United States
Environmental Protection
Agency
<&ERA Research and
Development
THIRD-GENERATION
FOAM BLOWING AGENTS
FOR FOAM INSULATION
Prepared for
Office of Air and Radiation
Prepared by
National Risk Management
Research Laboratory
Research Triangle Park, NC 27711

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EPA-600/R-93-133
October 1998
THIRD-GENERATION FOAM BLOWING AGENTS FOR FOAM INSULATION
By:
Philip H. Howard and Jay L. Tunkel
Syracuse Research Corporation
Environmental Science Center
6225 Running Ridge Road
North Syracuse, NY 13212
and
Sujit Banerjee
BRI
P.O. Box 7834
Atlanta, GA 30357
EPA Cooperative Agreement CR 824287
EPA Project Officer:
Robert V. Hendriks
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, D.C. 20460

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TECHNICAL REPORT DATA hbubiiiihibi mi m
NRMKL RTP-141 (Please read Instructions on the reverse before completi III llll II llllll III 11 1 111
1. REPORT NO. 2.
EPA-600/R~ 98-133
3. f III llll II lllllllllllllll IIII III
PB99-122095
4. TITLE AND SUBTITLE
Third-Generation Foam Blowing Agents for Foam
Insulation
S. REPORT DATE
October 1998
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
P. H. Howard and J. L. Tunkel (SRC), and
S. Banerjee (BRI) >
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND AOORESS
Syracuse Research Corp. BRI
6225 Running Ridge Rd. P. 0. Box 7834
North Syracuse, NY 13212 Atlanta, GA 30357
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CR 824287 (SRC)
12. SPONSORING AGENCY NAME AND AOORESS
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; 10/95 - 9/97
14. SPONSORING AGENCY CODE
EPA/600/13
^-supplementarynotes APPCD pro;ject officer is Robert v> HendrikS) Mail Drop 63, 919/
541-3928.
16. abstractrep0rj. gives results of a study of third-generation blowing agents for
foam insulation. (NOTE: The search for third-generation foam blowing agents has
led to the realization that, as the number of potential substitutes increases, new con-
cerns, such as their potential to act as greenhouse gases and their safe use,. are
generated. Unfortunately, the data required to assess a substitute's potential to con-
tribute to global warming or to form flammable mixtures in air are not available for
most new chemicals under consideration.) Addressing these data needs represents
two of the three phases of research performed in this project. The third phase fo-
cused on identifying blowing agent substitutes. The investigation concentrated on the
development of techniques to identify and replace deficiencies that may be present in
an individual substitute through the use of blowing agent azeotropic mixtures. The
two components of a mixture may display a synergistic effect where the overall char-
acteristics of the blowing agent are better than if either substance was used indivi-
dually. The avove concepts on blowing agent mixtures should encourage interested
parties to investigate the use of azeotropes in laboratory foaming trials on insulating
polyurethane foams.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. cos ATI Field/Group
Pollution Greenhouse Effect
Insulation
Foam
Blowing Agents
Azeotropes
Polyurethane Resins
Pollution Control
Stationary Sources
Global Warming
13B 04A
14G
11G
07D
111, 11J
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
150
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)

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ABSTRACT
The search for third-generation foam blowing agents has led to the realization that, as the
number of potential substitutes increases, new concerns, such as their potential to act as
greenhouse gases and their safe use, are generated. Unfortunately, the data required to assess the
substitute's potential to contribute to global warming or to form flammable mixtures in air are not
available for the majority of new chemicals under consideration. Addressing these data needs
represents two of the three phases of research performed in this project. The third phase of this
project focused on identifying blowing agent substitutes. The investigation concentrated on the
development of techniques to identify and replace deficiencies that may be present in an individual
substitute through the use of blowing agent azeotropic mixtures. The two components of a
mixture may display a synergistic effect where the overall characteristics of the blowing agent are
better than if either substance was used individually. The above concepts on blowing agent
mixtures should encourage interested parties to investigate the use of azeotropes in laboratory
foaming trials on insulating polyurethane foams.

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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

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¦f
NOTICE'
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED.
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
Reproduced from
best available copy.
ii

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Introduction
Table of Contents
l
Blowing Agent Flammability	5
Global Warming Potential	20
Introduction	20
Assigning GWPs to Substitute Blowing Agents	26
Re-Ranking the List of 105 Blowing Agent Substitutes	34
Blowing Agent Azeotropes 	54
Introduction	54
Methodology Development	57
Identifying Potential Blowing Agent Mixtures	65
Assigning GWPs to the Identified Azeotropic Blowing Agents	104
Conclusion			113
Flammability of Blowing Agent Substitutes	113
Third-Generation Azeotropic Blowing Agents 	114
References 	117
Appendix A. Flammability Limits Collected from the Literature	122
Appendix B. Chemical Name and ASHRAE Standard Designation of
Refrigerants Reference 	141
iii

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List of Tables
Table 1. Comparison of Experimental and Estimated UFLs for HFCs and HFEs 		9
Table 2. Comparison of Experimental and Estimated LFLs for HFCs and HFEs 	11
Table 3. Fragments Used in UFL Estimation Methodology Development 	14
Table 4. Fragments for HFC and HFE Flammability Limits	16
Table 5. Halogen:Hydrogen Index of Fluorinated Organics	19
Table 6. GWP Assignments Based on Atmospheric Lifetime	25
Table 7. Literature GWPs for the Initial List of 105 Chemical Substitutes	27
Table 8. Estimated GWPs for the Initial List of 105 Chemical Substitutes	28
Table 9. Ranking of the 105 Blowing Agent Substitutes	37
Table 10. UNIFAC Output for Acetone/Cyclopentane Binary Mixture	60
Table 11. Comparison of Experimental and Estimated Azeotrope Data	62
Table 12. Binary Azeotrope Data	66
Table 13. Estimated Azeotropes with Vapor Thermal Conductivity Less Than Either
Component	84
Table 14. Azeotrope Candidates	87
Table 15. Antoine Coefficients Located in the Literature	90
Table 16. Chemicals in Azeotrope Matrix	93
Table 17. Estimated Mole Fraction of Azeotropes 	94
Table 18. Estimated Vapor Thermal Conductivities of Azeotropes	95
Table 19. Estimated Boiling Points of Azeotropic Blowing Agents (°C)	96
Table 20. Azeotrope Matrix Summary 	97
Table 21. Azeotropes of Pentafluoroiodoethane and Difluoroiodomethane	102
Table 22. Azeotropes of HFC 245ca	103
Table 23. Literature GWPs for Initial Azeotrope Investigation Chemicals	105
Table 24. Estimated GWPs for Initial Azeotrope Investigation Chemicals	106
Table 25. Literature GWPs for Matrix Chemicals	108
Table 26. Estimated GWPs for Matrix Chemicals	109
Table 27. Approximate GWP of Azeotropic Blowing Agents	Ill
iv

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List of Figures
Figure 1. Atmospheric Lifetime for Organic Chemicals that React with Hydroxyl
Radicals vs. GWP	24
Figure 2. X-Y Diagram of Acetone-Cyclopropane Binary Mixture 	58
Figure 3. Reliability of Azeotrope Estimation Method for Boiling Point 	64
Figure 4. Reliability of Azeotrope Estimation Method for Mole Fraction	64
v

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Introduction
The chemicals that were initially used as blowing agents for the production of
polyurethane foams, the so-called first-generation blowing agents, were chlorofluorocarbons
(CFCs). 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
production and use. They had relatively low vapor thermal conductivities which is an important
physical property for insulating materials because the blowing agent becomes incorporated into
the foam and is, therefore, partially responsible for hindering the movement of heat through the
foam. The most commonly used first-generation polyurethane blowing agent, CFC 11 (boiling
point 23.8 °C), was well suited to the foaming process because it is a liquid at room temperature
which simplifies storage and formulation, yet it readily volatilizes to expand the foam. An
additional advantage of CFC 11 is that it is non-flammable and thus, it can be used without the
stringent safeguards required of explosive materials. These properties, combined with other
desirable characteristics such as low toxicity, wide commercial availability, and chemical stability
resulted in the extensive use of CFC 11 as a blowing agent in insulating polyurethane foams.
In a growing effort that began in the early 1970s, CFCs became recognized as major
contributors to the depletion of stratospheric ozone in the Earth's atmosphere. Stratospheric
ozone helps 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
1

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increased incidence of UV radiation, a phase out of CFC production was called for beginning
January 1, 1996, under the auspices of the Montreal Protocol and current U.S. law.
Worldwide efforts to replace CFC blowing agents led to the development of the so-called
second-generation blowing agents, the hydrochlorofluorocarbons, HCFCs (Knopeck et al., 1994;
Decaire et al., 1992). HCFCs have many of the desirable properties of the CFCs yet have
significantly lower ozone depletion potentials. Many of these second-generation blowing agents
were also attractive because they could be used directly as drop-in replacements for CFCs.
HCFCs, however, also face phase-out under the Montreal Protocol and subsequent agreements
due to their contribution to stratospheric ozone depletion and, thus, they represent only an interim
replacement for CFCs.
The need to identify suitable replacement chemicals that do not contribute to the depletion
of stratospheric ozone to be used as third-generation blowing agents (or in other applications that
relied on CFCs, such as refrigerants, fire exinguishants, and anesthetics) has led to a virtual
explosion of new research. Many new classes of chemical compounds have been investigated as
substitutes and existing classes have been expanded. These chemical classes include per-
fluorinated hydrocarbons (PFCs), partially fluorinated hydrocarbons (HFCs), per- or partially
fluorinated ethers (PFEs and HFEs, respectively), per-fluorinated amines, and iodo-fluorocarbons.
The chemicals in the most basic class of organic chemicals, hydrocarbons, have also been
considered as new blowing agent alternatives.
2

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The search for third-generation blowing agents has led to the inevitable realization that as
the number of potential substitutes increases, new concerns are generated. The work performed
in this project builds upon an earlier EPA co-operative agreement (CR 821920-01-0) on the
Identification of CFC and HCFC Substitutes for Blowing Polyurethane Foam Insulation Products
(Howard et al, 1995; 1995a) that addressed some of these concerns. In this project, 105 non
ozone depleting chemicals were ranked for their potential to be used as a blowing agent
substitutes based on four criteria; vapor thermal conductivity, boiling point, molecular weight,
and hydroxyl radical reaction rate as a surrogate for Global Warming potential (GWP). The
toxicity of the substitute chemicals was also reviewed. The first two factors addressed important
physical properties that a substitute blowing agent would require to perform adequately in the
manufacture of insulating polyurethane foams; the molecular weight was used to address the cost
associated with the use of the alternate blowing agent, and the hydroxyl radical rate provided an
indication of its environmental impact if it was released to the atmosphere.
A number of deficiencies were discovered in this initial work which led to difficulties in
evaluating and ranking the alternative chemicals for their potential to be introduced as commercial
blowing agents. Two of these areas are investigated in more detail in this project: 1) the inability
to obtain or accurately estimate the flammabilities of many of the candidate alternatives and 2) the
ability to convert a chemical's hydroxyl radical reaction rate into a meaningful GWP. Many of the
third-generation blowing agents under consideration are fluorinated organics. Increasing a
chemical's degree of fluorination tends to lower its vapor thermal conductivity and making it
more attractive substitute for an insulating foam blowing agent. A high degree of fluorination
3

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also tends to decrease the flammability of the substitute yet it also increases its atmospheric
lifetime and, therefore, increases its potential to contribute to global warming. At the other end of
the spectrum of potential third-generation blowing agents are the hydrocarbons which are
typically flammable, have higher vapor thermal conductivities, yet are not expected to significantly
contribute to global warming. Developing methodology and techniques to balance these opposing
effects for these, and other classes of candidate third-generation blowing agents, was undertaken
in this project.
This project also embarked on a new area of research to identify blowing agent mixtures
as potential third-generation substitutes. In a best-case scenario, the two components of a
mixture may display a synergistic effect where the overall characteristics of the blowing agent are
better than if either substance was used individually. The focus of this work was on a specific
type of mixture, the azeotropic or constant boiling mixture. This special type of mixture is
advantageous because the properties of the boiling agent would be constant throughout the
foaming process. This project resulted in the development of a methodology for predicting when
an azeotropic mixture will be formed as well as estimation techniques for determining the
properties of the resulting mixture that are important for assessing its use as a blowing agent. It is
hoped that this research will inspire interested parties to expand the results described herein to
laboratory trials and incorporate azeotropic mixtures into new rigid insulating polyurethane foam
formulations.
4

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Blowing Agent Flammability
The flammability limits of a blowing agent substitute are important to evaluate when
considering the overall safety of the manufacture, transport, use, and disposal of insulation
polyurethane foams. In Europe, various pentane isomers have been used commercially for a
number of years as blowing agents for polyurethane foams although the relatively high degree of
flammability of these hydrocarbons has often been cited as the reason for their cautious
development in North America (Volkert, 1996). First-generation blowing agents were fully
halogenated alkanes, and experience has shown that these compounds are non-flammable.
Halons, fully halogenated alkanes containing bromine and/or iodine, have the ability to suppress
fire and are used as extinguishing agents. HCFCs, HFCs, and HFEs lie in the middle of the
spectrum defined by the flammable alkanes at one end and the non-flammable halons, CFCs, and
PFCs at the other. Because HFCs and HFEs hold promise as third-generation blowing agents, an
investigation of flammability limits and, in the absence of experimental data, the predictive
methods used in their determination was undertaken.
Limits of flammability may be used to determine guidelines for the safe handling of
blowing agents and other volatile chemicals. The lower limit of flammability (LFL) is defined as
the minimum concentration of a combustible substance that is capable of propagating a flame
through a homogenous mixture in the presence of an ignition source (ASTM, 1991). The upper
limit of flammability (UFL) is similarly defined as the highest concentration that can propagate a
5

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flame. LFLs and UFLs are commonly reported as the volume percent or volume fraction of the
flammable component in air at 25 °C.
The flash point of a substance, defined as the minimum temperature at which it emits
sufficient vapor to form an ignitable mixture with air (Lyman et al., 1990), can also be used as an
indication of a blowing agent's flammability. The value of a chemical's flash point, however, is
not as important as the observation that it is flammable under typical operating conditions. The
flash point must also be used with caution because substances with a flash point less than 37.8 °C
(100°F) are commonly referred to as non-flammable as this is the flammability cutoff used in the
shipping industry. This is the reason that many halogen-containing chemicals have been described
as non-flammable when, in fact, they form explosive mixtures in air.
Auto ignition temperatures, or the minimum temperature at which a compound will initiate
and support the combustion process, also needs to be considered. This value is dependent on a
number of factors including the composition of the vapor-air mixture, the oxygen concentration,
rate and duration of heating, and any catalytic effects of nearby materials. Given the inability to
accurately anticipate the factors that influence a chemical's auto ignition temperature and the
problems associated with halocarbon flash points, LFLs and UFLs were deemed the most
appropriate values to investigate for potential blowing agent substitutes. Moreover, auto ignition
temperatures are typically over 200 °C for hydrocarbons and higher still for halogenated species.
Because these values are much higher than the temperatures typically observed during the
manufacture, distribution, and use of blowing agents, auto ignition temperatures are not expected
6

