., 1994) that trifluoroacetate can biodegrade to fluoroform (trifluoromethane).
Fluoroform is a volatile compound with a relatively long atmospheric half-life, Fluoroform may
also be a potential ozone-depleting compound (Chemical Marketing Reporter, 1994) as recent
workers have suggested that molecules containing the CF, group may represent a special case of
fluorine-catalyzed ozone loss through cycles involving trifluorooxy and peroxy radicals
(Ravishankara, AR. et al., 1994) although others have indicated that these reactions are not viable
(Wallington, TJ. et al., 1994). Given that research in this area has just begun, the best HFC
84
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blowing agent replacements from this group (as well as group M) may be those that do not
contain a CF3 group.
A number of workers have determined that highly fluorinated HFCs are expected to have
long atmospheric lifetimes (Ravishankara, AR. et ah, 1993; Zhang, Z. et al., 1994), as
determined by slow experimental rates constants for the gas-phase reaction with hydroxyl
radicals. These result are consistent with the method for ranking GWP used in this project as the
highly fluorinated HFCs ranked relatively low in the GWP ranking criteria.
Manufacture
Some members of this group are available commercially or have been synthesized from
research purposes. To our knowledge, none of the HFCs from this group are in large scale
commercial production (like those of group M, fluorinated ethanes and methane). Appendix A
has more information on the availability of these group members.
Toxicity
1,4-difluoro-butane has a LD50 in mice of 3400 pg/kg by intraperitoneal injection and
1,1,1,3,3,3-hexafluoropropane has a LC10 in mice of 44 pph/10 minutes by inhalation as reported
in RTECS.
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Group E - Pentanes and Hexanes
ch3
\
ch3
h3c
ch3 CH3 CH3
CH H3C—1—( H3C \
ch3 ch3 ch3
General
The five and six carbon alkanes that met the boiling point criteria were placed in this
group. They ranked relatively close together in the ordering exercise at positions 11,24, 34, and
51. Pentane and /'w-pentane have been used commercially as blowing agents for rigid
polyurethane foams (Taverna, M. and Corradi, P., 1994; ES&T, 1994),
Manufacture
The members of this group are all commercially available and are fairly inexpensive.
n-Pentane is obtained directly from the distillation of petroleum fractions and /so-pentane is
obtained from the acid catalyzed isomerization of n-pentane (Griesbaum, K. et aL, 1989). The
other members of this group are obtained by the cracking of petrochemical feedstocks followed
by distillation.
According to abstracted studies in TSCATS, toxicity following subchronic exposure was
observed in male rats receiving 0.5 or 2.0 g/kg n-pentane once daily by oral gavage. For iso-
pentane and 2,3-dirncthyl butane, there is some data that indicates a concern for oral subchronic
Toxicity
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toxicity in rats. In RTECS an LC50 in rats of 364 g/m3/4 hrs by inhalation and a intravenous LDS0
in mice of 446 mg/kg are reported for pentane.
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Group F - HFEs
F
General
The members of this group consist of both the cyclic and acyclic fluorinated ethers.
Because this group encompasses such a large variety of fluorination patterns and ether side
chains that represent large differences in all four of the ranking criteria, no generalized trends
be made concerning this group. Some members possess all the requisite properties to be
considered highly desirable as blowing agents.
88
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Manufacture
Only one member of this group is available commercially, bis-2,2,2-trifluoroethyl ether,
and a number have been synthesized in small quantities for research purposes.
Toxicity
Bis-2,2,2-trifluoroethylether has a LD5P in rats of 1260 mg/kg by intraperitoneal injection
and a LD50 in mice of 46 mg/kg by intravenous injection.
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Group G - Ethers
CH3
o-
U
ch3
General
The ethers from the initial list of compounds that met the boiling point criteria for this
project were grouped together. Although these compounds ranked relatively well in GWP and
molecular weight and reasonably well in boiling point, their thermal conductivities were among
the highest of the compounds that were looked at.
Manufacture
All compounds in this group are commercially available. Methyl-fcrf-butyl ether is
produced in billions of pounds annually by the catalyzed reaction of methanol with /so-butcnc
(Kiem, W. and Roper, M., 1985). Dimethoxy methane is produced by the reaction of
formaldehyde and methanol (Falbe, J. et al,, 1985).
According to abstracted studies in TSCATS, chronic exposure to relatively high levels of
methyi-fer/-butyl ether (4,000-8,000 ppm) caused progressive nephrosis or nephropathy in the
kidneys in male rats; exposure of male and female rats for long periods during mating and
gestation resulted in some developmental affects. High concentrations also had a sedative
affects.
Toxicity
90
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MethyRert-butyl ether has an oral LD50 in rats of 4 g/kg, a LC50 in rats of 23576 ppm/4
hrs by inhalation, a LD50 in rats of >148 mg/kg by intraperitoneal injection, and a LC50 in mice
141 g/m3/15 minutes by inhalation as listed in RTECS.
Methyl-/ert-butyl ether has an oral LDS0 in rats of 3899 mg/kg with ataxia and central
nervous system depression noted at 1900 to 3160 mg/kg, and the 4-hour inhalation LCS0 in rats
was 39,000 ppm resulting in irritation and prostration (Bosch, SJ. and Basu, DK., 1992). In
repeat exposure oral studies in rats, 14, and 90 days, the lowest effective dose was 100 mg/kg/day
which produced diarrhea, while doses greater than 300 mg/kg/day produced changes in organ
weight. In repeat exposure inhalation studies in rats and mice (9 and 13 exposures; 6 hours/day),
exposure produced irritation of the respiratory tract at 2970 ppm and ataxia at 4000 ppm.
Methyl-fcrr-butyl ether had little effect on reproduction in a one and two generation inhalation
study except at exposure levels in the range of 1200 to 3300 ppm in rats, mice, and rabbits.
According to abstracted TSCATS studies, dimethoxymethane has a LD50 for rats of 7.46
ml/kg of body weight by oral gavage and 16.0 ml/kg of body weight for rabbits by dermal
application and the LTJ0 for saturated vapor inhalation was 19.8 for male rats and 25.5 minutes
for females. Single applications of 5 g/kg dimethoxymethane resulted in no deaths with rabbits.
Dimethoxymethane has a LCJ0 in rats of 15,000 ppm by inhalation, a LCS0 in mice of 57 g/m3/7
hrs by inhalation, and a LDS0 in rabbits of 5,708 mg/kg orally as listed in RTECS.
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Group H - Carbonyl Compounds
o o o o
o o o o
F F F F F F F
General
This group is composed mainly of fluorinatcd acetone isomers including acetone itself,
and a fiuorinated ester. Although these compounds ranked well in the scoring exercise, there is a
concern, especially for the highly fiuorinated compounds, that they may react with the isocyanate
groups in the foam feedstocks. This is due to the high electronegativity of the fluorine groups
withdrawing electron density from the carbonyl compound such that a stable ketal could be
formed. For this reason, it is suggested that they be tested in foaming trials before they are
recommended as HCFC alternatives. Acetone itself has been utilized successfully in foaming
trials (Kaufman, CM. and Overcash, MR., 1993),
Man.ufac.ture
Acetone is an import industrial chemical and is widely available. Some of the fiuorinated
compounds are available in research quantities from commercial sources such as Aldrich
Chemical Company. In general, the synthesis of the remaining members of this group is not
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expected to be overly troublesome due to the ease of placing substituents next to a carbonyl
group.