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to be an important factor when choosing blowing agent substitutes. Therefore, LFLs and UFLs
were deemed the most appropriate values to investigate for establishing the flammability of
blowing agent substitutes.
In the initial stages of this project (Howard et al, 1995; 1995a), considerable effort was
spent gathering physical/chemical properties for the potential blowing agent candidates. Upper
and lower flammability limits were only found for 35 of the 105 members in the extensive data
collection exercises performed in this project. Methodology to fill these data gaps was required
to establish which potential blowing agent substitutes were most promising based on this
important safety issue.
There are a number of estimation methods available to determine LFLs and UFLs and,
thus, Syracuse Research Corporation (SRC) set out to determine which technique was most
appropriate for this project. A set of reasonably priced computer programs for estimating LFLs
and UFLs using the second-order group fragment constants of Benson and Buss (Benson and
Buss, 1958) were available. The author of this program is highly experienced in physical/chemical
property compilation and hazard potentials of chemical substances (Seaton, 1989). These
computer programs, however, did not contain the full set of group constants derived by Benson
and Buss and did not have fragments for fluorine substituents. The absence of fluorine fragments
did not allow the use of these estimation programs for this project.
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The DIPPR data compilation (Daubert and Danner, 1996) contains approximately 1,300
chemicals with either an upper or lower flammability limit. Of these, approximately 1,000
chemicals had an estimated values for either the UFL or LFL. This compilation used the method
of High and Danner (High and Danner, 1987) for UFLs and the method of Shebeko (Shebeko et
al., 1983) for LFLs when experimental values were not available. Given the reliable reputation of
this data collection, these flammability estimation methods were investigated first. Analysis of
these estimation methods revealed a number of problems related to their use for fluorinated
compounds. The method of High and Danner has fragment contributions for the -CF, -CF2, and -
CF3 groups, however, their values are all zero. This indicates that, statistically, these groups did
not significantly influence the UFL. This methodology accounts for the presence of fluorine
fragments to some extent by "diluting the effect of other groups," such as -CH3, -CH2, and -O-
(High and Danner, 1987). It appeared that this methodology would not adequately predict the
UFL of the HFCs and HFEs considered in this project because of the lack of discrimination
between the different fluorine group constants; a view that was confirmed after the data collection
stage of this task (discussed below). For the purposes of this discussion, the relevant data is
presented here. Table 1 provides a comparison of estimated UFLs for HFCs and HFEs obtained
using the method of High and Danner with experimental values collected from the literature.
Analysis of the data in Table 1 indicates that the estimation method described typically results in a
UFL within a factor of 2 of the experimental value for HFCs and HFEs that are known to form
explosive mixtures in air. For non-flammable chemicals, those that do not form explosive
mixtures in air (UFL = 0), the method of High and Danner does not provide reliable results.
8

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Table 1. Comparison of Experimental and Estimated UFLs for HFCs and HFEs
Name	Experimental UFL Estimated UFL (%)
(%)
Methane, difluoro-	33.5	27.0
Ethane, 1,1-difluoro-	17.5	25.9
1-Propene, 1,1,2,3,3,3-hexafluoro-	0	28.3
Ethane, fluoro-	18.0	17.2
Ethane, pentafluoro-	0	28.0
1,1,1,4,4,4-Hexafluorobutane	9.6	15.7
1,1,1,2,3-Pentafluoropropane	10.7	20.7
1,1,1,2,3,3-Hexafluoropropane	0	22.6
1,1,1,2,3,3,3-Heptafluoropropane	0	22.6
l-Methoxy-2,2,2-trifluoroethane	14.3	22.6
1,1,1,3,3-Pentafluoropropane	11.2	20.4
1,1,2,2,3-Pentafluoropropane	12.8	20.7
Ethane, 1,1,1,2-tetrafluoro-	0	24.5
Hexafluorocyclopropane	0	22.6
Difluoromethyl ether	0	37.4
1,1,1,2,2,3,3-Heptafluoropropane	0	22.6
9

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The LFL estimation method of Shebeko (Shebeko et al., 1983) contains atom fragment
constants for fluorine groups. The authors indicate that their methodology for fluorinated
compounds was based on a small data set and that the route mean square error for the LFL, 17%,
was at least better then other available estimation methods. Given that most chemical compounds
have an LFL that is less than 10% in air (that is, they have an experimental LFL of 10%), an error
of ± 17% is quite high. The use of this method for blowing agent substitutes was deemed
inappropriate after the data collection phase of this project was completed. Table 2 contains a
comparison of estimated LFLs for HFCs and HFEs using the method of Shebeko with
experimental values obtained from the available literature. Analysis of these data indicates that
this methodology is frequently off by a factor of 2 for flammable chemicals. More importantly,
this method is not capable of accurately predicting if a chemical is non-flammable (LFL = 0).
Therefore, neither of the methods used in the DIPPR compendium are suitable for this project
because they are incapable of identifying the promising HFC or HFE blowing agents, those that
are non-flammable.
There are also a number of other methods available for estimating a chemical's LFL or
UFL. These methods are based on a chemical's activation energy and other thermodynamic
properties. Given that the extensive literature searches we have performed on blowing agent
substitutes has revealed that thermodynamic data on new HFCs and HFEs are generally not
available, they would have to be estimated. Calculating flammability limits from thermodynamic
data that was itself estimated was not expected to result in the development of methodology that
10

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Table 2. Comparison of Experimental and Estimated LFLs for HFCs and HFEs
Chemical
Methane, difluoro-
Ethane, 1,1-difluoro-
1-Propene, 1,1,2,3,3,3-hexafluoro
Ethane, fluoro-
Ethane, pentafluoro-
1,1,1,4,4,4-Hexafluorobutane
1,1,1,2,3-Pentafluoropropane
1,1,1,2,3,3-Hexafluoropropane
1,1,1,2,3,3,3-Heptafluoropropane
1 -Methoxy-2,2,2-trifluoroethane
1,1,1,3,3-Pentafluoropropane
1,1,2,2,3-Pentafluoropropane
Ethane, 1,1,1,2-tetrafluoro-
Hexafluorocyclopropane
Difluoromethyl ether
1,1,1,2,2,3,3-Heptafluoropropane
* NF = Not Flammable
Experimental LFL
(%)
12.7
4.4
NF*
3.8
NF
7.3
9.6
NF
NF
4.5
8.9
8.3
NF
NF
NF
NF
Estimated LFL
(%)
21.2
5.6
6.6
4.2
11.1
3.2
4.5
5.5
7.1
4.3
4.5
4.5
7.7
6.6
9.2
7.1
11

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would allow the reliable identification of third-generation blowing agent substitutes and,
therefore, other techniques were pursued.
Because the available estimation programs were not capable of providing the required
information on blowing agent substitute flammabilities, SRC set out to establish if new
methodology could be developed for predicting LFLs and UFLs for organic compounds with an
emphasis on HFCs and HFEs. In order to perform this investigation, experimental UFLs and
LFLs were required. Data collection for this stage of the project focused on sources that
contained a large number of experimental values and those most likely to provide data on HFCs
and HFEs:
•	Physical and Thermodynamic Properties of Pure Chemicals. The compendium of
data from the DIPPR project (Daubert and Danner, 1996);
•	Air-Conditioning and Refrigeration Technology Institute's Refrigerant database
(ARTI, 1997);
•	The Merck Index Twelfth Edition on CD-ROM (Merck, 1996);
•	Sax's Dangerous Properties of Industrial Materials, eighth edition on CD-Rom
(Lewis, 1994); and
•	Individual papers on blown polyurethane foams such as those in the Proceedings
of the Polyurethanes World Congress.
At the completion of this process, LFLs or UFLs were located for over 500 compounds.
These data are presented in Appendix A.
SRC analyzed the largest of the two data sets, the UFL data, first by performing multiple
linear regressions on a matrix of fragment constants. Chemicals containing either a metal (i.e.,
non-organic chemicals) or a non-discrete fragment (i.e., compounds like methane, carbon
12

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monoxide, carbon disulfide that have fragments that cannot appear in any other compound) were
removed resulting in 384 experimental UFLs that could be used to develop the methodology.
Group fragments in these chemicals were initially identified electronically using the capabilities
built into SRC's suite of estimation programs (http://esc.syrres.com/estsoft.htm). As a starting
point, fragments were obtained from SRC's log octanol/water coefficient estimation program
because this program contained the largest fragment set. This technique rapidly identified 52
unique fragments (Table 3) which produced a correlation coefficient (r2) of 0.54 in a multiple
linear regression with the experimental UFLs. It was thought that results that explained over half
of the flammability limits would not occur this early in the methodology development. This initial
encouragement was short-lived, however, as efforts to improve the methodology by carefully
refining the group fragments failed to substantially increase the reliability of the method and
correlation coefficients exceeding 0.64 could not be achieved. These efforts suggested that either
extensive effort would be required to refine the techniques into a reliable, general estimation
technique for flammability limits or that there was an as yet undefined issue that required
resolution.
Effort was then focused on only halogen-containing compounds in general and HFCs and
HFEs specifically to establish if flammability limits could be obtained for blowing agent
substitutes. The database of collected flammability limits contained 115 halogen containing
compounds. Fragments were identified specifically for these halogen-containing compounds and
multiple linear regressions were performed. In short order, it became evident that limiting this
13

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Table 3. Fragments Used in UFL Estimation Methodology Development*
Fragment Fragment Coefficient	Fragment	Fragment Coefficient
#C	3.11	-NH2	21.40
-Br	-3.40	-N02	1.34
-C#N	5.84	-ArN02	0.40
-C(=0)C=	-1.93	-O-	14.90
-C(=0)C	0.81	Ar-O-Ar	-4.41
-ArC(=0)	-2.84	-=COC=	0.00
-C(=0)N	-1.87	-OP	-1.05
-C(=0)0	2.85	-OH	2.38
-ArC(=0)0	-0.65	-ArOH	0.00
-CH	-1.31	-ON02	-3.41
-CH2	-1.33	-S	9.23
-CH3	0.09	-S(=0)	1.40
-CHO	26.35	-tertC	-1.71
-ArCHO	-2.18	-=C	-2.38
-CL	-1.02	-=CH2	5.01
-ArCl	-0.68	-P	0.00
-C=CCL	0.85	-NCHO	-1.16
-COOH	-1.77	-ArC	-0.27
-F	-0.66	-ArN	-7.07
-ArF	0.96	-ArN5	0.00
-C=CF	6.36	-ArO	-0.02
-I	-1.57	-C	-1.82
-ArNC	9.90	-P(=0)	1.69
-NP	4.20	-C(=0)X	-7.17
-N<	-0.96	-OO	-0.61
-NH	1.65	-NCO	-0.24
* For the equation: UFL 10.78 + [(S number of fragments) x (fragment coefficient)]
14

-------
technique to just halogen-containing compounds would not produce results that were any better
than the general methodology discussed above. Moreover, a relatively large number of the
halogen-containing compounds were non-flammable (UFL = zero) and the regression equations
were not capable of predicting this result. Further limiting the scope of the estimation method to
only fluorine-containing compounds using the fragments in Table 4 produced reasonable results
(r2 = 0.63 for 30 compounds), although the size of the data set was becoming too small to provide
a high degree of confidence in the results. Therefore, it did not appear worthwhile to attempt to
refine the methodology further.
At this stage of the project, the reason that the existing flammability estimation methods
(as well as the methods under development) were not adequate for blowing agent substitutes
became clear. These methods were developed to estimate the flammability limits of compounds
that were expected to be flammable. In essence, the flammability estimation methods were
designed to do the opposite of what was required for this project, predict which blowing agents
substitutes were non-flammable. This realization led to another course of action.
The 105 halogen-containing compounds with experimental LFLs and UFLs were re-
examined to establish what degree of substitution might render a chemical non-flammable.
Analysis of the collected data set indicated that for saturated (no double or triple bonds)
15

-------
Table 4. Fragments for HFC and HFE Flammability Limits*

Fragment
Fragment
Coefficient
-CF3
2.30
-CF2
5.90
-CF
2.09
-CH3
0.44
-CH2
3.24
-CH
-3.45
-0
-7.78
-C=CF
11.58
-Hydrogens
5.46
-Carbons
-7.70
* For the equation: UEL 7.91 + [(E number of fragments) x (fragment coefficient)]
16

-------
compounds that do not contain iodine, the compound was non-flammable if the halogen (CI, Br,
or F) to hydrogen index was < 1.2:
halogen:hydrogen index = (# of halogens + # of hydrogens) / # of halogens	(1)
Thus, if the halogen:hydrogen index < 1.2, the compound is expected to be non-flammable. It is
important to note that a compound may have a halogen:hydrogen index of >1.2 and still be non-
flammable, and this represents a limitation in equation 1. The advantage of equation 1 is that it
works successfully if other functional groups are present, and can be applied to potential blowing
agent substitutes such as the HFEs. Unsaturated compounds were excluded from this analysis as
the double (or triple) bonds in the molecule support combustion. Iodo-compounds were excluded
as those included in Appendix A are all non-flammable. The iodo-compounds in Appendix A are
all relatively small compounds and typically contain additional halogen atoms and, therefore, it
would not be reasonable to suggest that all iodo-compounds are non-flammable.
The above exercise was repeated with only fluorine containing, saturated, non-iodine-
containing organic compounds to establish if the fluorine:hydrogen index differed substantially
from the halogenrhydrogen index:
fluorine:hydrogen index = (# of fluorines + # of hydrogens) / # of fluorines	(2)
17

-------
The available data indicates that the fluorinerhydrogen index cut-off for flammability is < 1.3.
Therefore, HFCs and HFEs with a fluorinerhydrogen index < 1.3 are expected to be non-
flammable. There were, however, only 23 chemicals (Table 5) used for this evaluation and it
may not be as broadly based as the halogen:hydrogen index which was based on 115 chemicals.
There are examples of other techniques that can be used to establish if a chemical
compound is expected to be nonflammable. Group additivity principles have been used to
estimate combustion enthalpies using the extensive compilations of group fragments available
(Hendriks, 1998). In this regard, HFCs having combustion enthalpies below approximately 7,850
kJ kg"1' were non-flammable at room temperature.
The halo gen: hydro gen index for predicting which blowing agent substitutes are expected
to be non-flammable addresses an important aspect in the selection of alternatives. In a later
section of this report, the initial list of 105 blowing agent substitutes is re-ranked and updated
using new data generated in this project. The experimental or estimated flammability data for the
105 blowing agent substitutes are included in a later section of the report (Table 9).
18