Toxicity
According to abstracted studies in TSCATS, there is a concern for developmental and
reproductive toxicity in rats for hexafluoroacetone. Hexafiuoroaeetone causes testicular damage,
bone marrow effects, and kidney damage in rats, and increases lung weight in dogs (Kennedy,
GL., 1990). Acetone has an oral LDS0 in rats of 5800 mg/kg, a LC50 in rats of 50100 mg/m3/8 hrs
by inhalation, LD50 in rats of 5500 mg/kg by intravenous injection, an oral LD50 in mice of 3
g/kg, a LD50 in mice of 1297 mg/kg by intraperitoneal injection, an oral LDS0 in rabbits of 5340
mg/kg, a LD50 in rabbits of 20 g/kg by dermal application, and a LD50 in guinea pigs of >9400
mg/kg by dermal application as reported in RTECS. 1,1,1,3,3,3-Hcxafluoro-2-propanonc has an
oral LD10 in rats of 191 mg/kg and a LC50 in rats of 275 ppm/3 hrs by inhalation. All fluorinated
members of this group that are sold by Aldrich are listed as lachrymators which would require
exposure controls to reduce occupational exposure.
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Group I - Fluorinated Olefins
F F
F
CF
F
General
The fluorinated olefins were investigated as they were expected to have a number of
properties that offered advantages over their saturated analogues, the HFCs. These properties
were a lower expected vapor thermal conductivity and shorter atmospheric lifetime and, of
course, a somewhat lower molecular weight. Although the members of this group did rank
relatively high in the GWP scoring, modest gains in molecular weight were more than offset by
unexpected large drops in boiling point. Identifying new members of this group that better
balance molecular weight (i.e., not too high due to a high degree of fluorination) and boiling
point (i.e., one that is not a gas at room temperature) may produce a highly ranking blowing agent
substitute.
Manufacture
Two members of this group are commercially available, 3,3,3-trifluoro-1 -propene and
1,1,2,3,3-hexafluoro-1 -propcnc; the former is a relatively high volume feedstock for
polypropylene plastics.
Toxicity
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According to abstracted studies in TSCATS, the approximate lethal inhalation
concentration of hexafluoropropene in rats was 735 ppm. Hexafluoropropene was classified as
weakly positive for clastogenicity in male mice. For hexafluoro-i.w-butylene, there is a concern
for mutagenicity in mice and bacteria. For 3,3,3 -trifluoropropene, there is a concern for acute
toxicity by inhalation in mice with an LC50 value of 1.75 g/L (445,000 ppm). It was also
classified as mutagenic in the Ames assay.
Hexafluoro-propene has a LC50 in rats of 1200 mg/m3/4 hrs by inhalation and a LCS0 in
mice of 750 ppm/4 hrs by inhalation as reported by RTECS. 3,3,3-Trifluoro-2-(trifluoromethyl)-
propene has a LC50 in rats of 1425 ppm/4 hrs by inhalation and 3,3,3-trifluoropropene has a LC50
in mice of 1691 g/m3/2 hrs by inhalation.
The fluorinated olefin perfluoro-iso-butene appeared on the initial list of potential
blowing agent substitutes. This compound is listed in the Chemical Weapons Convention treaty
(C&E News, 1993) because it is extremely toxic (Kennedy, GL., 1990) and, therefore, it was
removed from further consideration. The toxicity of perfluoro-wo-butene arises from the
formation of hydrofluoric acid by hydrolysis (in the lung tissue). The geometric isomer
perfluoro-2-butene does not display this high level of toxicity. Because of these large changes in
toxicity with relatively minor structural changes, more thorough toxicological investigation of the
members of this group is required before they can be considered acceptable blowing agent
substitutes.
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Group J - Cyclopropanes
L ' ».c^ ,X /T' l^x'
General
Little experimental data are available for this novel group of alternative blowing agents.
Surprisingly, the non-fluorinated compounds in this group ranked higher than the fluorinated
one. This may be an artifact of the boiling point term in the scoring exercise as the regression
equations used in the estimation of boiling points may not work well for the cyclopropane
functional group. An interesting area for future work would be to obtain experimental data for
this group of compounds.
Manufacture
None of the compounds in this group are commercially available.
Toxicity
No data were located.
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Group K - Fluorinated Cyclopentanes
F
F
F
F
F
F
F
F
F
F
F
F F
General
With the commercial success of cyclopentane as a blowing agent as well as its high
ranking in this scoring exercise, fluorinated cyclopentanes were considered for investigation in
this study. To the best of our knowledge, members of this group have not previously been
considered as blowing agents. The interest in these compounds was based on an expected
decrease in the vapor thermal conductivity with the addition of fluorine groups. Similar to the
fluorinated cvclobutanes, the members of this group ranked relatively close together (position 36
to 69) but, surprisingly, lower than cyclopentane itself. Given the potential for relatively large
errors in estimated physical/chemical properties for cyclic compounds (as discussed above for the
cyclobutane group) experimental measurements would aid in the assessment of the potential of
these compounds as alternative blowing agents.
Manufacture
No members of this group are commercially available.
Toxicity
No data were located.
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Group L - Fluoroiodoalkanes
H.
F F u H
,-^F H'
F F
F F
I-) fH
F F
F F.
F F
F F.
F
General
Consideration of fluoroiodoalkanes arose from their initial marketing as a haJon and CFC
replacement by a small research organization (Nimitz, J. and Lankford, PE., 1993; Lank ford. PB.
and Nimitz, J., 1993). The potential advantages from this class of compounds come from their
expected low vapor thermal conductivity (due to their high degree of fluorination) and expected
low atmospheric lifetime due to direct photolysis of the carbon-iodine bond. A major
disadvantage of the members of this group is their high molecular weight.
Members of this group possessed the lowest overall vapor thermal conductivity; the seven
members ranked 7th, 1st, 8th, 4th, 2nd, 5th, and 3rd in order of their appearance as shown above. In
the molecular weight category, all members of this group ranked near the bottom, as expected.
Overall, the fully fluorinated members of this group did not score very well The best
showing was for pentafluoroiodoethane at position 77. It is important to note that the fully
fluorinated members of this group could not be ranked for GWP using our scoring criteria. We
based the GWP on the atmospheric half-life, which, in turn, was determined from the
atmospheric reaction rate with photochemically produced hydroxyl radicals. For a saturated
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compound to react with hydroxyl radicals in the atmosphere, it must contain a hydrogen atom (at
least within the restraints of our estimation program). Therefore, the fully fluorinated members
of this group scored at the very bottom in the GWP category. Moreover, the three members of
this group that contain a hydrogen atom were also estimated to be essentially unreactive towards
atmospheric hydroxyl radicals and, thus, also scored near the bottom of the GWP category.
This group of compounds is unique in that of all the different types of compounds looked
at for this project, the fluoroiodoalkanes are the only ones that are expected to undergo efficient
atmospheric removal by a process other than oxidation by hydroxyl radicals. A carbon-iodine
bond is well known to be susceptible to photolysis. The estimated atmospheric lifetime of
methyl iodide is 5 days (Rasmussen, RA. et al., 1982; Chemeides, WL. and Davis, DD., 1980).
Although experimental evidence is lacking, the members of this group are expected to have short
atmospheric lifetimes as the fluorine substituents should not significantly diminish the rate of
carbon-iodine photolysis. Therefore, the members of this group are not expected to have a high
GWP, at least not as high as our ordering exercise suggests.
The largest potential drawback of the members of this group is, therefore, their high
molecular weight. The low vapor thermal conductivity and other desirable properties of some
members of this group dictate that they should be given further consideration as potential
polyurethane blowing agent substitutes, although their high molecular weights are likely to
increase the cost associated with the production of the rigid foam.
Manufacture
Iodofluoromethane, iododifluoromethane, and l-iodo-l,l,2,2-tetrafluoroethane are the
members of this group that are not commercially available. Trifluoroiodmethane is undergoing
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extensive research as a replacement for the fire-fighting agent Halon 1301 and ASTM is
currently developing a research and testing material specification for this compound (ASTM,
1994). The other members of this group are available in research quantities (Nimitz, J. and
Lankford, PE„ 1993).
Toxicity
Heptafluoro-l-iodo-propane has a LC.50 in mice of 404 g/m:V2 hrs by inhalation as
reported in RTECS.
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Group M - Fluorinated Methane and Ethanes
F f f H H H F F
HrAc H^F ("F H~) fF H~) fF
H3C F H p F H H H F F
General
This is the second group of HFCs and is limited to methane and ethane analogues. The
general properties for this group are the same as those discussed for Group D. In general, this
group did not score very well in our ordering exercise due, mainly, to their low boiling points (all
members of this group are a gas at room temperature). Some members of this group that show
promise in the literature as blowing agent replacements include HFC 143 (1,1,2-trifluoroethane)
and 134a (1,1,1,2-tetrafluoroethane) (Barthelemy, PP. et al., 1993; Cecchini, C. et al., 1993;
Yu-Halada, LC. and Reichel, C.T., 1993).
Manufacture
Several commercial plants have recently come on line to provide large amounts of
HFC 134a (1,1,2,2-tetrafluoroethane), 125 (pentafluoroethane), and 143a (1,1,1 -trilluoroethane)
to be used as R502 and CFC 12 replacements in refrigeration units.
Toxicity
According to an abstracted study in TSCATS, 1,1-difluoroethane has an oral LDJ0 greater
than 1500 mg/kg in rats although there is some evidence for sub-chronic inhalation toxicity at
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very high concentration levels. For 1,1,2,2-tetrafluoroethane, there is a concern for a teratologic
effects by inhalation in rats.
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Group N - Silicon Containing Compounds
CH3
CH3-Si-CH3
CH3
General
In the course of this project, the investigation of silicon compounds was considered, given
the well known chemical inertness and utility of many silicon containing materials. For many of
the compounds under consideration, however, experimental boiling points and thermal
conductivity values were not available. Indeed, Task 1 of this project involved the determination
of a method for estimating vapor thermal conductivity values for silicon containing compounds.
Only one of the approximately twenty silicon compounds considered in this project
possessed a boiling point appropriate for the final scoring exercise, tctramethylsilane. Although
tetramethylsilane ranked 53rd overall, it came near the very bottom in the vapor thermal
conductivity ranking.
Manufacture
Tetramethylsilane is widely available.
Toxicity
No data were located.
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Information Gaps
The research described herein represents a systematic search to screen a large number of
compounds to identify chemical candidates as substitutes for CFCs and HCFCs used for making
polyurethane foam insulation products. A wide variety of chemical compounds were considered
for this project. Some of these compounds were initially proposed as alternative blowing agents
by commercial, governmental, or private research organizations and some were first considered
as a blowing agent substitute in this project. When screening a large number of chemical
compounds for any research project, initial effort is best spent focusing on the collection of
readily available information. This project has collected, compiled, reviewed, and analyzed
extensive amounts of readily available information and has identified, defined, and prioritized
those compounds and chemical groups that hold the highest potential to become viable third-
generation blowing agents based on this information. Additional information is needed before a
select list of the best blowing agent replacements can be obtained. Several areas of research that
would aid in this endeavor are described below.
Additional experimental information to fill existing data gaps on the boiling point and
thermal conductivity would help evaluate new blowing agents. This effort would involve
searching the chemical literature to identify papers where the compound of interest is specifically
discussed, a process that is overly resource intensive to perform during a screening study. This
would also allow experimental sources of other physical/chemical properties such as specific
gravity, heat of vaporization, and flammability limits to be identified, compiled, and considered.
Also, as noted in our report, the boiling points that were used for the vapor thermal conductivity
estimates were prepared using a less precise method. It would be a worthwhile exercise to re-
estimate the vapor thermal conductivities using the more accurate boiling point estimates.
104
-------
It may be desirable to add other ranking criteria for sorting the alternative blowing agent
candidates. Also, adding weights to the ordering criteria will better differentiate the blowing
agent candidates. For example, molecular weight is probably not linear in importance in
identifying third generation blowing agents relative to boiling point and GWP.
Another area that needs further examination is the flamability of potential alternatives.
The CFCs and IICFCs exhibit low flammability characteristics. However, the commercial use of
cyclopentane (Volken, O., 1993; Walker, GW. et al., 1993; Kuhn, E. and Schindler, P., 1993)
demonstrates that highly flammable materials can be used, but require additional, often
expensive safety precautions. Information on flammability should be collected and estimates
calculated for chemicals lacking experimental data.
Other information that would aid in the development of blowing agent candidates would
be the commercial availability and ease of synthesis of the blowing agent candidates. Although
all readily available blowing agent candidates were identified for this project, many of the
compounds may be available from speciality chemical or overseas manufacturers. If a
commercial source for a blowing agent candidate cannot be identified, the compound-specific
literature search described above would also provide details of successful laboratory-scale
synthesis routes that could be utilized to produce sufficient quantities of the compound for
foaming trials and physical/chcrnical property measurements.
Information that would be useful in establishing the likelihood of a blowing agent
candidate holding potential to attain commercial viability is detailed toxicological data. Because
of resource limitations, only screening searches of the available literature were possible. A more
in-depth review would have two stages. The first would be a complete compound-specific
literature search of the toxicology literature followed by the review and analysis of all
105
-------
experimental data retrieved. Data would be reviewed in the areas of acute, subchronic, chronic,
neurological, reproductive, developmental, carcinogenic, and immunological effects. For those
compounds that do not possess experimental toxicology data as well as for those that possess
data gaps, the second stage would be to develop simple structure/activity relationships based on
functional moieties to predict the importance of the above adverse affects.
Additional information on the use of mixed solvent systems as blowing agents could be
valuable. The unique capability of UNIFAC activity coefficients to represent vapor-liquid and
liquid-liquid equilibria for binary and multi component mixtures containing a wide variety of
compounds such as hydrocarbons, ketones, esters, nitriles, and so on (Reid, RC, et al., 1987)
could be used in this identification. Investigation of mixed solvent systems as blowing agents is
advantageous because it will allow a blowing agent to be designed by blending the properties of
one or more chemical substances. For example, fluoroiodomethane ranked number 1 in the
vapor thermal conductivity, but ranked poorly in boiling point criteria. By mixing this compound
with, for example, 1,2-difluorcylobutane which ranked number 1 in the boiling point criteria, a
new blowing agent system that offers advantages over each of the individual components can be
studied. Moreover, the UNIFAC method allow the proportions of each component of the
mixture to be varied until the desired characteristics can be maximized.
UNIFAC is particularly appropriate for these calculations since it is the only general
method for determining the properties of chemical mixtures at different temperatures. This
method will allow desired physical/chemical properties to be reached by blending two or more
compounds rather than by designing, synthesizing, and testing a large number of chemical
compounds. A number of blowing agent candidates from Table 4 would be selected based on
their unique physical/chemical properties. These compounds would then be blended using the
106
-------
UN1FAC. approach to achieve the optimum range of values for thermal conductivity, solubility,
and flammability as well as other important properties. This process will allow the identification
of blowing agent mixtures for rigid polyurethane foams and represents a new area of endeavor in
the search for third-generation blowing agents.