-------
Table 5. Halogen:Hydrogen Index of Fluorinated Organics
Experimental Experimental FluorinerHydrogen
Name	LEL (%) UEL (%)	Index
Perfluorocyclobutane
NF*
NF
1.0
Hexafluorocyclopropane
NF
NF
1.0
T etrafluoromethane
NF
NF
1.0
Hexafluoroethane
NF
NF
1.0
Octafluoropropane
NF
NF
1.0
Decafluorobutane
NF
NF
1.0
1,1,1,2,3,3,3-Heptafluoropropane
NF
NF
1.1
1,1,1,2,2-Pentafluoroethane
NF
NF
1.2
1,1,1,2,3,3-Hexafluoropropane
NF
NF
1.3
T rifluoromethane
NF
NF
1.3
1,1,2,2,3-Pentafluoropropane
8.3
12.8
1.4
1,1,1,3,3-Pentafluoropropane
8.9
11.2
1.4
bis(difluoromethyl) ether
NF
NF
1.5
1,1,1,2-Tetrafluoroethane
NF
NF
1.5
1,1,2,2-Tetrafluoroethane
NF
NF
1.5
1,1,1,4,4,4-Hexafluorobutane
7.3
9.6
1.7
Difluoromethane
12.7
33.5
2.0
1,1,2-Trifluoroethane
5.8
24.4
2.0
1,1,1 -T rifluoroethane
9.2
18.4
2.0
2-(Methoxy)-1,1,1 -trifluoroethane
4.5
14.3
2.7
1,1 -Difluoroethane
4.4
17.5
3.0
1,2-Difluoroethane
3.6
21.8
3.0
Fluoroethane
3.8
18.0
6.0
*NF= Not Flammable
19

-------
Global Warming Potential
Introduction
When considering the tremendous amount of chemical that is used in blowing foams, and
the potential for all of it to eventually enter the atmosphere, blowing agents could provide a
significant portion of the man-made contribution to global warming. The higher the potential for
a third-generation blowing agent to contribute to greenhouse warming, the less attractive it is as a
substitute. A quantitative determination of a chemical's potential to contribute to the greenhouse
effect is its GWP. GWPs are determined mathematically by calculating how long a chemical
survives in the atmosphere, how much infra red (IR) energy it absorbs, and how much thermal
energy it re-emits to the atmosphere relative to that of a reference compound. Carbon dioxide is
typically used as the reference compound, although CFC-11 was commonly used in early
investigations. The higher a chemical's GWP, the higher its possibility to trap thermal radiation
and contribute to the warming of the Earth's surface.
Determining the GWP of potential substitutes has been problematic because of the limited
data available and the sophisticated nature of current predictive models which tend to be highly
resource intensive. In a recent report (Tunkel et al., 1996), SRC developed a simple methodology
for a qualitative determination of a chemical's GWP. Key aspects of this study are provided
below.
20

-------
For a chemical compound to contribute to global warming, there are three characteristics
that it must possess:
•	a sufficiently high vapor pressure to allow volatilization to the atmosphere;
•	a sufficiently long atmospheric life time to allow an appreciable concentration to
accumulate in the atmosphere; and
•	functional groups capable of absorbing IR radiation.
Volatilization to the atmosphere can be assessed from a chemical's vapor pressure. Eisenreich et
al. (1981) and Bidleman (1988) have shown that organic compounds with vapor pressures greater
than lxlO4 mm Hg exist almost entirely in the gas phase in the atmosphere and compounds with
vapor pressures less than lxlO"8 mm Hg exist almost entirely as a particulate; those compounds
with a vapor pressure between these cut-offs exist as a mixture of gas and particulate. If a
compound is expected to exist as a gas in the atmosphere, then it is reasonable to expect that it at
least has the potential to reside in the atmosphere.
To perform its intended purpose, a blowing agent has to volatilize during the foaming
process. The initial list of 105 potential blowing agent substitutes was chosen, in part, from
chemicals that have a boiling point in the range from -60 to 60 °C. Chemicals with a boiling point
in this range will typically have vapor pressures greater than lxlO2 mm Hg. Therefore, all of the
potential blowing agent substitutes considered in this project meet the first requirement for a
chemical to contribute to global warming, the potential to volatilize to the atmosphere.
Factors that determine a blowing agent's atmospheric lifetime were discussed extensively
in our previous report (Howard et al, 1995; 1995a). A few key points deserve mention here.
21

-------
Atmospheric degradation processes for organic chemicals are dominated by their oxidation by
photochemically-produced hydroxyl radicals, the most prevalent oxidant in the atmosphere
(Atkinson, 1994). Atmospheric hydroxyl radical reaction rates are available from the literature or
can be readily estimated. Based on the hydroxyl radical reaction rate, an atmospheric lifetime (t)
can be calculated using the 24 hour average atmospheric hydroxyl radical concentration of 8xl05
molecules/cm3 (Prinn et al., 1992):
x (yr) = 1 / (OH* rate constant in cm3 / molecule - sec) x 8xl05 molecule /cm3 x
(min / 60 sec) x (hr / 60 min) x (d / 24 hr) x (yr / 356 d)	(3)
For organic chemicals containing at least one hydrogen atom or those containing a double (or
triple) bond, the reaction with hydroxyl radicals is typically the most important degradative
process in the atmosphere. The rate constants for this reaction are readily available in the
literature or can be easily obtained by validated estimation techniques. One major exception is
iodine-containing chemicals, which undergo a facile degradation by direct photolysis because of
the relatively weak carbon-iodine bond. This process gives iodine-containing compounds,
including fluoro-iodo compounds, a very short atmospheric lifetime.
The final characteristic that a global warming chemical must possess is the ability to
absorb IR (thermal) radiation in the 7-13 micron (800-1200 cm"1) range, the so-called window
region. In this region, naturally occurring, long-lived gases (such as methane, carbon dioxide, and
22

-------
water vapor) only weakly absorb IR radiation. An anthropogenic chemical will have its greatest
contribution to global warming if it absorbs thermal energy in this area because naturally
occurring greenhouse gases do not (Wuebbles and Edmonds, 1991; Harvey, 1993; IPCC, 1990,
1992, 1994). In other words, anthropogenic chemicals absorbing in the window region will trap
thermal radiation that otherwise would escape to space.
In a recently completed project to identify long-lived global warmers (Howard et al.,
1995b), functional groups that were expected to absorb radiation in the 7-13 micron range were
investigated by SRC. Infrared spectra were obtained for 186 volatile chemicals in 36 different
chemical groups. All 186 anthropogenic chemicals were found to absorb IR radiation in the 7-13
micron range to some degree. All of the alternative blowing agents considered to date possess at
least one functional group that adsorbs IR radiation in the window region.
With this information in hand, SRC was able to correlate GWP to atmospheric lifetime for
those organic chemicals that are expected to undergo atmospheric degradation by the reaction with
hydro xyl radicals. The most important aspect of this analysis is provided in Figure 1, which is a
plot of atmospheric lifetime vs. GWP (100 year time horizon relative to C02). The correlation
coefficient for these data is very good (r2= 0.96). Based on these data, qualitative GWP
assignments can be made using the atmospheric lifetime ranges shown in Table 6. All of the
potential third-generation blowing agents considered in this project, with the exception of the
perfluorinated alkanes used in the initial azeotrope investigations and fluoroiodocarbons, undergo
23

-------
6,000
o
TJ
¦ MB
X
8 5,000
o 4,000
o 3,000
0)
>
"Jo 2,000
0)
DC
£¦ 1,000
0
10
50
20	30	40
Lifetime (years)
Figure 1. Atmospheric Lifetime for Organic Chemicals that React with Hydroxyl Radicals vs. GWP
60

-------
Table 6. GWP Assignments Based on Atmospheric Lifetime
Estimated Atmospheric Lifetime	Likely GWP Relative to C02
(years)
(100 year horizon)
0 - 0.3
Zero - <1
0.3 - 0.5
1 - 10
0.5 - 1.2
10 - 200
1.2 - 5
200 - 1,000
5 - 10
1,000 - 2,000
10 - 20
2,000 - 3,500
20 - 30
3,500 - 5,000
> 30
> 5,000
25

-------
atmospheric degradation by the reaction with hydroxyl radicals, and their GWPs can be assigned
using this method.
Assigning GWPs to Substitute Blowing Agents
In order to reduce the contribution of insulating polyurethane foam blowing agents on
global warming, substitutes that have low GWPs, meet the required foam performance
characteristics, and have appropriate safety factors are the most desirable. In our initial
investigation of CFC and HCFC blowing agent substitutes (Howard et al., 1995; 1995a), the
hydroxyl radical reaction rate constant was used as a surrogate for GWP in the ranking exercise.
Based on the more recent work discussed above, the GWP of the 105 blowing agent candidates
can be refined to better allow the most promising blowing agent substitutes to be identified. This
technique can also be utilized for the components of azeotropic mixtures.
SRC's earlier project on GWPs (Tunkel et al., 1996) involved collecting published data
and developing a database of known GWPs. Linking these data with the 105 blowing agent
candidates that appeared in the initial ranking exercise revealed that 13 substitutes possessed
published GWPs (Table 7). Of the remaining 92 members of the initial list, 82 candidates are
expected to react with hydroxyl radicals, and their GWP can be assigned based on their estimated
atmospheric lifetime and ranges provided in Table 6. GWP assignments for these candidates are
presented in Table 8. There were 6 iodofluoroalkanes (iodofluoromethane, iododifluoromethane,
26

-------
Table 7. Literature GWPs for the Initial List of 105 Chemical Substitutes
Name
Butane, 2-methyl-
Pentane
Acetone
Butane, 2,2-dimethyl-
Butane, 2,3-dimethyl-
Cyclopentene
Methane, difluoro-
Ethane, 1,1,1,2-tetrafluoro-
1,1,1,2,3,3,3-
Heptafluoropropane
Ethane, 1,1-difluoro-
Ethane, pentafluoro-
Cyclopentane
Methane, trifluoroiodo-
GWP
0.0004 *CFC 11
0
0 *C02
0 *C02
0 *C02
0 *C02
1800(20),580(100),180
(500) *C02
3300(20),1300(100),420
(500) *C02
4500(20),3300(100),1100
(500) *C02
460(20),140(100),44(500)
*C02
4800(20),3200(100),1100
(500) *C02
<0.001 *CFC 11
<5 (20),«1(100),«<1
(500) *C02
Reference
Heilig and Wiederman (1993)
Ballhaus and Hahn (1993)
Ashida et al. (1994)
Ashida et al. (1994)
Ashida et al. (1994)
Ashida et al. (1994)
Albritton et al. (1995)
Albritton et al. (1995)
Albritton et al. (1995)
Albritton et al. (1995)
IPCC (1996)
Heilig and Wiederman (1993)
Albritton et al. (1995)
*CFC 11 = GWP relative to CFC 11 as the reference gas
*C02 = GWP relative to C02 as the reference gas. The time horizon is in parentheses
27

-------
Table 8. Estimated GWPs for the Initial List of 105 Chemical Substitutes
OH Rate Constant Lifetime Estimated GWP
Name	x lxlO12	(years) (100 year horizon)
(cm3/molecule-sec)
Tetramethyl silane
0.1
4.06e-01
Zero to 1
2-Butene
56.388
7.21e-04
Zero to 1
1 -Pentene
31.4
1.29e-03
Zero to 1
2-Pentene
57.2678
7.10e-04
Zero to 1
Dimethoxymethane
6.87
5.92e-03
Zero to 1
1-Propene, 1,1,2,3,3,3-
hexafluoro-
7.04
5.77e-03
Zero to 1
Cyclobutane
1.2
3.39e-02
Zero to 1
Bis-2,2,2-trifluoroethyl ether
0.0943
4.31e-01
1-10
Ethane, fluoro-
0.232
1.75e-01
Zero to 1
Propane, 2-fluoro-2-methyl-
0.5573
7.29e-02
Zero to 1
2-Propanone, 1,1,3,3-
tetrafluoro
0.0143
2.84e+00
200- 1,000
1,4-Difluorobutane
2.0518
1.98e-02
Zero to 1
1,1,2,2-
T etrafluorocyclobutane
0.6136
6.62e-02
Zero to 1
1-Propene, 3,3,3-trifluoro-2-
(trifluoromethyl)-
51.4
7.91e-04
Zero to 1
1,1,2,3,3,3-Pentafluoropropyl
methyl ether
0.0768
5.29e-01
10-200
1,1,1,4,4,4-Hexafluorobutane
0.1622
2.51e-01
Zero to 1
Propane, 1,1,1-trifluoro-
0.2486
1.63e-01
Zero to 1
Trifluoromethyl methyl ether
0.072
5.64e-01
10-200
2-Propanone, 1,1,1-trifluoro
0.0151
2.69e+00
200- 1,000
(Continued)
28

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Table 8. (continued)
Name
1-Methoxy-1,1,2,2-
tetrafluoroethane
1,1 -Difluoroacetone
1,1,1,2,3 -Pentafluoropropane
Methyl trifluoroacetate
1,1,1,2,3,3-
Hexafluoropropane
2-Propanone,	1,1,1,3,3-
pentafluoro
1.3-Difluoroacetone
1,1,1 -Trifluorobutane
1-Methoxy-2,2,2-
trifluoroethane
1,1,1,3,3 -Pentafluoropropane
Difluoromethyl fluoromethyl
ether
Trimethylene oxide
1,1,2,2-Tetrafluoroethyl ethyl
ether
2-Butene,	2-methyl-
1-Butene, 3,3-dimethyl-
1-Butene, 2-methyl-
1.4-Pentadiene
Cyclopropane, methyl-
Fluorocyclobutane
OH Rate Constant
x lxlO12
(cm3/molecule-sec)
0.0783
0.0712
0.0588
0.0518
0.0116
0.002
0.1261
1.3479
0.4914
0.0294
0.0504
3.73
1.0733
86.9
28.5
60.7
53.3
0.2849
0.6442
Lifetime
(years)
5.19e-01
5.71e-01
6.91e-01
7.85e-01
3.50e+00
2.03e+01
3.22e-01
3.02e-02
8.27e-02
1.38e+00
8.06e-01
1.09e-02
3.79e-02
4.68e-04
1.43e-03
6.70e-04
7.62e-04
1.43e-01
6.31e-02
Estimated GWP
(100 year horizon)
10-200
10-200
10-200
10-200
200- 1,000
3,500-5,000
1 -10
Zero to 1
Zero to 1
200- 1,000
1 -10
Zero to 1
Zero to 1
Zero to 1
Zero to 1
Zero to 1
Zero to 1
Zero to 1
Zero to 1
29
(Continued)