107
-------
Appendix A. Commercial Availability of Blowing Agent Candidates
CAS#
Name
Availability
000591935
1,4-Pentadiene
Readily
123812806
3-Fluorocyclobutene
Not available
000142290
Cyclopentene
Readily
000563462
1-Butene, 2-methyl-
Readily
000504609
1,3-Pentadiene
Readily
000109671
1 Pentene
Readily
000109682
2-Pentene
Readily
000542927
1,3-Cyclopentadiene
Readily
000078795
1,3-Butadiene, 2-methyl-
Readily
000679867
1,1,2,2,3-Pentafiuoropropane
HFC 245ca (Aldrieh)
002366521
Butane, 1-fluoro-
Nar Chem
000513359
2-Butene, 2-methvl-
Readily
66
1,1,1,2,3-Pentafluoropropane
HFC 245eb
000558372
1-Butene, 3,3-dimethyl-
Readily
000374129
1,1,2.2-Tetraflucrocyclobutane
Columbia Organics
000461632
Difluoromethyl fluoromethyl ether
Synthesized by AEERL
345
1,1,2,3.4,4-HexafIuoro-1 -butene
Not available
000107017
2-Butene
Readily
000078784
Butane, 2-methyl-
Readily
000691372
1-Pentene, 4-methyl-
Readily
6102
1,2-Difluorocyclobutane
Not known
6103
1,1 -Difluorocyclobutane
Not known
000407590
1,1,1,4,4,4-Hexafluorobutane
HFC 356mff (Allied)
000666160
Fluorocyclobutane
Not known
000287923
Cyclopentane
Readily
6104
1,2,3-Tri fluorocyclobutane
Not known
000677214
1-Propene, 3,3,3-trifluoro-
Aldrieh
000287230
Cyclobutane
Readily
000460731
1,1,1,3,3-PentafIuoropropane
HFC 245fa Synthesized by AEERL
000067641
2-Propanone
Readily
108
-------
-------
Appendix A. Commercial Availability of Blowing Agent Candidates (continued)
CAS#
Name
Availability
000109660
Pentane
Readily
000421501
2-Propanone, 1,1,1 -trifluoro
Aldrieh
001115088
1,4-Pentadiene, 3-methyl-
Aldrich
6115
1,1 -Difluorobutane
Not known
6117
1,4-Difluorobutane
Not available
001191964
Cyclopropane, ethyl-
Not known
333
1,2,3,4-Tctrafluorocyclobutane
Not known
000690222
Trifluoromethyl ethyl ether
Not available
6119
Trifluoromethoxymethoxymethane
Not known
000079298
Butane, 2,3 dimethyl-
Aldrich
6118
1,1,1 -Trifluorobutane
Not available
000460435
l-Methoxy-2,2,2-trifluoroethane
Not known
001493034
Methane, iododifluoro-
Not known
000512516
1.1,2,2-Telrafluoroethyl ethyl ether
Not known
000353617
Propane, 2-lluoro-2-methyl-
Not known
000503300
Trimethylene oxide
Aldrich
000594116
Cyclopropane, rnethyl-
Not known
6116
1,2-Difluorobutane
Not available
000680002
1,1,2,2,3,3-Hexafluoropropane
HFC 236ca
000109875
Dimethoxymethane
Aldrich
024270664
1,1,2,3,3-Pentafluoropropane
HFC 245ea
040723635
1,1.2.2-Tetratluoropropane
Not known
000819498
1 -Trifluoromethoxy-2-fluoroethane
Not known
6108
1,2,3-Trifluorocyclopentane
Not known
6101
1,1 -Difluoroacetone
Not known
000382343
1,1,2,3,3,3-Pentaflucropropvl methyl ether
Not known
20
1,1,3,3-Tetrafluorooxetane
Synthesized by AEERL
000075763
Tetramethyl silane
Readily
000075832
Butane, 2,2-dimcthyl-
Readily
000425887
1 -Methoxy-1,1,2,2-tetrafIuoroethane
Not known
109
-------
Appendix A. Commercial Availability of Blowing Agent Candidates (continued)
CAS#
Name
Availability
000421078
Propane, 1,1,1-trifluoro-
HFC 263fh
6107
1,2-Difluorocyclopentane
Not known
000431470
Methyl trifluoroacetate
Aldrich
6109
1,2,3,4-Tetrafluorocyclopentane
Not known
6105
Fluorocyelopentane
Not known
6106
1,1 -Difluorocyclopentane
Not known
000075376
Ethane, 1,1-difluoro-
HFC 152a (Aldrich)
000116154
1 -Propene, 1,1,2,3,3,3-hexathioro-
Aldrich
6114
1,3-Difluoroacetone
Not known
000075105
Methane, difluoro-
HFC 32
032778168
l-Difluoromethoxy-2,2-difluoroethane
Not known
6111
1 -Fluoro-2-ethylcyclopropane
Not known
069948294
1 -Difluoromethoxy 1,1 difluoroethane
Not known
6112
1,1,1,3-Tetrafluoroacetone
Not known
123768183
1,1,2,2,3,3-Hexafluorocyclopentane
Not known
056281926
1 -Difluoromethoxy-1,2,2-trifluoroethane
Not known
000360521
2 Propanone, 1,1,3.3-tetrafluoro
Not known
6110
2-Fluoroethyleyclopropane
Not known
000677565
1,1,1,2,2,3-Hexafluoropropar.e
HFC 236cb Synthesized by AEERL
000353366
Ethane, fluoro-
Should be available
001634044
t-Butyl methyl ether
Aldrich
000354643
Ethane, pentafluoroiodo-
Aldrich
000431710
2-Propanone, 1,1,1,3,3-pentafluoro
Not known
000811972
Ethane, 1,1.1,2-tetrafluoro-
HFC 134a (Aldrich)
136975092
1 -Trifluoroniethyl-1,2,2-trifluorocyclobutanc
Not known
000373535
Methane, iodofluoro-
Not known
000431630
1,1,1,2,3,3-Hexalluoropropane
HFC 236ea Synthesized by AEERL
003831490
Ethane, 1-iodo-l, 1,2,2-tetralluoro-
Not known
000754347
Propane, 1,1,1,2,2,3,3-heptaf1uoro-3-iodo-
Aldrich
032778113
1 -Difluoromethoxy-1,1,2,2-tetrafluoroethane
Not known
110
-------
Appendix A, Commercial Availability of Blowing Agent Candidates (continued)
CAS # Name
000677690 Propane, 1,1,1,2,3,3,3-heptattuoro 2-iodo-
001691174 Difluromethyl ether
002314978 Methane, trifluoroiodo
001814886 1,1,1,2,2-Pentafluoropropane
000382105 1-Propene,
3,3,3-trifluoro-2-(trifluoromethyl)-
000690391 1,1,1,3,3,3-Hexatluoropropane
000333368 Bis 2,2,2-trifluoroethyl ether
000354336 Ethane, pentafluoro-
000421147 Trifluoromethyl methyl ether
000931919 Hexafluorocyclopropane
18 1,1,2,2,3-Pentafluorooxetane
002252848 1,1,1,2,2,3,3-Heptafluoropropane
000431890 1,1,1,2,3,3,3-Heptafluoropropane
444 2,3.4,5-Tetrafluorotetrahydrofuran
001479498 Trifluoromethyl ether
003822682 Trifluoromethyl difluoromethyl ether
000425821 1,1,2,2,3,3-Hexafluorooxetane
000684162 2-Propanone, hexafluoro
Availability
Aldrich
Synthesized by AEERL
Aldrich
HFC 245eb Synthesized by AEERL
Not known
HFC 236fa
Aldrich
HFC 125
Synthesized by AEERL
Not known
Synthesized by AEERL
HFC 227ca Synthesized by AEERL
HFC 227ea Synthesized by AEERL
Not known
Synthesized by AEERL
Synthesized by AEERL
Synthesized by AEERL
Aldrich
111
-------
Appendix B. Boiling Points of Blowing Agent Candidates at 760 mm Hg
CAS # Name
000067641 Acetone
000075105 Methane, difluoro-
000075376 Ethane, 1.1-difluoro-
000075763 Tetramethy! silane
000075832 Butane, 2,2-dimethyl-
000078784 Butane, 2-merhyl-
000079298 Butane, 2,3-dimethyl-
000107017 2-Butene
000109660 Pentane
000109671 1-Pentene
000109682 2-Pentene
000109875 Dlmethoxymethane
000116154 1-Propene, 1,1.2.3,3,3-hexafiuoro-
000142290 Cyclopentene
000287230 Cyclobutane
000287923 Cyclopentane
000333368 Bis-2,2,2-trifluoroethyl ether
000353366 Ethane, fluoro-
000353617 Propane, 2-fIuora-2-methyl-
000354336 Ethane, pentafluoro-
000354643 Ethane, pentafluoroiodo-
000360521 2-Propanone, l,l,3,34etrafluoro
000372907 1,4-Difluorobutane
000373535 Methane, iodofluoro-
000374129 1,1,2,2-TetrafIuorocyclobutane
000382105 l-Propene, 3,3,3-trifluoro-2-
(trifluoromethyl)-
000382343 1,1,2,3,3,3-Pentaf uoropropyl methyl ether
000407590 1,1,1,4,4,4-Hexafluorobutane
000421078 Propane, 1,1,1-trifluoro-
000421147 Trifluoromethyl methyl ether
000421501 2-Propanone, 1,1,1 -trifluoro
000425821 1,1,2,2,3,3-Hexafluorooxetane
000425887 1 -Methoxy-1,1,2,2-tetrafluoroethane
000431050 1,1-Difluoroacetone
000431312 1,1,1,2,3-Pentafluoropropane
000431470 Methyl tritluoroacetate
000431630 1,1,1,2,3,3-Hexafluoropropane
000431710 2-Propanone, 1,1,1,3,3-pentafluoro
000431890 1,1,1,2,3,3,3-Heptaf luoropropane
000453145 1,3-Difluoroacetone
00)460344 1,1,1 -Trifluorobutane
000460435 1 -Methoxy-2.2,2-trifluoroethane
000460731 1,1,1,3,3-Pentafluoropropane
000461632 Difluoromethyl fluoromethyl ether
000503300 Trimethylene oxide
000512516 1,1,2,2-Tetrafluoroethy! ethyl ether
000513359 2-Butene, 2-methyl-
000558372 1-Butene, 3,3-dimethyl-
000563462 1-Butene, 2-methyl-
000591935 1,4-Pentadiene
000594116 Cyclopropane, methyl-
BP (°C) Reference
56.00 Atdrich (1994)
-51.65 Yu-halada, LC. and Reichel, CJ, (1993)
-25.00 Aldrich (1994)
26.00 Aldrich (1994)
50.00 Aldrich (1994)
28,00 Aldrich (1994)
58.00 Aldrich (1994)
1.00 Aldrich (1994)
36.10 Aldrich (1994)
29.90 Aldrich (1994)
37.00 Aldrich (1994)
41.00 Aldrich (1994)
-28.00 Aidrich (1994)
44.00 Aldrich (1994)
12.50 Daubert, TE. and Danner, RP. (1989)
50.00 Aldrich (1994)
9.50
-37 JO Daubert, TE. and Danner, RP. (1989)
-5.02
-48.50 Creazzo, JA. and Hammel, HS. (1991)
12.00 Nimitz, J. and Lankford, PW. (1993)
23.31
28.82
53.40 Nimitz, J. and l ankford, PE. (1993)
0.76
-29.10
-7.07
24.90 Knopeck, GM. etal. (1993)
-13.00 Decaire, BR, et al. (1992)
-24.10 Smith, ND. (1993)
26,21
-28.20 Smith, ND. (1993)
-12.54
34.13
22.70
43.00 Aldrich (1994)
6.00 Decaire, BR. etal. (1992)
15.28
-18.70 Decaire, BR. et ai. (1992)
49.87
0.38
1.45
15.30 Knopeck, GM. et al. (1993)
29.90
50.00 Aldrich (1994)
14.95
35.00 Aldrich (1994)
41.00 Aldrich (1994)
31,00 Aldrich (1994)
26.00 Aldrich (1994)
4.00
112
-------
Appendix B. Boiling Points of Blowing Agent Candidates at 760 mm Hg (continued)
CAS # Name
000666160 Fluorocyclobutane
000677214 1-Propene, 3,3,3-trifluoro-
000677565 1,1,1,2,2,3-Hexafluoropropane
000677690 Propane, 1,1,1,2,3,3.3-heptaftuoro-2-iodo-
000679867 1,1,2,2,3-Pentafluoropropane
000680002 1,1,2,2,3,3-Hexaf iuoropropane
000680546 1,1,2,3,4,4-Hexafluoro-l -butene
000684162 2-Propanone. hexafiuoro
000686657 1,2-Difluorobutane
000690222 Trifluoromethyl ethyl ether
000690391 1,1,1,3,3,3-Hexafluoropropane
000691372 1-Pentene, 4-methyl-
0OD754347 Propane, l,l,l,2,2,3,3-heptafluoro-3-iodo-
003811972 Ethane, 1,1,1,2-tetrafluoro-
000819498 1 -Trifluoromethoxy-2-fluoroethane
000931919 Hexafiuorocyclopropane
001115088 1,4-Pentadiene, 3-methyl-
001120203 1,1 -Dlfluorocyclopentane
001191964 Cyclopropane, ethyl-
001479498 Trifluoromethyl ether
001481363 Fluorocyclopentane
001493034 Methane, iododifluoro-
001634044 t-Butyl methyl ether
001691174 Dlfluromethyl ether
001814886 1,1,1,2,2-Pentafluoropropane
002252848 1,1,1,2,2,3,3-Heptafiuoropropane
002314978 Methane, trifluoroiodo-
002358385 1,1-Difluoro butane
002366521 Butane, 1-fluoro-
003822682 Trifluoromethyl difluoromethyl ether
003831490 Ethane, 1 -iodo-1,1,2,2-tetrafiuoro-
022669096 1,1 -Difluorocyclobutane
024270664 1,1,2,3,3-Pentafluoropropane
032778113 1-Difluoromethoxy-l. 1,2,2-
tetrafluoroethane
032778168 l-Difluoromethoxy-2,2-difluoroethane
040723635 1,1,2,2-Tetrafluoropropane
050422769 1 -Fluoro-2-ethylcyclopropane
056281926 1 -Difluoromethoxy-1,2,2-trifluoroethane
069750681 2-Fluoroethy Icyclopropane
069948294 1 -Difluoromethoxy-1,1 -difl uoroethane
072507858 1,2-Difluorocyclobutane
113742908 1,2-Difluorocyclopentane
123768183 1,1,2,2,3,3-Hexafiuorocyclopentane
123812806 3-Fluorocyclobutene
129362976 1,2,3,4-Tetrafiuorocyclobutane
133360006 2,3,4,5-Tetrafluorotetrahydrofuran
136975092 1 -Trifluoromethyl-1,2,2-trif luorocyciobutane
144109035 1,1,2,2,3-Pentaf luorooxetane
154330402 1,1,3,3-Tetrafl uorooxetc ne
6104 . 1,2,3-Trifluorocydobutane
6108 1,2,3-Trifluorocyclopentane
6109 1,2,3,4-Tetrafluorocyclopentane
BP fC) Reference
29.19
-18.00 Aldrich (1994)
-1.20 Decaire, BR. et al. (1992)
38.00 Nimitz J. and Lankford, PE. (1993)
25.10 Decaire, BR. etal. (1992)
10.00 Decaire, BR, etal. (1992)
-3,77
-26.00 Aldrich (1994)
8.56
1,45
-0.07 Decaire, BR. etal. (1992)
53.00 Aldrich (1994)
40.00 Nimitz, J. and Lankford, PE, (1993)
-26.50 Decaire, BR. et al. (1992)
4.14
-47.70
55.00 Aldrich (1994)
46.57
34,50
-58,70 Smith, ND. (1993)
57.64
21,60 Nimitz, J, and Lankford, PE, (1993)
55,00 Aldrich (1994)
4.70 Smith, ND. (1993)
-17.60 Decaire, BR. etal. (1992)
-17.70 Decaire, BR. etal. (1992)
-22.50 Nimitz, J. and Lankford, PE. (1993)
8.56
32.50
-34.60 Smith, ND. (1993)
41.00 Nimitz, J. and Lankford, PE. (1993)
17.69
39.30 Knopeck, GM. et al. (1993)
-3.10 Smith, ND. (1993)
-1.54
-1,60 Decaire, BR. ef al, (1992)
45.44
-15.58
52.94
-12.54
24,07
52,71
13.58
32,67
13.74
49,77
9,73
3.40 Smith, ND, (1993)
21.20 Smith, ND, (1993)
18.92
47.75
42.76
113
-------
Appendix B. Boiling Points of Blowing Agent Candidates at 760 mm Hg (continued)
CAS # Name BP (°C) Reference
6112 1,1,1,3-Tetrafluoroacetone 28,81
6119 Trifluoromethoxymethoxymethane 29.52
114
-------
Appendix C, Physical Properties of Blowing Agent Candidates I - Environmental Fate
CAS No.