-------
Table 8. (continued)
OH Rate Constant Lifetime Estimated GWP
Name	x lxlO12	(years) (100 year horizon)
(cm3/molecule-sec)
1-Propene, 3,3,3-trifluoro-
26.3
1.55e-03
Zero to 1
1,1,1,2,2,3-
Hexafluoropropane
0.107
3.80e-01
1 - 10
1,1,2,2,3-Pentafluoropropane
0.1302
3.12e-01
1 - 10
1,1,2,2,3,3-
Hexafluoropropane
0.0463
8.78e-01
1 - 10
1,1,2,3,4,4-Hexafluoro-1 -
butene
7.0683
5.75e-03
Zero to 1
1,2-Difluorobutane
0.9094
4.47e-02
Zero to 1
Trifluoromethyl ethyl ether
1.067
3.81e-02
Zero to 1
1,1,1,3,3,3-
Hexafluoropropane
0.0047
8.65e+00
1,000 - 2,000
1-Pentene, 4-methyl-
30.1132
1.35e-03
Zero to 1
1 -Trifluoromethoxy-2-
fluoroethane
0.7295
5.57e-02
Zero to 1
1,4-Pentadiene, 3-methyl-
54.6158
7.44e-04
Zero to 1
1,1 -Difluorocyclopentane
4.4625
9.11e-03
Zero to 1
Cyclopropane, ethyl-
1.381
2.94e-02
Zero to 1
Fluorocyclopentane
3.458
1.18e-02
Zero to 1
t-Butyl methyl ether
2.8224
1.44e-02
Zero to 1
Difluoromethyl ether
0.0179
2.27e+00
200- 1,000
1,1,1,2,2-Pentafluoropropane
0.1858
2.19e-01
Zero to 1
1,1,1,2,2,3,3-
Heptafluoropropane
0.0231
1.76e+00
200 - 1,000
1,1 -Difluoro butane
1.398
2.91e-02
Zero to 1
(Continued)
30

-------
Table 8. (continued)
OH Rate Constant Lifetime Estimated GWP
Name	x lxlO12	(years) (100 year horizon)
(cm3/molecule-sec)
Butane, 1-fluoro-
2.2927
1.77e-02
Zero to 1
Trifluoromethyl
difluoromethyl ether
0.009
4.52e+00
200- 1,000
1,1 -Difluorocyclobutane
0.9204
4.42e-02
Zero to 1
1,1,2,3,3-Pentafluoropropane
0.0223
1.82e+00
200- 1,000
1 -Difluoromethoxy-1,1,2,2-
tetrafluoroethane
0.0478
8.50e-01
1,000-2,000
1 -Difluoromethoxy-2,2-
difluoroethane
0.0152
2.67e+00
200- 1,000
1,1,2,2-T etrafluoropropane
0.2089
1.95e-01
Zero to 1
1 -Fluoro-2-ethylcyclopropane
1.31
3.10e-02
Zero to 1
1 -Difluoromethoxy-1,2,2-
trifluoroethane
0.0243
1.67e+00
200- 1,000
2-Fluoroethylcyclopropane
1.14
3.56e-02
Zero to 1
1 -Difluoromethoxy-1,1-
difluoroethane
0.0594
6.84e-01
10-200
1,2-Difluorocyclobutane
0.3297
1.23e-01
Zero to 1
1,2-Difluorocyclopentane
2.314
1.76e-02
Zero to 1
1,1,2,2,3,3-"
Hexafluorocyclopentane
2.2312
1.82e-02
Zero to 1
3 -Fluorocyclobutene
56.2565
7.22e-04
Zero to 1
1,2,3,4-
T etrafluorocyclobutane
0.0518
7.85e-01
10-200
2,3,4,5-
T etrafluorotetrahydrofiaran
0.1404
2.89e-01
Zero to 1
1 -Trifluoromethyl-1,2,2-
trifluorocyclobutane
0.6136
6.62e-02
Zero to 1
31
(Continued)

-------
Table 8. (continued)
Name
1,2,3,4-
Tetrafluorocyclopentane
1,1,1,3-Tetrafluoroacetone
Trifluoromethoxymethoxy
methane
OH Rate Constant
x lxlO12
(cm3/molecule-sec)
1,1,2,2,3-Pentafluorooxetane 0.0257
1,1,3,3-Tetrafluorooxetane 0.0226
1,2,3-Trifluorocyclo butane
1,2,3-Trifluorocyclopentane
0.1315
1.246
0.525
0.0091
3.434
Lifetime
(years)
1.58e+00
1.80e+00
3.09e-01
3.26e-02
7.74e-02
4.47e+00
1.18e-02
Estimated GWP
(100 year horizon)
200- 1,000
200 - 1,000
1 -10
Zero to 1
Zero to 1
200- 1,000
Zero to 1
32

-------
tetrafluoroiodoethane, pentafluoroiodoethane, and two heptafluoroiodoopropanes). The only
atmospheric lifetime available in the literature for fluoroiodocarbons is iodotrifluoromethane,
which has a maximum lifetime of less than one month based on its atmospheric half-life of 2 days
(Solomon et al., 1994). Its rapid atmospheric degradation arises from the facile photolytic
cleavage of the carbon-iodine bond, a process also expected to be the dominant fate process for
the other members of this group. Therefore, the 6 fluoroidocarbons in the initial list are expected
to have atmospheric lifetimes <0.3 years because of the rapid atmospheric photolysis of the
carbon-iodine bonds. These short atmospheric lifetimes suggest that their GWP will be zero or
near zero (the zero to 1 classification). The remaining 4 members of the initial list of candidates
(hexafluorocyclopropane, trifluoromethyl ether, hexafluorooxetane, and hexafluoroacetone) are
fully fluorinated and are not expected to react with hydroxyl radicals in the atmosphere. Fully
flourinated organics are generally classified as having very long atmospheric lifetimes and
correspondingly high GWPs, and are not acceptable as blowing agent substitutes.
33

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Re-Ranking the List of 105 Blowing Agent Substitutes
In our earlier project (Howard et al., 1995; 1995a), the initial list of 105 potential blowing
agent substitutes was ranked using four criteria: boiling point, vapor thermal conductivity,
molecular weight, and hydroxyl radical reaction rate. The hydroxyl radical reaction rate was used
a surrogate for GWP because 1) it is a readily available or easily estimated and 2) it provided a
reasonable estimate for GWP given that this value is directly related to atmospheric lifetime and
that the reaction with hydroxyl radicals is the most dominant atmospheric removal process. The
ranking exercise did, however, possess a number of limitations:
•	Blowing agent substitutes with only very small differences in their hydroxyl radical
reaction rate where given different scores in this criterion. For practical purposes,
however, their GWP would be the same;
•	One group of chemicals, the iodofluorocarbons, do not react with hydroxyl
radicals in the atmosphere (rapid degradation by direct photolysis occurs, instead)
and were scored as having high GWPs in the initial ranking exercise when, instead,
they do not contribute to global warming; and
•	The boiling point, vapor thermal conductivity, and molecular weight were all
ranked with the same weight as the GWP criteria. Boiling point and molecular
weight were used to address how the blowing agent substitute would function in
manufacture and use, molecular weight was used to address its cost, and GWP to
address its environmental impact. Given that the only reason third-generation
blowing agents are actively being searched for is because of the adverse
environmental impact (i.e., the destruction of stratospheric ozone by CFCs and
HCFCs ) of first and second generation chemicals, the most attractive substitutes
would be those free from adverse environmental effects. Therefore, it is
reasonable that the GWP ranking criterion should be of a higher weight than the
other three factors.
34

-------
Based on the development of better techniques for the determination of a chemical's
potential to contribute to global warming reported herein, a new ranking strategy was devised to
better identify the most promising third-generation blowing agents from the initial list of 105
candidates. In this new strategy, the boiling point, vapor thermal conductivity, and molecular
weight criteria remain unchanged:
•	Boiling point. 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). 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 = |BPcfcu - BPsubstitute |.
The compound with the smallest ABP was ranked number 1 while that with the
largest was ranked number 105.
•	Molecular weight. The molecular weight 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. For the molecular weight ranking, the
lowest molecular weight compound was ranked number 1.
•	Vapor thermal conductivity. The vapor thermal conductivity of the blowing agent
is a major contributor to the overall insulating ability of the foam. The lower the
vapor thermal conductivity, the better the insulation. For this criterion, the
compound with the lowest value was ranked number 1.
After the ranks for each of these three areas were assigned, the scores (ranging from 1 to 105 for
each criteria) were added together. To this sub total was added the chemical's GWP (ranging
from 0 to 4,000) to obtain a final score. If an estimated GWP range was used, the lowest value
was added to the sub total. When the exercise was complete, those candidates with the lowest
overall scores would be considered the more attractive third-generation blowing agent substitutes.
This ranking method accomplishes two things. First, it weights a chemical's potential to
contribute to global warming as the most important criterion as the range of possible GWP scores
35

-------
(0 to 4,000) is much higher than that of the other three criteria (1 to 105). In essence, it moves
those candidates with the highest GWPs to the bottom of the list. Second, for those compounds
not expected to significantly contribute to global warming (those with a zero or near-zero GWP),
the original scoring criteria that address cost and function (boiling point, vapor thermal
conductivity, and molecular weight) become the discriminating factors. The results of this
exercise are provided in Table 9.
Also presented in Table 9 are the experimental (where available) or estimated flammability
data for the blowing agent candidates. For those chemicals without experimental values, the
halo gen: hydro gen index was first determined to establish if the chemical was expected to be non-
flammable. If the halogen:hydrogen index was > 1.3, then the chemical was expected to be
flammable and the literature LFL estimation method of Shebeko (Shebeko et aL, 1983) was used.
Although the flammability limits were not used in the updated ranking exercise, they are included
to aid interested parties in selecting the most appropriate blowing agent substitutes for their
applications.
It is also important to note that a candidate's toxicity is also an important consideration
when selecting an alternative blowing agent. In our earlier report (Howard et al.,1995; 1995a),
the blowing agent candidates were divided into 14 groups based on chemical structure and the
toxicity of each group was reviewed to provide an indication of their potential health and
ecological effects. Because of the large number of variables required to address if toxic effects
will be expressed (e.g., level, route, duration of exposure, end point,
36

-------
Table 9. Ranking of the 105 Blowing Agent Substitutes
000461632 Difluoromethyl fluoromethyl ether
]	GWP: 1.00	BP: 29.90
Old Rank: 15	Rank: 17
LFL:	UFL:
000679867 1,1,2,2,3-Pentafluoropropane
2	GWP: 1.00	BP: 25.10
Old Rank: 9 Rank: 5
LFL:0	UFL: 0
000142290 Cyclopentene
3	GWP: 0.00	BP: 44.00
Old Rank: 1 Rank: 52
LFL: 1.5	UFL: 12.1
000591935 1,4-Pentadiene
^	GWP: 0.00	BP: 26.00
Old Rank: 2	Rank: 7
LFL:	UFL:
000360521 2-Propanone, 1,1,3,3-tetrafluoro
^	GWP: 10.00 BP: 23.31
Old Rank: 22	Rank: 2
LFL:	UFL:
000431312 1,1,.1,2,3-Pentafluoropropane
£	GWP: 10.00 BP: 22.70
Old Rank: 14	Rank: 4
LFL: 9.6	UFL: 10.7
MW : 100.04 TC : 10.30 i I H
F H

43
Estimated UFL:
21
MW: 134.05	TC : 8.81
69 9
Estimated UFL:
MW : 68.12	TC : 10.80
F I "H
F F
o
24
Estimated UFL:
h2c-
•CH„
MW : 68.12 TC : 12.60
10	68
Estimated UFL:
MW : 130.04 TC : 9.63 H
62	16
Estimated UFL: 4.79
H F
MW : 134.05 TC : 8.92
70	10
Estimated UFL:
fVV*
F H F
(Continued)
BP = Boiling point in degrees C	LFL = Lower Flammabilrty Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
37

-------
Table 9. (continued)
001493034 Methane, iododifluoro-
~J	GWP: 0.00	BP: 21.60
Old Rank: 45	Rank: 6
LFL:	UFL
000431050 1,1-Difluoroacetone
g	GWP: 10.00 BP: 34.13
Old Rank: 20	Rank: 28
LFL:	UFL
072507858 1,2-Difluorocyclobutane
9	GWP: 0.00 BP: 24.07
Old Rank: 17	Rank: 1
LFL:	UFL:
000407590 1,1,1,4,4,4-Hexafluorobutane
] Q	GWP: 0.00	BP : 24.90
Old Rank: 21	Rank: 3
LFL:7.3	UFL: 9.6
000563462 1-Butene, 2-methyl-
] ]	GWP: 0.00	BP : 31.00
Old Rank: 3	Rank: 20
LFL: 1.4	UFL:
123812806 3-Fluorocyclobutene
] 2	GWP: 0.00	BP : 32.67
Old Rank: 4	Rank: 25
LFL:	UFL:
002366521 Butane, 1-fluoro-
] 3	GWP: 0.00	BP : 32.50
Old Rank: 7	Rank: 23
LFL:	UFL:
MW: 177.92
96
Estimated UFL:
MW: 94.00
36
Estimated UFL:
MW: 92.00
34
Estimated UFL:
MW: 166.07
92
Estimated UFL:
MW : 70.14
13
Estimated UFL:
MW : 72.00
17
Estimated UFL:
MW : 76.11
22
TO : 6.25
2

TO : 11.00
32
TO : 12.70
73
TO : 9.50
TO : 12.90 f^c
76
CHj
3
TO : 12.50
67


TC : 12.50
65
Estimated UFL: 2.02
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
38

-------
Table 9. (continued)
000421501 2-Propanone,	1,1,1-trifluoro
14 GWP: 10.00	BP: 26.21
Old Rank: 39	Rank: 9
LFL:	UFL:
000109682 2-Pentene
] ^ GWP: 0.00	BP : 37.00
Old Rank: 5	Rank: 34
LFL:	UFL
000109671 1-Pentene
16 GWP: 0.00	BP : 29.90
Old Rank: 6	Rank: 18
LFL: 1.5	UFL: 8.7
000666160 Fluorocyclobutane
] ~J GWP: 0.00	BP : 29.19
Old Rank: 19	Rank: 15
LFL:	UFL:
6104 1,2,3-Trifluorocyclobutane
] g GWP: 1.00	BP : 18.92
Old Rank: 28	Rank: 12
LFL:	UFL:
000067641 Acetone
] 
-------
Table 9. (continued)
022669096 1,1 -Dif luorocyclobutane
2]	GWP: 0.00 BP: 17.69
Old Rank: 23	Rank: 19
LFL:	UFL
000372907 1,4-Difluorobutane
22	GWP: °-00 BP •' 28 82
Old Rank: 18	Rank: 14
LFL	UFL
000680002 1,1,2,2,3,3-Hexafluoropropane
23	GWP: 1.00 BP: 10.00
Old Rank: 50	Rank: 35
LFL:	UFL
000558372 1 -Butene, 3,3-dimethyl-
24	GWP: 0.00 BP: 41.00
Old Rank: 10	Rank: 44
LFL: 1.2	UFL: 9.0
000287923 Cyclopentane
25	GWP: 0.00	BP : 50.00
Old Rank: 13	Rank: 68
LFL: 1.4	UFL: 9.4
129362976 1,2,3,4-Tetrafluorocyclobutane
25	GWP: 10.00 BP: 13.74
Old Rank: 43	Rank: 26
LFL:	UFL:
000287230 Cyclobutane
27	GWP: 0.00
Old Rank: 26
LFL: 1.8
BP: 12.50
Rank: 31
UFL: 11.1
MW: 92.00
35
Estimated UFL:
MW: 94.11
38
TC : 12.80
74
nf
TC : 13.00
77
Estimated UFL: 2.28
MW: 152.04 TC : 9.27
82	12
Estimated UFL: 5.57
H,C
^/CH3
' CH,
HjC ^
MW : 84.16
26
Estimated UFL:
MW : 70.14
11
Estimated UFL:
MW : 128.00
58
Estimated UFL:
MW: 56.11
5
Estimated UFL:
TC : 12.40
61
TC : 12.10
54
o
TC : 11.40
39
~
TC : 14.80
99
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
40
-------
Table 9. (continued)
000513359 2-Butene, 2-methyl-
28	GWP: °-00 BP •' 35-00
Old Rank: 8	Rank: 30
LFL1.4	UFL: 9.6
000594116 Cyclopropane, methyl-
29	GWP: 0.00	BP: 4.00
Old Rank: 35 Rank: 51
LFL:	UFL:
040723635 1,1,2,2-Tetrafluoropropane
3Q	GWP: 0.00 BP: -1.60
Old Rank: 42	Rank: 65
LFL:	UFL:
000354643 Ethane, pentafluoroiodo-
3 ]	GWP: 0.00	BP : 12.00
Old Rank: 77	Rank: 32
LFL:0	UFL: 0
000431470 Methyl trifluoroacetate
32	GWP: 10.00 BP: 43.00
Old Rank: 49	Rank: 49
LFL:	UFL:
000075763 Tetramethyl silane
33	GWP: °-00 BP: 26-00
Old Rank: 53	Rank: 8
LFL: 1.5	UFL: 6
000107017 2-Butene
34	GWP: 0.00	BP: 1.00
Old Rank: 12	Rank: 58
LFL:	UFL:
MW: 70.14
15
Estimated UFL:
MW: 56.11
4
Estimated UFL:
MW: 116.06
53
TC : 14.10
93

r
^CH3
TC : 13.50
84
ItjC
A
TC: 10.70
23
Estimated UFL: 5.13
MW : 245.92
103
Estimated UFL:
MW : 128.00
57
TC : 8.30
7
F Lp
F H H
F F
I-)	("F
F	F
TC : 10.90
26
'>lAr
F^ I	^CH3
0
Estimated UFL: 5.61
MW : 88.23
33
Estimated UFL:
MW: 56.11
3
Estimated UFL:
TC : 15.50
102
CHj—Si-CH3
CHj
H,C

TC : 13.50
83
BP = Boiling point in degrees C	LFL = Lower Fiammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Fiammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
41
-------
Table 9. (continued)
000691372 1 -Pentene, 4-methyl-
35	GWP: 0.00	BP: 53.00
Old Rank: 16	Rank: 76
LFL1.2	UFL: 9.4
001191964 Cyclopropane, ethyl-
GWP: 0.00	BP: 34.50
Old Rank: 30	Rank: 29
LFL:	UFL
003831490 Ethane, 1-iodo-1,1,2,2-tetrafluoro-
37	GWP: 0.00 BP: 41.00
Old Rank: 81	Rank: 43
LFL:	UFL:
000109660 Pentane
33	GWP: 0.00
Old Rank: 24
LFL: 1.5
MW: 84.16
25
Estimated UFL:
MW: 70.14
16
Estimated UFL:
MW: 227.93
102
Estimated UFL:
MW : 72.15.
19
Estimated UFL:
BP: 36.10
Rank: 33
UFL: 7.8
000677690 Propane, 1,1,1,2,3,3,3-heptafluoro-2-iodo-
39	GWP: 0.00	BP: 38.00 MW: 295.93
Old Rank: 84 Rank: 37	105
LFL:0	UFL: 0	Estimated UFL:
000754347 Propane, 1,1,1,2,2,3,3-heptafluoro-3-iodo-
40	GWP: 0.00 BP : 40.00 MW : 295.93
Old Rank: 82	Rank: 42	104
LFL:0	UFL: 0	Estimated UFL:
6119	Trifluoromethoxymethoxymethane
4]	GWP: 0.00	BP: 29.52 MW: 130.00
Old Rank: 27	Rank: 16	61
LFL:	UFL:	Estimated UFL:
TO : 11.70 HjC
43
TO : 15.60
103


CH3
TC : 7.45
3
s	e
H3C
CH3
TO : 14.80
98
TC : 8.54
8
,F
TC : 8.06
4
,F
h3c

CF,
TC : 12.80
75
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
42
-------
Table 9. (continued)
000453145 1,3-Difluoroacetone
42 GWP: 100 BP ¦' 49 87
Old Rank: 59	Rank: 67
LFL:	UFL:
000333368 Bis-2,2,2-trifluoroethyi ether
GWP: 1-00 BP: 9-50
Old Rank: 67	Rank: 38
LFL:	UFL
000686657 1,2-Difluorobutane
44	GWP: 0.00 BP : 8.56
Old Rank: 46	Rank: 39
LFL:	UFL:
000512516 1,1,2,2-Tetrafluoroethyl ethyl ether
45	GWP: 0.00 BP : 14.95
Old Rank: 44	Rank: 24
LFL:	UFL:
000460344 1,1,1-Trifluorobutane
GWP: 0.00	BP: 0.38
Old Rank: 40	Rank: 60
LFL:	UFL:
000677214 1-Propene, 3,3,3-trifluoro-
47	GWP: 0.00 BP : -18.00
Old Rank; 25	Rank: 90
LFL:	UFL:
000421078 Propane, 1,1,1-trifluoro-
48	GWP: 0.00 BP : -13.00
Old Rank: 57	Rank: 86
LFL:	UFL:
MW : 94.06
37
Estimated UFL:
MW: 182.00
99
TO : 12.00
48
TC : 9.93
17

Estimated UFL 3.47
MW: 94.11
39
Estimated UFL:
MW: 146.00
76
Estimated UFL:
MW: 112.00
49
Estimated UFL:
MW : 96.05
41
TC : 13.00
78
TC : 12.20
57
TC : 12.00
49
TC : 10.90
27
Estimated UFL: 2.15
MW: 98.07 TC: 11.00
42	31
Estimated UFL 3.97
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
CH„
F F
F F
CH3
CHj
(Continued)
43
-------
Table 9. (continued)
002358385 1,1-Difluorobutane
49	GWP: 0.00	BP : 8.56
Old Rank: 37	Rank: 40
LFL:	UFL:
123768183 1,1,2,2,3,3-Hexaf luorocyclopentane
MW: 94.11
40
Estimated UFL:
CH,
5Q	GWP: 0.00
Old Rank: 36
LFL:
BP: 13.58
Rank: 27
UFL:
000374129 1,1,2,2-TetrafIuorocyclobutane
5 ]	GWP: 0.00	BP : 0.76
Old Rank: 54	Rank: 59
LFL:	UFL:
000373535 Methane, iodofluoro-
52	GWP: 0.00	BP : 53.40
Old Rank: 78 Rank: 77
LFL:	UFL:
000677565 1,1,1,2,2,3-Hexafluoropropane
53	GWP: 1.00	BP: -1.20
Old Rank: 71 Rank: 63
LFL:	UFL:
000109875 Dimethoxymethane
54	GWP: 0.00	BP: 41.00
Old Rank: 33 Rank: 45
LFL: 1:6	UFL: 17.6
000460435 1 -Methoxy-2,2,2-trifluoroethane
55	GWP: 0.00	BP : 1.45
Old Rank: 65 Rank: 55
. LFL: 4.5	UFL: 14.3
MW : 178.00
97
Estimated UFL:
MW: 128.07
59
TO : 13.00
79
TO: 11.20 *\_J
37
TC : 11.90
45
F
-F
VF
F
Estimated UFL: 3.38
MW: 159.93
87
Estimated UFL:
MW: 152.04
83
TC: 5.11
1
TC : 10.00
18
Estimated UFL: 5.57
CH,'
CH,
MW : 76.00
21
Estimated UFL:
MW: 114:00
51
Estimated UFL:
TC : 14.90
101
TC : 12.50 F
62
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
44
-------
Table 9. (continued)
000503300 Trimethylene oxide
56	GWP: 0.00	BP: 50.00
Old Rank: 38 Rank: 70
LFL:2.8	UFL 37
000079298 Butane, 2,3-dimethyl-
57	GWP: 0.00	BP: 58.00
Old Rank: 34 Rank: 83
LFL1.2	UFL 7.0
6108	1,2,3-Trifluorocyclopentane
58	GWP: 0.00 BP: 47.75
Old Rank: 52	Rank: 62
LFL:	UFL:
000690222 Trifluoromethyl ethyl ether
59	GWP: 0.00 BP: 1.45
Old Rank: 58	Rank: 56
LFL:	UFL
000819498 1 -T rifluoromethoxy-2-fluoroethane
~
MW : 58.00
6
Estimated UFL:
MW: 86.18
27
Estimated UFL:
MW: 124.00
56
Estimated UFL:
MW: 114.00
52
TO : 13.80
92
TO : 12.40
60
H3C-
CH3
TC : 12.00
52

H3C
TC : 12.50
63
CF,
60	GWP: °-°0 Bp: 4-14
Old Rank: 62	Rank: 50
LFL:	UFL:
001120203 1,1 -Difluorocyclopentane
61	GWP: 0.00	BP : 46.57
Old Rank: 41 Rank: 57
LFL:	UFL:
001115088 1,4-Pentadiene, 3-methyl-
62	GWP: °-00 Bp ¦' 55-00
Old Rank: 31	Rank: 79
LFL:	UFL:
Estimated UFL: 4.35
MW: 132.00 TC : 12.10
67	55
Estimated UFL: 5.77
MW : 106.00
47
Estimated UFL:
MW: 82.15
24
Estimated UFL:
TC : 12.60
69
TC : 12.70
. 71
'CH3
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
45
-------
Table 9. (continued)
6109	1,2,3,4-Tetrafluorocyclopentane
£3	GWP: 0.00	BP: 42.76
Old Rank: 69	Rank: 47
LFL:	UFL:
000075832 Butane, 2,2-dimethyl-
£4	GWP: 0.00	BP: 50.00
Old Rank: 51	Rank: 69
LFL: 1.2	UFL 7.0
050422769 1 -Fluoro-2-ethylcyclopropane
£5	GWP: 0.00	BP: 45.44
Old Rank: 63	Rank: 54
LFL:	UFL:
113742908 1,2-Dif luorocyclopentane
GWP: 0.00	BP: 52.71
Old Rank: 61	Rank: 74
LFL:	UFL:
000353617 Propane, 2-fluoro-2-methyl-
(yj	GWP: 0.00	BP: -5.02
Old Rank: 73	Rank: 73
LFL:	UFL:
FYVP
MW : 142.00 TC : 12.00
53
74
Estimated UFL:
MW: 86.18
28
Estimated UFL:
MW : 88.00
31
Estimated UFL:
CH3
TC : 13.20
81
H^C-
\
CH3 CH3
TC : 14.50
95