Name
MP
WS
Tmp
Kow
VP
Tmp
HL
000067641
2-Propanone
-94.70
le6
25
-0.24
230.00
25
000075105
Methane, difluoro-
-136.00
2.00E-01
12.6CX3.00
25
000075376
Ethane, IJ-difluoro-
-117.00
7.50E-01
4,437.10
25
000075763
Tetramethyl silane
-99.00
1,96
25
3,85
718.00
25
000075832
Butane, 2,2-dlmethyl-
-100.00
18
25
3.82E+00
320.00
25
000078784
Butane, 2-methyl-
-159.90
4.80E+01
25
2.30E+00
689,00
25
1.40E+00
000079298
Butane, 2,3-dimethyl-
-129.00
n
20
3.85E+00
235.00
25
000107017
2-Butene
-140.00
2.33E+00
1,360.00
20
1.54E-01
000109660
Pentane
-130,00
3.80E+01
25
3.39E+00
• 514.00
25
1.25E+00
000109671
1-Pentene
-165.22
148
25
638.00
25
000109682
2-Pentene
-138.00
203
25
528.00
25
000109875
Dlmethoxymethane
-105.15
244
16
398.70
25
000116154
1 Propene, 1,1,2,3,3,3-hexafluoro
-153.00
4,903.00
25
000142290
Cyclopentene
-135.00
380,00
25
000287230
Cyclobutane
-91.00
1,170.00
25
000287923
Cyclopentane
-94.40
1.56E+02
25
3.00E+00
318.00
25
1.88E-01
000333368
Bls-2,2,2-trifluoroethyl ether
000353366
Ethane, fluoro-
-143.00
6,840.00
25
000353617
Propone, 2-fluoro-2-mett^
000354336
Ethane, pentafluoro-
-103.00
3.90E+01
25
1.43E+00
10,499.00
25
3.05E+00
000354643
Ethane, pentafluoroiodo-
-95.00
717.00
10
Imp
000360521 2-Propanone, 1,1,3,3-tetrafluoro
000372907 1,4-Difluorobutane
000373535 Methane, iodofluoro-
000374129 1,1,2,2-Tetrafluarocyclobutane
000382105 1 -Propene, 3,3,3-trifluaro-2-
(trifluoromethyl)-
000382343 1,1,2,3,3,3-Pentafluoropropyl methyl ether
000407590 1,1,1,4,4,4-Hexafluorobutane
000421078 Propane, 1,1,1-trifluoro-
000421147 Trifluoromethyt methyl ether
000421501 2-Propanone, 1,1,1 -trifluoro
000425821 LI,2,2,3,3-Hexafiuarooxetane
000425887 1 -Methoxy-1,1,2,2-tetrafluoroethane
000431050 1,1-Difluoroacetone
000431312 1,1,1,2,3-Pentafluo'oprcoane
00)431470 Methyl trifluoroocetate
000431630 1,1,1,2,3,3-Hexafluoropropane
000431710 2-Propanone, 1,1,1,3,3-pentafluoro
000431890 1,1,1,2,3,3,3-Heptafluoropropane
000453145 1,3-Difluoroacetone
000460344 1,1,1-Trifluorobutane
000460435 1 -Methoxy-2,2.2-trifluoroettiane
MP = Melting Point in °G
WS = Water solubility in mg/kg
Tmp = Temperature in °C
Kow = Log octanol/water partition coefficieint
VP = Vapor pressure in mm hg
HL = Henry's Law constant in atm cu-m/mole
-146.10
25
25
25
25
25
115
-------
Appendix C, Physical Properties of Blowing Agent Candidates I - Environmental Fate (continued)
CAS No.