MW: 106.00 TC: 12.50
46
Estimated UFL:
MW : 76.11
23
66
ch.
TC : 13.80
91
H3C-
ch.
Estimated U FL 1.85
136975092 1 -T rifluoromethyl-1,2,2-trifluorocyclobutane
68	GWP: 0.00
Old Rank: 74
LFL:
000353366 Ethane, fluoro-
69	GWP: 0.00
Old Rank: 80
LFL: 3.8
BP: 9.73
Rank: 36
UFL:
BP: -37.70
Rank: 101
UFL: 17.3
F
r^TCF 3
MW : 178.00 TC : 12.10
98
Estimated UFL:
MW: 48.06
1
Estimated UFL:
56
TC : 13.80
90
n	«
BP =-Soiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year, time horizon
(Continued)
46
-------
Table 9. (continued)
001481363 Fluorocyclopentane
7Q	GWP: 0.00	BP: 57.64
Old Rank: 66	Rank: 82
LFL:	UFL:
000680546 1,1,2,3,4,4-Hexafluoro-1 -butene
7 ]	GWP: 0.00	BP : -3.77
Old Rank: 55	Rank: 72
LFL:	UFL:
002314978 Methane, trifluoroiodo-
72	GWP: 0.00 BP: -22.50
Old Rank: 87	Rank: 92
LFL:0	UFL: 0
000116154 1 -Propene, 1,1,2,3,3,3-hexafluoro-
73	GWP: 0.00
Old Rank: 64
LFL:0
BP: -28.00
Rank: 97
UFL: 0
001814886 1,1,1,2,2-Pentafluoropropane
74	GWP: 0.00	BP: -17.60
Old Rank: 85 Rank: 88
LFL:	UFL:
069750681 2-Fluoroethylcyciopropane
75	GWP: 0.00	BP: 52.94
Old Rank: 76 Rank: 75
LFL:	UFL:
001634044 t-Butyl methyl ether
75	GWP: 0.00	BP: 55.00
Old Rank: 72	Rank: 80
LFL: 2.0	UFL: 15.1
MW: 88.00
29
Estimated UFL:
MW: 164.00
88
Estimated UFL:
MW: 195.91
101
Estimated UFL:
MW: 150.02
81
Estimated UFL:
MW: 134.05
72
TO : 13.30
82
TC : 11.00
34
TC : 8.06
5
TC : 10.47
22
TC : 11.50
41
Estimated UFL: 4.55
MW : 88.00
32
Estimated UFL:
MW: 88.00
30
Estimated UFL:
TC : 14.50
96
TC : 14.40
94
BP = Boiling point in degrees C	LFL = Lower Fiammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammabilrty Limit In % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
47
-------
F F
Table 9. (continued)
000425887 1-Methoxy-1,1,2,2-tetrafluoroethane	F F
~J~j	GWP: 10.00 BP: -12.54 MW: 132.00 TC: 12.00
Old Rank: 88	Rank: 84	64	47
LFL:	UFL	Estimated UFL: 5.77
069948294 1-Difluoromethoxy-1,1-difluoroethane
~JQ	GWP: 10.00 BP: -12.54 MW: 132.00 TC: 12.00
Old Rank: 90	Rank: 85	66	51
LFL:	UFL	Estimated UFL 5.77
CH,
CHF,
000382343 1,1,2,3,3,3-Pentafluoropropyl methyl ether
F _
79	GWP: 10.00 BP: -7.07
Old Rank: 91	Rank: 78
L£L:	UFL:
000421147 Trifluoromethyl methyl ether
gQ	GWP; 10.00 BP: -24.10
Old Rank: 96
LFL:
Rank: 93
UFL:
133360006 2,3,4,5-Tetrafluorotetrahydrofuran
81	GWP: 0.00
Old Rank: 97
LFL:
BP: 49.77
Rank: 66
UFL:
MW: 182.00	TC: 11.00
100	30
Estimated UFL:
MW : 100.04	TC : 13.70
44	87
Estimated UFL:	10.08
MW: 144.00	TC : 14.80
CH,
h,c^ ^cf3
TT
75
Estimated UFL:
100
MW : 66.05
8
Estimated UFL:
TC : 11.50 h,c
40
000075376 Ethane, 1,1 -difluoro-
02	GWP: 140.00 BP: -25.00
Old Rank: 68	Rank: 94
LFL: 4.4	UFL: 17.5
000382105 1-Propene, 3,3,3-trrfiuoro-2-{trifluoromethyl)-
83	GWP: 0.00	BP: -29.10 MW: 164.05 TC : 17.00
Old Rank: 99	Rank: 99	89	105
LFL:	UFL:	Estimated UFL: 3.56
BP = Boiling point in degrees C	LFL = Lower Rammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
r
A
CF,
H
(Continued)
48
-------
TC : 8.19
6
Table 9. (continued)
000460731 1,1,1,3,3-Pentafluoropropane
Q4	GWP: 200.00 BP: 15.30 MW: 134.05 TC: 9.39
Old Rank: 32	Rank: 21	71	13
LFL8.9	UFL 11.2
6112	1,1,1,3-Tetrafluoroacatone
Q5	GWP: 200.00 BP: 28.81 MW: 130.00 TC: 11.00
Old Rank: 48	Rank: 13	60	36
LFL:	UFL
024270664 1,1,2,3,3-Pentafluoropropane
g£	GWP: 200.00 BP: 39.30
Old Rank: 47	Rank: 41
LFL:	UFL
154330402 1,1,3,3-Tetrafluorooxetane
QJ	GWP: 200.00 BP: 21.20-
Old Rank: 60	Rank: 10
LFL:	UFL
000431630 1,1,1,2,3,3-Hexafluoropropane
gg	GWP: 200.00 BP: 6.00
Old Rank: 75	Rank: 46
LFL:0	UFL 0
001691174 Difluoromethyl ether
Q9	GWP: 200.00 BP: 4.70 MW: 118.03 TC: 12.50
Old Rank: 83	Rank: 48	54	64
LFL:0	UFL 0
032778168 1-Difluoromethoxy-2,2-difluoroethane
9Q	GWP: 200.00 BP:.-1.54 MW: 132.00 TC : 12.00 F
Old Rank: 89	Rank: 64	65	50
LFL:	UFL:	Estimated UFL 5.77
BP = Boiling point in degrees C	LFL = Lower Rammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Rammabilif/ Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
MW: 134.05
71
Estimated UFL
MW: 130.00
60
Estimated UFL
MW: 134.05
68
Estimated UFL
MW: 130.04
63
Estimated UFL
MW: 152.04
85
Estimated UFL
MW: 118.03
54
Estimated UFL
-F
-F
TC : 12.20
58

TC : 10.20
F * F
20
y°y;
CHF,
(Continued)
49
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0' 2
Table 9. (continued)
056281926 1 -Difluoromethoxy-1,2,2-trifluoroethane
p	r*r» tl
9]	GWP: 200.00 BP: -15.58 MW: 150.00 TC: 11.70	'
Old Rank: 95	Rank: 87	80	44 F
LFL:	UFL:	Estimated UFL: 5.05
144109035 1,1,2,2,3-Pentafluorooxetane	F\Z°\	i
92 GWP: 200.00 BP: 3.40	MW: 148.03 TC: 13.00 F
Old Rank: 94 Rank: 53	78 80
LFL: UFL:	Estimated UFL:
002252848 1,1,1,2,2,3,3-Heptafluoropropane	F F
92 GWP: 200.00 BP : -17.70	MW : 170.03 TC : 11.00 Fx
Old Rank: 98 Rank: 89	95	35 F F
LFL:0 UFL: 0	Estimated UFL:
003822682 Trifluoromethyl difluoromethyl ether	E
94	GWP: 200.00 BP: -34.60 MW: 136.02 TC: 16.20
Old Rank: 103	Rank: 100	73	104
LFL:	UFL:	Estimated UFL:
'°\^F
\ H
000075105 Methane, difluoro-	F
95	GWP: 580.00 BP: -51.65 MW: 52.02 TC: 11.00
Old Rank: 70	Rank: 104	2	29
LFL: 12.7	UFL: 27.2 Estimated UFL:
000690391 1,1,1,3,3,3-Hexafluoropropane	F
H
OA	GWP: 1,000. BP: -0.07 MW: 152.04 TC : 10.10
00
Rank: 61	84	19
Old Rank: 86
LFL:	UFL:	Estimated UFL: 5.57
F>
F
H I ~F
F F
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air	(Continued)
TC = Vapor thermal conductivity in mW/(m - K)UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
50
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Table 9. (continued)
032778113 1-Difluoromethoxy-1,1,2,2-tetrafluoroethane
07	GWP: 1,000. BP: -3.10
00
Rank: 71
Old Rank: 93
LFL:	UFL:
000811972 Ethane, 1,1,1,2-tetrafluoro-
98
F F
GWP: 1,300.
00
BP: -26.50
Rank: 96
MW: 168.00	TC :11.50s
93	42
Estimated UFL:	6.34
MW: 102.03	TC:9.10
F F
CHF.
a	h
Old Rank: 79
LFL:0
UFL: 0
45
Estimated UFL:
11
000354336 Ethane, pentafluoro-
99
GWP: 3,200.
00
BP: -48.50
Rank: 103
Old Rank: 92
LFL:0	UFL: 0
000431890 1,1,1,2,3,3,3-Heptafluoropropane
TOD GWP: 3,300. BP: -18.70
00
Rank: 91
Old Rank: 101
LFL:0	UFL: 0
000431710 2-Propanone, 1,1,1,3,3-pentafluoro
101
MW: 120.02	TC : 10.90 F
55 25
Estimated UFL:
MW: 170.03	TC: 11.00
94 33
Estimated UFL:
t
H I F
F F
GWP: 3,500.
00
BP: 15.28
Rank: 22
MW : 148.03 TC : 9.56 F
Old Rank: 56
LFL:	UFL:
000931919 Hexsifluordcyclopropane
1 09 GWP: 4'000- BP : "47-70
00
Rank: 102
77
Estimated UFL
15
MW : 150.00 TC : 10.90 F
Old Rank: 100
LFL: 0
UFL: 0
79
Estimated UFL:
28
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Limit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
(Continued)
51
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Table 9. (continued)
001479498 Trifluoromethyi ether
1 QQ GWP: 4,000. BP: -58.70
00
Rank: 105
Old Rank: 102
LFL:	UFL:
000684162 2-Propanone, hexafluoro
104
GWP: 4,000.
00
BP: -26.00
Rank: 95
Old Rank: 105
LFL:	UFL:
000425821 1,1,2,2,3,3-Hexafluorooxetane
105 GWP: 4,000. BP : -28.20
Old Rank: 104
LFL:
Rank: 98
UFL:
MW: 154.01 TC: 12.70

86
Estimated UFL:
72
MW : 166.02 TC : 13.70 F
91	89
Estimated UFL:
Ix°XF
MW: 166.02 TC: 13.70 F X F
F F
90	88
Estimated UFL:
BP = Boiling point in degrees C	LFL = Lower Flammability Limit in % in air
TC = Vapor thermal conductivity in mW/(m - K) UFL = Upper Flammability Umit in % in air
MW = Molecular weight in g/mole
GWP = Global Warming Potential relative to carbon dioxide at the 100 year time horizon
52
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affected organ, test species, and number of studies), toxicity was not included in the ranking
exercise. Further, the results of toxicity studies on HFCs and related chemcials are appearing on
an increased frequency. The interested reader is encouraged to perform a complete review of the
toxicity of the blowing agent candidates to ensure that an up-to-date evaluation can be made.
53
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Blowing Agent Azeotropes
Introduction
The use of mixed blowing agents greatly expands the potential number of potential third-
generation blowing agents that can be used in rigid polyurethane foams. In a properly designed
mixture, the properties of one component can be used to compensate for any deficiencies in the
other component. In a best-case scenario, the two (or more) components of a mixture may have a
synergistic effect where the overall characteristics of the blowing agent are better than if either
substance was used individually. The ability to design a new blowing agent by careful selection of
mixture components greatly expands the number of third-generation alternatives.
An azeotrope can be considered the most desirable type of mixed blowing agent. An
azeotrope is defined as a liquid mixture of two or more substances which behaves like a single
substance in that the vapor produced by partial evaporation of liquid has the same composition as
the liquid (Sax and Lewis, 1987). Because the gas-phase composition of the components remain
constant, the effect of an azeotropic blowing agent on the resulting foam can be predicted more
accurately than for normal mixtures that vary in composition as the foaming process proceeds.
Azeotropic mixtures offer a number of advantages in the search for third-generation
blowing agents. These advantages, many of which have been addressed in various stages of this
project, include:
54
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•	Boiling point - The boiling point of an azeotropic mixture is either below that of
the lowest boiling component or above that of the highest boiling component. If
used in an azeotropic mixture, blowing agent substitutes with unsuitable boiling
points (i.e., boiling points substantially different than that of CFC 11, 23.8 °C) may
become more attractive because it is the boiling point of the mixture and not the
individual chemicals that is important;
•	Molecular weight - Chemicals that appeared as attractive blowing agents except
for their high molecular weight (and expected higher cost) can be paired with
lower molecular weight components. The resulting mixture could be designed to
provide the appropriate number of molecules per unit weight required to produce a
cost-effective foam;
•	Vapor thermal conductivity - One component of the mixture could have a very low
vapor thermal conductivity but has advantages in all other regards. A chemical
that ranks poorly only in vapor thermal conductivity could be formulated as an
azeotrope with a chemical that has a very high vapor thermal conductivity to
engineer a blowing agent mixture that possesses the required insulating property;
•	Global Warming Potential (GWP) - Some otherwise highly ranked blowing agent
candidates may have high GWPs. In a mixture, the amount of this chemical in the
resulting foam would be diminished. The result would be that less of this
compound is available to be released to the environment, thus reducing its
potential contribution to radiative forcing (warming of the Earth's surface);
•	Toxicity - An azeotropic mixture will not reduce the toxicity of an individual
component. If the toxic component is present as only a small amount in the
mixture, its level of use may be reduced to a point where potential adverse effects
to health or the environment are no longer a concern; and
•	Flammability - A mixture comprised of a flammable and non-flammable blowing
agent reduces the total amount of vapors that can support combustion. The
reduced quantity of vapor may prevent an explosive concentration (i.e., the lower
flammability limit) from developing during manufacturing, transport, or use. This
may allow the explosive component to be used in a mixture without the addition of
extensive engineering safeguards.
Careful choice of the components of the azeotropic mixtures would allow the desirable aspects of
each of these factors to be engineered into the blowing agent substitute.
55
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There is a general paucity of data available on the use of azeotropic blowing agents in the
manufacture of foams and a specific lack of data on using azeotropic blowing agents for the
preparation of insulating polyurethane foams. Similarly, limited data is available on azeotropes
formed from many of the most promising blowing agent substitutes, including HFC, HFE, and
iodo-fluorocarbon azeotropes. The patent literature contains a number of recent citations on
azeotropic compositions albeit limited in experimental detail.
Ashida and coworkers (Ashida et al. 1994, 1995) studied azeotropes formed by aliphatic
hydrocarbons, cyclic hydrocarbons, C4 ethers, carbonyl compounds, and carboxylic esters for
isocyanate-based foams. They found that the lowest foam density was formed when the liquid
blowing agent was in the same component proportions as the azeotropic ratio. Interestingly,
these workers also investigated the ternary azeotropic blowing agents by adding perfluoralkanes
as nucleating agents. A blowing agent of approximately 1:2:2 perfluorpentane:n-penatane:methyl
formate lowered the thermal conductivity of the resulting foam by 12% over a foam blown
without the PFC.
Werner (Werner et al., 1996) looked at azeotropes of isomeric pentanes with
perfluorohexane, 1,1,1,3,3-pentafluoropropane (HFC 245fa), 1,1,1,4,4,4-hexafluorobutrane (HFC
356mmf), or 1,3-dioxolane. Azeotropes of HFC 245 (various isomers) with perfluoroalkanes or
N-alkylperfluoromorpholine, trifluoromethyl difluoromethyl ether (HFE 125) with propane,
propene, cyclopropane, dimethyl ether, or ammonia, and HFC 356mmf or perfluorocyclohexane
with various pentane and hexane isomers have also been reported (Minor, 1996; Nalewajek et al.,
56
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1995; Werner et aL, 1996a). A particularly relevant patent by Minor (Minor, 1996a) investigated
azeotropes of octafluorobutanes (HFCs 338q, 338mee, 338mf, and 338pcc) with a series of cyclic
and acyclic fluoro-ethers (HFE c-234, c-327, and 236 isomers).
Methodology Development
The boiling behavior of binary mixtures can be explained by the Calusisus-Clapeyron
relationship. Differences in the behavior of binary systems relative to pure substances are due to
varying forces of interaction between the two components. Mixtures in which the molecules of
the two components repel each other display an increase in partial pressure due to these forces
and a corresponding decrease in boiling point. Components of a mixture that display attractive
forces have decreased partial pressures which results in an increase in boiling point. Ideal
mixtures are formed when one component is attracted to all other components equally. As
discussed above, an azeotrope is a special case when the vapor and liquid compositions are equal.
Low boiling azeotropes, the most common type, are formed when the two components repel each
other and high boiling azeotropes are formed when they attract (Stichilmair, 1988). The ability of
the UNEFAC method to predict the degree of these molecular-level interaction as well as the
resulting properties of the mixture was utilized to develop a technique to estimate the boiling
point, molar ratio (also discussed as mole fraction, azeotropic ratio, or component ratio), and
vapor thermal conductivity of azeotropic blowing agent substitutes.
57
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The process used to develop this methodology had four main stages. The first stage
required deriving the computer code for the UNIFAC estimation method for azeotropes.
Although a detailed description of this process is outside the scope of this document, there are a
number of good reference on the UNIFAC method are available (Fredenslund et al., 1975; Hansen
et al., 1991). For the azeotropic calculations, the UNIFAC procedure estimates X-Y diagrams of
binaries, where X is the mole fraction in the liquid phase, and Y is the corresponding gas phase
mole fraction. BRI's UNIFAC 6.0 package was used which allows structures to be entered
through CAS number or molecular formula. A typical X-Y diagram of acetone-cyclopropane is
shown below (Figure 2). The azeotropic concentration is the point at which the curve crosses
the central line, i.e. at a mole fraction of 0.37. In order to search for new azeotropes, different
combinations of mixtures should be evaluated, and the ones where the curve intersects the line as
in Figure 2 should be tentatively selected.
1: ACETONE
2:CYCLOPENTANE
Temp: 314 K
8.00QE-01
6.000E-01
2.000E-01
0.8
0.6
0.4
0.2
XI
Figure 2. X-Y Diagram of Acetone-Cyclopropane Binary Mixture
58
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Since an azeotrope boils at a constant temperature, the next step is to determine the
composition of the mixture at that temperature. A typical output from the program is shown
below (Table 10). Note that X^Y, at X^.37 (Figure 2). Note also that the total pressure
equals 1 bar at this composition. At the boiling point the vapor pressure equals atmospheric
pressure (1.013 bars). For convenience, this is approximated to 1 bar, and the boiling point of
this mixture is taken to be 314 K. The value of 314 K is found by trial and error through a number
of iterations. Suitable azeotropes are, thus, found through two steps. In the first, various binaries
are run until a crossover pattern such as that in Figure 2 is observed. This binary is then re-run at
various temperatures, until X=Y at a pressure of «1 to obtain the boiling point of the azeotropic
mixture.
The second stage required the identification of suitable azeotropes to test the estimation
method. The Texas Thermodynamic Database was searched for compounds of suitable boiling
point and properties (e.g., chemicals without chlorine) that could potentially be used in blowing
agent mixtures and had the appropriate experimental parameters available. Pairs of these
compounds were then processed with the UNIFAC computer model which constructs x-y
diagrams through which azeotropes can be identified. Usually, several dozen pairs needed to be
processed before an azeotropic mixture was found. That is, for every azeotrope found, 25 to 50
mixtures were investigated
Once techniques for finding azeotropic mixtures were identified, the next stage was to
expand the UNIFAC parameters for fluorinated chemicals. UNIFAC parameters were available
-------
Table 10. UNIFAC Output for Acetone/Cyclopentane Binary Mixture