Name
MP
000460731
1,1,1,3,3-Pentaftuoropropane
000461632
Difluoromethyi fluoromethyl ether
000503300
Trimethylene oxide
000512516
1,1,2,2-Tetrafluoroethyf ethyl ether
000513359
2-Butene, 2-rnetbyl-
-134.00
000558372
1-Butene, 3,3-dimethyl-
-115.00
000563462
1-Butene, 2-methyl-
-137.00
000594116
Cyclopropane, methyi-
000666160
Fluorocyclobutane
000677214
1-Propene, 3,3,3-trifluoro-
000677565
1,1,1,2,2,3-Hexafluoropropane
000677690
Propane, 1,1,1,2,3,3,3-heptaf!uoro-2-iodo-
000679867
1,1,2,2,3-Pentafluoropropane
-73.40
000680002
1,1,2,2,3,3-Hexafluoropropane
000680546
1,1,2,3,4,4-Hexafluoro-l -butene
000684162
2-Propcnone, hexafluoro
000686657
1,2-Dlfluorobutane
000690222
Trlfluoromethyl ethyl ether
000690391
1,1,1,3,3,3-Hexafiuoropropane
000691372
1-Peritene, 4-methyl-
-153.00
000754347
Propane, 1,1,1,2,2,3,3-heptafluoro-3-fod o-
-95.00
00811972
Ethane, 1,1,1,2-tetrafluofo-
-101.00
000819498
l-Trifluoromethoxy-2-fluoroethane
£*30931919
Hexafluorocyclopropane
001115088
1,4-Pentcsdiene, 3-methyl-
0)1120203
1,1 -Difluorocyclopentane
001191964
Cyclopropane, ethyS-
001479498
Trifluoromethyl ether
001481363
Fiuorocyclopentane
031493034
Methane, iododifluoro-
001634044
t-Butyl methyl ether
-115.00
001691174
Difiuromethyl ether
001814886
1,1,1,2,2-Pentafiuoropropane
002252848
1,1,1,2,2,3,3-Heptafiuoropropane
002314978
Methane, trifluoroiodo-
002358385
1,1-Difiuorobutane
002366521
Butane, 1-fluoro-
003822682
Trifluoromethyi difluoromethyi ether
003831490
Ethane, 1 -iodo-1,1,2,2-tetrafluoro-
022669096
1,1 -Difluorocyclobutarte
024270664
1,1,2,3,3-Pentafluoropropane
032778113
1 -Difluoromethoxy-1,1,2,2-
tetrafluoroethane
MP = Melting Point in °C
WS = Water solubility in mg/kg
Tmp = Temperafure in °C
Kow = Log octanol/water partition coefficielnt
VP = Vapor pressure In mm hg
HL = Henry's Law constant in atm cu-m/mole
WS Tmp Kow VP Tmp HL Tmp
324,00 25
610.00 25
430.00 25
610,00 25
5,074.00 25
271.00 25
6.70E+01 25 1.27E+00 430,00 25 1.53E+00 25
51000 25 1.24 249,00 25
4,395.00 20
2.00E+00
116
-------
Appendix C. Physical Properties of Blowing Agent Candidates I - Environmental Fate (continued)
CAS No, Name MP WS Tmp Kow VP Tmp HL
032778168 l-Difluoromethoxy-2,2-dlflitoroe!bane
040723635 1,1,2,2-Tetrafluoropfopane
050422769 1 -Fluoro-2-ethylcyclopropane
056281926 1 -Difluoromethoxy-1,2,2-trlfluoroethane
069750681 2-Fluoroethylcyclopropane
069948294 1 -Difiuoromettioxy-1,1 -diflucroethana
072507858 1,2-Dsfluorocyclobutarie
113742908 1,2-Difiuorocyciopentane
123768183 1,1,2,2,3,3-Hexafluoroeyclopenfane
123812806 3-Ruorocyclobutene
129362976 1,2,3,4-Tetrafiuorocyclobutane
13336Q0Q6 2,3,4,5-Tetrafluorotetrahydrofuran
136975092 1-IrifluoromethyH ,2,2-
trifluorocyclobutane
144109035 1,1,2,2,3-Pentafiuorooxetane
154330402 1,1,3,3-Tetrafluoroaxetane
6104 1,2,3-Trifluorocyclobutan©
6108 1,2,3-TrIfluorocyclopsntane
6109 1,2,3,4-Tetrafluorocyctopentone
6112 1,1,1,3-Tetrafluoroacetone
6119 Trifluoromethoxymethoxyme thane
MP = Melting Point in "C
WS = Water solubility in mg/kg
Tmp = Temperature in °C
Kow = Log ootanol/water partition coefficient
VP = Vapor pressure in mm hg
HL = Henry's Law constant in atm cu-m/mole
117
-------
Appendix D. Physical Properties of Blowing Agent Candidates II - Environmental Fate
CAS No.
Nam©
SpecGrav tmp HeatVap tmp Flash Pt Meth
000067641
2-Propanone
0.79
7.48
25
-9.00 TOC
000075105
Methane, difluoro-
-89.00
000075376
Ethane, 1,1-dlfluoro-
0.91
20
4.561
25
000075763
Tetramethyl silane
0.65
5.785
26
-27.00
000075832
Butane, 2,2-dimeihyi-
0,64
25
6,618
25
-34.00 TCC
000078784
Butane, 2-methyl-
0.61
25
5.937
25
-57.00 CC
000079298
Butane, 2,3-dimethyl-
0.66
25
6,961
25
-33,00 TCC
000107017
2-Butene
-30.00 TCC
000109660
Pentane
0.62
25
6.32
25
-40,00 TOC
000109671
1-Pentene
0.64
25
6.088
25
-28.00 TCC
000109632
2-Pentene
0.65
25
8.42
25
-45.00 TCC
000109675
Dimethoxymethane
0.85
15
60904
25
000116154
1-Pr opens. 1,1,2,3,3,3-hexafluoro-
000142290
Cyclopentene
0.77
25
-34 30 TCC
000287230
Cyciobutane
-64.00
000287923
Cyciopentane
0.74
25
6.808
25
-37.00
000333368
Bis-2,2.2-trifluoroethy1 ether
000353366
Ethane, fluoro-
-89,00
000353617
Propane. 2-fiuoro-2-methyl-
000354336
Ethane, pentafluoro-
-28.00
000354643
Ethane, pentafluoroiodo-
2.09
000360521
2-Propanane, 1,1.3,3-tetrafluoro
000372907
1,4-Difluorobutane
000373535
Methane, lodofluoro-
2,37
000374129
1,1,2,2-Tetrafluorocyc!obutane
000382105
1 -Propene, 3,3,3-trlfluoro2-
000382343
1.1,2,3.3.3-Pentafluoropropyl methyl ether
000407590
1,1,1.4.4.4-Hexafluorobutane
000421078
Propane, 1,1,1 -trifluoro-
000421147
Trifluoromethyt methyl ether
000421501
2-Propanone, 1,1,1 -trifluoro
1.25
-23.00 TCC
000425821 1,1,2,2,3,3-Hexafluorooxetane
000425887 t -Methoxy-1,1,2.2-tetrafluoroethane
000431050 1,1-Difluoroacetone
000431312 1.1,1,2.3-Penlafluoropropaoe
000431470 Methyl trifluoroacetate
000431630 1,1,1,2,3,3-Hexafluoropropane 1.39
000431710 2-Propanone, 1,1,1.3.3-pentafluoro
000431890 1.1,1,2.3,3,3-Heptafluoropropane
000453145 1,3-Dlfluoraacetone
SpecGrav = Specific gravity
tmp = Temperature in degrees C
HeatVap = Heat of Vaporization In cat/g
Flash Pt = Flash point in degrees C
Meth = Flash point method
LEL = Lower explosion limit
DEL = Upper explosion limit
118
-------
Appendix D. Physical Properties of Blowing Agent Candidates II
- Environmental Fate (continued)
CAS No,
Name
000460344
1,1,1 -Trifluorobutane
000460435
1 -Methoxy-2,2,2-trifluoroethane
000460731
1,1,1,3,3-Pentafluoropropane
000461632
Dlfluoromethyl fluaramethyl ether
000503300
Trimethylene oxide
000512516
1,1,2,2-Tetrafluaroethyl ethyl ether
000513359
2-Butene, 2-methyl-
000558372
1-Butene, 3,3-dimethyl-
000563462
1 -Butene, 2-rnethyi-
000594116
Cyclopropane, methyl-
000666160
Flu orocyclo butane
000677214
1 -Propene, 3,3,3-tiifluoro-
000677565
1,1,1,2,2,3-Hexafluorapropane
000677690
Propane, 1,1.1,2,3,3,3-heptafluoro-2-iodo-
000679867
1,1,2,2,3-PentafIuoropropane
000680002
1,1,2,2,3,3-Hexafluoropropane
000680546
1,1,2,3,4,4-Hexafluoro-l -butene
000684162
2-Propanone, hexafluoro
000686657
1.2-Difluorobutane
000690222
Trifluoromethyl ethyl ether
000690391
1,1,1,3,3,3-Hexafluoropropane
000691372
1 -Pentene, 4-methyi-
000754347
Propane, 1,1,1,2,2,3,3-heptafluoro-3-iodo-
OT0S11972
Ethane, 1,1.1,2-tetrafluoro-
000819498
1 -Trifluoromethoxy-2-fluoroethane
000931919
Hexafluorocyclopropane
001115088
1,4-Pentadiene, 3-methyl-
001120203
1,1 -Difluorocyclopentane
001191964
Cyclopropane, ethyl-
001479498
Trifluoromethyl ether
001481363
Fiuorocyclopentane
001493034
Methane, iododifluoro-
001634044
t-Butyl methyl ether
001691174
Difluromethyl ether
001814886
1,1,1,2,2-Pentafluoropropane
002252848
1,1,1,2,2,3,3-Heptafiuoropropane
002314978
Methane, trifluaroiodo-
002358385
1,1-Difluorobutane
002366521
Butane, 1-fluoro-
003822682
Trifluoromethyl dlfluoromethyl ether
SpecGrav = Specific gravity
tmp = Temperature in degrees C
HeatVap = Heat of Vaporization in cal/g
Flash Pt = Flash point in degrees C
Meth = Flash paint method
LEL = Lower explosion limit
UEL = Upper explosion limit
SpecGrav tmp HeatVap tmp Flash Pt Meth LEL UE1
0,89 -28.00 TCC 2.8 37
0.66 -45.03 TCC 1.4 9.6
0.65 -28.00 TCC 1.2 9,0
0.65 -34,00 TCC
2,10
1.34 0 0
0.67 -31.CO TCC 1.2 9.4
2.06 ,11
0.67 -34.00 TCC
3.24
0.74 -10.00 TCC
2,36 .038
119
-------
Appendix D. Physical Properties of Blowing Agent Candidates II - Environmental Fate (continued)
CAS No. Name SpecGrav tmp HeatVap tmp Flash Pt Mefh
003831490 Ethane, 1 -iodo-1,1,2,2-tetrafluoro-
022669096 1,1-Difluorocyctobutane
024270664 1,1,2,3,3-Penfafluoropropane
032778113 1 -Difluoromettioxy-1,1,2,2-tetrafluoroethane
032778168 1 -Dlfluoromethoxy-2,2-difluoroethane
040723635 1.1,2,2-Tetrafluoropropane
050422769 1 -Ruoro-2-ettiylcyciopropane
056281926 1 -Difluoromethoxy-1,2,2-trifluoroethone
069750681 2-Fiuoroethyl cyclopropane
069948294 1 -Difluoromethoxy-1,1-dlfluoroethane
072507858 1,2-Difluorocyclobutane
113742908 1,2-Difluorocyclopentane
123768183 1,1,2,2,3,3-Hexafluorocyclopentane
123812806 3-Fluorocyclobutene
129362976 1,2,3,4-Tetrafluorocyctobutane
133360006 2,3,4,5-Tefrafiuorotetrahydrofuran
136975092 1 -TrifluoromethyH,2,2-ttftuorocyclobutane
144109035 1,1,2,2,3-Pentafluorooxetane
154330402 1,1,3,3-Tetrafluorooxefane
6104
1,2,3-Trlfluorocyclobutane
6108
1,2,3-Trifluorocyclopentane
6109
1,2,3,4-Tetrafluorocyclopentane
6112
1,1,1,3~Tetraf luoroacetone
6119
Trlfluoromethoxymethoxymethane
SpecGrav = Specific gravity
tmp = Temperature In degrees C
HeatVap = Heat of Vaporization in cal/g
Flash Pt = Flash point in degrees C
Meth = Flash point method
LEL = Lower explosion limit
UEL = Upper explosion limit
120
-------
Appendix E. References for Experimental Physical Properties from Appendices C and D
CAS No.
Ret MP
RefWS
Ref Kow
Ref VP
Ref HI
Ref SG
Ref HV
Ref 1
000067641
RIDDI
RIDDI
H&L
DD
ALDRI
RIDDI
RIDDI
000075105
DD
H&L
DD
.DD
000075376
ALDRI
H&L
RIDDI
RIDDI
RIDDI
000075763
ALDRI
RIDDI
H&L
DD
ALDRI
RIDDI
DD
000075832
ALDRI
RIDDI
H&L
RIDDI
RIDDI
RIDDI
ALDRI
000078784
RIDDI
RIDDI
H&L
DD
RIDDI
RIDDI
RIDDI
000079298
ALDRI
RIDDI
H&L
DD
RIDDI
RIDDI
ALDRI
000107017
ALDRI
H&L
OB
ALDRI
000109660
ALDRI
RIDDI
H&L
DD
RIDDI
RIDDI
RIDDI
000109671
RIDDI
RIDDI
RIDDI
RIDDI
RIDDI
ALDRI
000109682
RIDDI
RIDDI
RIDDI
RIDDI
RIDDI
ALDRI
000109875
RIDD!
RIDDI
RIDDI
RIDDI
RIDDI
00)116154
ALDRI
DD
000142290
ALDRI
DD
ALDRI
ALDRI
000287230
DD
DD
DD
000287923
ALDRI
YA
H&L
DD
RIDDI
RIDDI
RIDDI
000333368
000353366
DD
DD
DD
000353617
000354336
DD
DD
DD
000354643
IKON
IKON
IKON
000360521
000372907
000373535
IKON
000374129
000382105
000382343
000407590
000421078
000421147
000421501
ALDRI
ALDRI
000425821
000425887
000431050
000431312
000431470
000431630
000431710
000431890
000453145
000460344
000460435
RefEL
DD
DD
DD
DD
ALDRI = Aldfich (1994); DD = Daubert and Danner (1989); H&L = Hansch and Leo (1985)
IKON = Lankford, PE„ and Nimitz, J, (1993); Riddi = Riddick, JA. et al. (1986)
OB = Obenaus, F. et al. (1985); YK = Yalkowsky, SH, et al (1987)
BE = Bennet, GM, and Phillip, WG. (1928); FU = Fujiwara, Y, et al, (1984)
121
-------
Appendix E. References for Experimental Physical Properties from Appendices C and D (continued)
CAS No.
Ref MP Ref WS
Ref Kow
Ref VP
Ref HL
Ref SG
000460731
0)0461632
000503300
DD
ALDRI
000512516
000513359
ALDRI
DD
ALDRI
000558372
ALDRI
DD
ALDRI
000563462
ALDRI
DD
ALDRI
000594116
000666160
000677214
000677565
000677690
IKON
000679867
000680002
000680546
000684162
DD
000686657
000690222
000690391
000691372
DD
DD
ALDRI
000754347
IKON
000811972
000819498
000931919
001115088
ALDRI
001120203
001191964
001479498
001481363
001493034
IKON
001634044
ALDRI BE
FU
DD
ALDRI
001691174
001814886
002252848
002314978
IKON
IKON
002358385
002366521
H8tL
003822682
003831490
022669096
024270664
032778113
RefHV RefFP Ref
ALDRI
ALDRI
ALDRI
ALDRI
DD
DD
DD
ALDRI DD
IKON
ALDRI
ALDRI
ALDRI = Aldrich (1994); DD = Daubert and Danner (1989); H&L = Hansch and Leo (1985)
IKON = Lankford, PE.. and Nimite, J. (1993); Rlddl = Riddick, JA, et al, (1986)
OB = Obenaus, F. et a!. (1985); YK = Yalkowsky, SH, et a! (1987)
BE = Bennet, GM. and Phillip, WG. (1928); FU = Fujiwara, Y, et al. (1984)
122
-------
Appendix E. References for Experimental Physical Properties from Appendices C and D (continued)
CAS No. Ref MP RefWS Ref Row RefVP Ref HI RefSG RefHV RefFP Ref EL
032778168
040723635
050422769
056281926
069750681
069948294
072507858
113742908
123768183
123812806
129362976
1333600)6
136975092
144105035
154330402
6104
6108
6109
6112
6119
ALDRI = Aidrich (1994); DD = Daubert and Danner (1989); H&L = Hansch and Leo (1985)
IKON = Lankford, PE., and Nimitz, J, (1993); Riddi = Riddick, JA. et al. (1986)
OB = Obenaus, F. et al. (1985); YK = Yalkowsky, SH. ©t al (1987)
BE = Ben net, GM. and Phillip, WG. (1928); FU » Fujiwara, Y, et al. (1984)
123
-------
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