Acetone


Cyclopentane
X,
T,
Y,
X2
r2


6.633E00

1.
1.000E00
1.
0.05
5.021E00
0.167
0.95
1.007E00
0.833
0.1
3.960E00
0.246
0.9
1.027E00
0.754
0.15
3.230E00
0.291
0.85
1.057E00
0.709
0.2
2.708E00
0.32
0.8
1.097E00
0.68
0.25
2.323E00
0.34
0.75
1.147E00
0.66
0.3
2.032E00
0.355
0.7
1.206E00
0.645
0.35
1.808E00
0.368
0.65
1.276E00
0.632
0.4
1.632E00
0.379
0.6
1.357E00
0.621
0.45
1.493E00
0.391
0.55
1.449E00
0.609
0.5
1.381EOO
0.404
0.5
1.555E00
0.596
0.55
1.291E00
0.418
0.45
1.674E00
0.582
0.6
1.219E00
0.435
0.4
1.811E00
0.565
0.65
1.160E00
0.455
0.35
1.966E00
0.545
0.7
1.113E00
0.48
0.3
2.142E00
0.52
0.75
1.076E00
0.512
0.25
2.343E00
0.488
0.8
1.047E00
0.554
0.2
2.571E00
0.446
0.85
1.026E00
0.61
0.15
2.833E00
0.39
0.9
1.011E00
0.689
0.1
3.132E00
0.311
0.95
1.003E00
0.807
0.05
3.476E00
0.193
1.
1.000E00
1.

3.872E00

Pressure (bar)
7.618E-01
8.746E-01
9.339E-01
9.657E-01
9.831E-01
9.925E-01
9.974E-01
9.994E-01
9.994E-01
9.974E-01
9.934E-01
9.867E-01
9.766E-01
9.622E-01
9.422E-01
9.149E-01
8.784E-01
8.303E-01
7.673E-01
6.859E-01
5.809E-01
60
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for the CF3, CF2, and -(CF)- groups, and we wanted to expand the interaction parameters to
include CHF2, CH2F, and CHF groups in order to better represent potential blowing agent
substitutes. A complete literature search was performed to identify known azeotropes containing
a fluorinated hydrocarbon with the expectation of deriving the required parameters from
experimental data. No useful data could be located in the available literature and the required
parameters were instead derived by anaolgy using corresponding data for related halogen
containing compounds (CI, Br, and I). A sensitivity analysis demonstrated that this technique was
sufficient to obtain the required UNIFAC group parameters.
The final stage of the methodology development was validation of the technique. A
literature search was initiated to identify azeotrope data. The most useful source was the CRC
Handbook of Chemistry and Physics (Lide, 1994) which contained 50 binary azeotropes.
UNIFAC azeotrope estimations were performed for these 50 binary pairs and the results were
compared with the experimental values listed in the CRC handbook. This comparison is
presented in Table 11. For the 50 binaries considered, the mixture boiling temperature was
typically estimated to within 1°C and the molar composition to within 0.05 mole fraction units.
These results are also presented graphically in Figures 3 and 4, respectively. The correlation
coefficient between the experimental and estimated boiling points was very good, r2 = 0.98. The
correlation between experimental and estimated composition (mole fraction) of the binaries was
also very good, r2 = 0.92 when comparing the experimental and estimated mole fraction of one
component of the mixture (the first component listed in Table 11).
61
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Table 11. Comparison of Experimental and Estimated Azeotrope Data
CRC azeotrope
Binary

*2
BP(C°)
water, ethanol
0.10
0.90
78
water, butanol
0.75
0.25
93
water, 1-octene
0.71
0.29
88
water, hexyl acetate
0.93
0.07
97
water, butyl ether
0.78
0.22
93
acetaldehyde, ethyl ether
0.85
0.15
19
acetonitrile, isopropyl acetate
0.79
0.21
80
methyl formate, isoprene
0.53
0.47
23
methyl formate, n-pentane
0.58
0.42
22
methyl formate, 2-methylbutane
0.52
0.48
17
methyl formate, 2,3-dimethylbutane
0.89
0.11
31
acetone, isopropyl ether
0.67
0.33
54
acetone, methyl acetate
0.54
0.46
56
acetone, cyclopentane
0.40
0.60
41
acetone, n-pentane
0.24
0.76
33
acetone, cyclohexane
0.71
0.29
53
acetone, hexane
0.68
0.32
50
acetone, heptane
0.94
0.06
56
ethyl formate, pentane
0.29
0.71
33
ethyl formate, methylcyclopentane
0.70
0.30
51
ethyl formate, hexane
0.70
0.30
49
carbon tetrachloride, acetone
0.05
0.95
56
carbon tetrachloride, acetonitrile
0.57
0.43
65
chloroform, acetone
0.57
0.43
64
chloroform, hexane
0.74
0.26
60
2-butanone, methyl propionate
0.65
0.35
79
62
UNIFAC azeotrope

Xj
BP(°C)
0.21
0.79
78
0.76
0.24
90
0.66
0.34
69
0.82
0.18
88
0.77
0.23
81
0.84
0.16
19
0.67
0.23
80
0.53
0.47
26
0.55
0.45
21
0.45
0.55
17
0.78
0.22
28
0.70
0.30
54
0.36
0.64
55
0.37
0.63
41
0.25
0.75
33
0.75
0.25
54
0.63
0.37
50
0.93
0.07
56
0.25
0.75
33
0.70
0.30
51
0.68
0.32
50
0.05
0.95
56
0.58
0.42
65
0.63
0.37
64
0.77
0.33
60
0.40
0.60
78
(Continued)
-------
Table 11. (continued)
CRC azeotrope	UNIFAC azeotrope
Binary

*2
BP(C°)

*2
BP(°C)
2-butanone, ethyl acetate
0.15
0.85
77
0.23
0.37
77
2-butanone, cyclohexane
0.43
0.57
72
0.43
0.57
70
2-butanone, hexane
0.32
0.68
64
0.35
0.65
63
2-butanone, heptane
0.76
0.24
77
0.73
0.27
76
2-butanone, 2,5-dimethylhexane
0.97
0.03
79
0.84
0.16
78
ethyl acetate, cyclohexane
0.55
0.45
72
0.54
0.46
71
ethyl acetate, methycyclopentane
0.37
0.63
67
0.40
0.60
66
ethyl acetate, hexane
0.39
0.61
65
0.37
0.63
65
methyl propionate, chlorobutane
0.39
0.61
77
0.30
0.70
78
methyl propionate, methyl cyclohexane
0.90
0.10
79
0.92
0.08
79
propyl formate, hexane
0.29
0.71
64
0.30
0.70
65
trichloroethylene, cyclohexane
0.11
0.89
81
0.20
0.80
81
ethyl methyl sulfide, hexane
0.60
0.40
64
0.60
0.40
64
ethyl methyl sulfide, methylcyclopentane
0.66
0.34
66
0.66
0.34
65
ethyl methyl sulfide, 2,2-dimethylpentane
0.91
0.09
66
0.88
0.12
66
isopropyl methyl sulfide, cyclohexane
0.29
0.71
80
0.34
0.66
79
methyl propyl sulfide, methylcyclohexane
0.79
0.21
95
0.69
0.31
94
butyl acetate, octane
0.52
0.48
119
0.50
0.50
120
2-pentanone, methyl butyrate
0.54
0.46
102
0.46
0.54
101
methyl acetate, cyclopentane
0.37
0.63
44
0.38
0.62
43
methyl acetate, hexane
0.64
0.36
52
0.68
0.32
52
methyl acetate, 2,2,3-trimethylbutane
0.80
0.20
55
0.80
0.12
56
methyl acetate, 2-methyl hexane
0.91
0.09
56
0.88
0.12
56
dioxane, cyclohexane
0.24
0.76
80
0.13
0.87
80
63
-------
Azeotrope Boiling Point in °C
140
120
• 100
C
E 80
L
«
& 60
ui
40
20
0
0 20 40 60 80 100 120 140
Calculated
r-«quared = 0.98
Figure 3. Reliability of Azeotrope Estimation Method for
Boiling Point
£ 1
P
a
E
§0.8
•I
h.
fo.6
o
0
20.4
IL
«
a 0.2
¦o
«
1	0
O o 0.2 0.4 0.6 0.8 1
£	Experimental Mole Fraction (first component)
r-squared = 0.92
Figure 4. Reliability of Azeotrope Estimation Method for Mole
Fraction
Azeotrope Mole Fraction


• •


•


* • #


.•V *


:k i


• •
"

• •


•••


•


••
_
• *
•

• • *
•

• •

- % •
• •

•
I
i.i,!
64
-------
Identifying Potential Blowing Agent Mixtures
With the development and validation of the UNIFAC method for estimating azeotropes
completed, work began on identifying potential blowing agent mixtures. Initial effort focused on
defining mixtures that were expected to form an azeotrope. That is, picking solvents of dissimilar
chemical structure (closely related compounds, in general, do not form useful azeotropes), and
performing the azeotrope estimation on the resulting mixture. A total of 348 binary azeotropes
were identified from 55 different chemicals in this phase of the project. These azeotropes, along
with their boiling point, vapor thermal conductivity, and molecular weight, are provided in Table
12. The properties of the pure components used in these calculations are also provided in Table
12.
Initial analysis of the data contained in Table 12 revealed the following:
•	164 of the azeotropes had vapor thermal conductivities lower than at least one
component of the mixture;
•	In some instances, the vapor thermal conductivity of the predominant component
was significant lowered by the inclusion of a relatively small amount of a second
substance;
•	14 mixtures had vapor thermal conductivities lower than both components (Table
13). For example, 1,1-difluorobutane (X = 13.00) and 2-methyl-l-butene (A, =
12.90) had a resulting A = 12.1; and
•	The azeotrope formed was typically a low-boiling azeotrope. That is, the boiling
point of the azeotrope was typically lower than the boiling point of either
component.
65
-------
Table 12. Binary Azeotrope Data
F
1,4-pentadiene
isoprene
1,1, 1-trifluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
26.00	12.60	0.40
34.00	14.40	0.14
12.00
0.38
Mixture Data
Mixture TC
(mW/m-K)
12.88
12.96
Mixture BP
(°C)
14.00
17.00
acetone
1,2-difluorobutane
1,1,2-trimethylcyclopropane
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
56.00	11.25	0.43
8.56	13.00	0.64
15.20
53.00
Mixture Data
Mixture TC
(mW/m-K)
13 .70
14.40
Mixture BP
(°C)
42 .00
48.00
1,1 -difluoro-2-methylpropane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.30
33.00
Mixture Data





Fraction
Mixture TC
Mixture BP

BP ('
3C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,3 -cyclopentadiene
42
. 00
13
. 10
0.39
12.12
31.00
1,3-pentadiene
42.
. 00
12
.10
0.25
12.28
32.00
2-pentene
37 .
.00
12
.70
0 . 28
12.43
32.00
1,4-pentadiene
26.
. 00
12
. 60
0 . 67
12.53
22.00
2-methyl-2-butene
35 .
. 00
14.
.10
0.13
12.54
33.00
pentane
36.
.10
14.
.80
0.10
12.55
33 .00
2-methyl- 1-butene
31.
00
12 .
. 90
0 . 58
12. 67
29.00
isoprene
34.
00
14 .
.40
0'. 52
12.69
27.00
methylcyclobutane
35.
50
15 .
00
0.20
12.82
32.00
ethylcyclopropane
34.
50
15 .
60
0.25
13.09
32 .00
1-pentene
29.
90
13 .
60
0 . 63
13 .13
28.00
cyclopentene
1,1-difluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
13.00
8.56
Mixture Data
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
44.00	10.80	0.40
Mixture TC
(mW/m-K)
10.96
Mixture BP
(°C)
39.00
66
(Continued)
-------
Table 12. (continued)
1 -methylcyclobutene
1,3-cyclopentadiene
1.3-pentadiene
2-methyl-l-butene
2-pentene
1.4-pentadiene
isoprene
2-methyl-2-butene
methylcyclobutane
CH,
I 3
On -CH3
CH ^
I
cyclopentene
1 -methylcyclobutene
cyclopentane
2-pentene
2-methyl-1 -butene
2,3-dimethylbutane
2,2-dimethylbutane
2-methyl-2-butene
pentane
methylcyclobutane
isopentane
tetramethyl silane
ethylcyclopropane
F
cyclopentene
1,3 -cyclopen tadiene
1.3-pentadiene
2-pentene
1.4-pen	tadiene
isoprene
2-methyl-2-butene
41. 50
11.90
0 .45
11.41
40.00
42.00
13 .10
0. 60
11.42
35.00
42.00
12.10
0.48
11.54
37.00
31.00
12 .90
0 . 66
12.12
37.00
37.00
12 .70
0.73
12 .24
36.00
26 . 00
12 . 60
0.81
12.30
24.00
34.00
14.40
0 . 69
12.36
31.00
35.00
14.10
0 . 67
13 .06
37.00
35.50
15 . 00
0 .95
14.78
36.00
1,1 -dimethoxyethane
Vapor Hernial Conductivity (TC) in mW/m-K:	11.98
Boiling Point (BP) in °C:	85.00
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
44. 00
10. 80
0 . 82
11.10
42 . 00
41. 50
11.90
0.79
11.90
39.00
50.00
12 .10
0.72
12 .10
45.00
37.00
12 .70
0.88
12 . 60
36.00
31.00
12 . 90
0.95
12.90
31.00
58 . 00
12 .40
0 . 65
13.10
45 .00
50.00
13 .20
0.67
13 .30
44.00
35.00
14.10
0 . 85
13 .80
37.00
36.10
14.80
0 . 84
14.30
34.00
35.50
15 . 00
0.85
14.50
35.00
28.00
14.80
0.95
14. 60
27.00
26.00
15 . 50
0 . 85
15 .00
26.00
34. 50
15 . 60
0 . 85
15.00
34. 00
1,2-difluoro-2-methylpr opane
Vapor Thermal Conductivity (TC) in mW/m-K:	11.20
Boiling Point (BP) in °C:	36.00
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
o
o
10.80
0.25
11.13
34.00
42.00
13 .10
0 . 50
11.46
30.00
42.00
12 .10
0.50
11.67
32.00
37.00
12 .70
0 .45
11.88
32.00
26.00
12 . 60
0 . 68
12.16
20 . 00
34.00
14.40
0. 56
12.20
26.00
35 . 00
14.10
0.35
12.20
33 .00
67
(Continued)
-------
Table 12. (continued)
2-methyl-l-butene
pentane
1-pentene
methylcyclobutane
ethylcyclopropane
3-methyl-1	-butene
isopentane
F
cyclopentene
1 -methylcyclobutene
1,3-cyclopentadiene
2-pentene
1,3-pentadiene
cyclopentane
isoprene
2,2-dimethylbutane
2-methyl-2-butene
1,1,2-trimethylcyclopropane
pentane
1.1-difluorobutane
1.2-difluoro-2-methylpropane
2,2-difluorobutane
acetone
1 -methylcyclobutene
1,1 -difluoro-2-methylpropane
fluorobutane
1,2-difluorobutane
2-fluorobutane
methylcyclobutane
31.00
12 .90
0.62
12 .26
28.00
36.10
14.80
0.42
12. 69
33 .00
29.90
13 . 60
0 . 65
12.75
27.00
35.50
15.00
0.45
12.84
32.00
34.50
15 . 60
0 .47
13 .18
33 .00
20.00
14.00
0.88
13 . 65
20.00
28.00
14. 80
0.90
14.43
28 .00
1,2-difluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K;	13.00
Boiling Point (BP) in °C:	8.56
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
44.00
10 . 80
0. 62
12.10
42 .00
41.50
11.90
0.89
12 .20
41.00
42.00
13 .10
0 .70
12.50
35 .00
37.00
12 .70
0.89
12.80
36.00
42.00
12.10
0.65
12.80
37.00
50.00
12.10
0.53
13 .00
47.00
34.00
14.40
0.75
13 .30
30.00
50.00
13 .20
0.48
14.00
47.00
35.00
14.10
0.89
14.10
38.00
53 .00
15.20
0.36
14.40
48.00
36 .10
14.80
0.73
14. 60
35.00
1,3-cyclopentadiene
Vapor Thermal Conductivity (TC) in mW/m-K:	13.10
Boiling Point (BP) in °C:	42.00
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
8.56
13 . 00
0 .40
11.42
35.00
36.00
11.20
0.50
11.46
30.00
31.00
11.40
0 . 69
11.51
30.00
56.00
11.25
0.19
11. 62
42 .00
41. 50
11.90
0.40
11.78
39.00
33 .00
¦ 12.30
0. 61
12.12
31.00
32 .50
12 . 50
0.61
12 .20
30.00
8.56
13 .00
0.30
12 . 50
35 .00
24.50
13 .00
0.92
12.90
25.00
35.50
15 . 00
0.86
14. 56
36.00
68
(Continued)
-------
Table 12. (continued)
1,3-pentadiene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.10
42.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,1 -difluorobutane
8.56
13 .00
0.52
11.54
37.00
1,2-difluoro-2-methylpropane
36. 00
11.20
0.50
11.67
32 .00
1 -methylcyclobutene
41.50
11.90
0 .70
11.96
41.00
1,1 -difluoro-2-methylpropane
33 .00
12.30
0.75
12.28
32.00
fluorobutane
32 . 50
12 . 50
0. 80
12.41
31.00
2,2-difluorobutane
31.00
11.40
0.90
12.48
31.00
1,2-difluorobutane
8.56
13 .00
0.35
12.80
37.00
1,4-pentadiene
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
12.60
26.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,2-difluoro-2-methylpropane
36.00
11. 20
0.32
12.16
20.00
2,2-difluorobutane
31.00
11.40
0.33
12 .22
23 .00
1,1-difluorobutane
8 . 56
13 . 00
0 .19
12 .30
24.00
1,1 -difluoro-2-methylpropane
33 .00
12.3 0
0 .33
12.53
22. 00
fluorobutane
32.50
12.50
0 .33
12.56
23 .00
2-fluorobutane
24.50
13 . 00
0.47
12 .80
20.00
1,1,1 -trifluorobutane
0.38
12.00
0 . 60
12.88
14.00
HjC
CH,
methyl t-butyl ether
dimethoxymethane
HC
^^CH2
1,4-pentadiene-3-methyl
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.70
55.00
Mixture Data
Fraction •
BP (°C) TC (mW/m-K) in mixture (%)
55.00	14.40	0 .55
41.00	14.90	0.65
Mixture TC
(mW/m-K)
12.66
13 .80
l-buten-3-yne
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Mixture BP
(°C)
52.00
37.00
13.80
5.10
Mixture Data
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
Mixture TC
(mW/m-K)
Mixture BP
(°C)
69
(Continued)
-------
Table 12. (continued)
methylcyclopropane
2-butene
neopentane
cyclobutane
acetone
1,1-difluorobutane
acetone
1,3-cyclopentadiene
ethyl formate
1.1-dimethoxyethane
1,3-pentadiene
methyl acetate
1.2-difluorobutane
1-pentyne
isoprene
methyl formate
dimethoxymethane
methyl isopropyl ether
methylcyclobutane
perfluoropentane
2,2-difluorobutane
1,2-difluoro-2-methylpropane
4. 00
1. 00
9.50
12.50
13 . 50
13.50
15 .00
14.80
0. 58
0 . 60
0.42
0 . 32
13 . 60
14.20
14. 50
14.50
1.00
2 .00
2 .00
4.00
1-butene, 3,3-dimethyl
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (¦»
56.00 11.25	0.25
12.40
41.00
Mixture Data
Mixture TC
(mW/m-K)
12.18
Mixture BP
(°C)
39.00
1-methylcyclobutene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:'
11.90
41.50
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
8 .56
13 .00
0 . 55
11.41
40.00
56.00
11.25
0.30
11.72
36.00
42.00
13 .10
0 . 60
11.78
39.00
54.50
11. 80
0.30
11.87
37.00
85.00
11.98
0.21
11.90
39.00
42.00
12.10
0.30
11.96
41.00
56.50
12 .20
0.28
11.99
38.00
8.56
13 .00
0 .11
12.20
41.00
40.00
13 . 60
0. 52
12.70
38.00
34.00
14.40
0.90
12.89
34.00
31.50
13 .90
0 .58
12.97
24.00
41.00
14.90
0 .47
13.75
28.00
31.00
15 .20
0 . 87
14.79
31.00
35.50
15.00
0 . 60
15.32
26.00
1-pentene
Vapor Thermal Conductivity (TC) in mW/m-K:	13.60
Boiling Point (BP) in °C:	29.90
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
28.50 9.36 0.44 11.82	13.00
31.00 11.40 0.42 12.67	29.00
36.00 11.20 0.35 12.75	27.00
70	(Continued)
-------
Table 12. (continued)
1,1 -difluoro-2-methylpropane 33,00 12.30
0.37
13.13
28.00
1-pentyne
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
13.60
40.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
2-pentene
37.00
12.70
0.88
12.70
37.00
1 -methylcyclobutene
41,50
11.90
0.48
12.70
38.00
2,2-dimethylbutane
50.00
13.20
0.05
13.40
36.00
2-methyl-2-butene
35.00
14.10
0.64
13.90
37.00
pentane
36.10
14.80
0.80
14.50
35.00
methylcyclobutane
35.50
15.00
0.73
14.60
35.00
ethylcyclopropane
34.50
15.60
0.75
15.10
35 .00
2,2-difluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
11.40
31.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,3 -cyclopentadiene
42 .00
13.10
0.31
11.51
30 .00
isoprene
34.00
14.40
0.45
12.12
27.00
2-methyl-1 -butene
31.00
12.90
0.50
12.16
29.00
1,4-pentadiene
- 26.00
12.60
0.67
12.22
23.00
1,3-pentadiene
42.00
12 .10
0.10
12.48
31.00
1-pentene
29.90
13 . 60
0.58
12. 67
29. 00
CH,
h3c-
"Y
CH, CH3
2,2-dimethylbutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
13.20
50.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K)
in mixture (%)
(mW/m-K)
CO
1,1 -dimethoxyethane
85.00
11.98
0.33
13 .30
44.00
1-pentyne
40 .00
13.60
0.95
13 .40
36.00
methyl formate
31.50
13 .90
'0.70
13.91
26.00
1,2-difluorobutane
8.56
13.00
0.52
14.00
47.00
dimethoxymethane
41.00
14.90
0 . 57
14.94
31.00
(Continued)
71
-------
Table 12. (continued)
h3c-
j^CH,
CH,
1,1 -dimethoxyethane
methyl fonnate
dimethoxymethane
2,3-dimethylbutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
85.00	11.98	0.35
31.50	13.90	0.89
41.00	14.90	0.65
12.40
58.00
Mixture Data
Mixture TC
(mW/m-K)
13.10
13.90
14.97
Mixture BP
(°C)
45.00
31.00
35 .00
l-buten-3-yne
2-butene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
5.10	13.80	0.40
13.50
1.00
Mixture Data
Mixture TC
(mW/m-K)
14.20
Mixture BP
(°C)
2.00
CH,
, CHj
perfluoropentane
2-fluoro-2-methylpropane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
28.50	9.36	0.18
13.80
-5.02
Mixture Data
Mixture TC
(mW/m-K)
12.87
Mixture BP
(°C)
10.00
2-fluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
13.00
24.50
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K). in mixture (%)
(mW/m-K)
(°C) .
1,4-pentadiene
26.00
12.60
0.53
12. 80
20. 00
1,3-cyclopen tadiene
42.00
13 .10
0.08
12.90
25.00
2-methyl-l-butene
31.00
12.90
0 . 50
12.90
25.00
isoprene
34.00
.13.50
0.30
13.00
24.00
isopentane
28.00
14.80
0 .10
13.20
25 .00
3-methyl-l-butene
20.00
14.00
. 0.75
13 .70
19.00
(Continued)
72
-------
Table 12. (continued)
2-methyl-l-butene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.90
31.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,1-difluorobutane
8.56
13 .00
0.34
12 .12
37.00
2,2-difluorobutane
31.00
11.40
0 .50
12.16
29 .00
1,2-difluoro-2-methylpropane
36.00
11.20
0.38
12.26
28.00
1,1 -difluoro-2-methylpropane
33 .00
12.30
0.42
12.67
29.00
fluorobutane
32 .50
12 . 50
0 .40
12.73
29.00
2-fluorobutane
24.50
13.00
0 . 50
12.90
25.00
1,1 -dimethoxyethane
85.00
11.98
0 .05
12 . 90
31.00

H^c
CH,
2-methyl-2-butene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
14.10
35.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,2-difluoro-2-methylpropane
36.00
11.20
0.65
12.20
33 .00
perfluorohexane
56.30
8 .42
0.28
12 .41
30 . 00
1,1 -difluoro-2-methylpropane
33 .00
12.30
0.87
12.54
33 .00
1,1-difluorobutane
8.56
13.00
0 .33
13.06
37.00
1,1-dimethoxyethane
85.00
11.98
0 .15
13 .80
37.00
1-pentyne
40 .00
13 . 60
0.36
13 .90
37.00
1,2-difluorobutane
8.56
13 .00
0.11
14.10
38.00
methylcyclobutane
35.50
15 . 00
0. 85
14. 86
36. 00
2-pentene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.70
37.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
perfluorohexane
56.30
8 .42
0.27
11. 60
28 . 00
1,2-difluoro-2-methylpropane
36.00
11.20
0 . 55
11.88
32.00
1,1-difluorobutane
8.56
13 . 00
0.27
12 .24
36.00
1,1 -difluoro-2-methylpropane
33 .00
12 .30
0.72
12 .43
32.00
acetone
56.00
11.25
0.20
12 .44
35.00
fluorobutane
32.50
12 .50
0 . 80
12 .53
32 . 00
1,1 -dimethoxyethane
85.00
11.98
0 .12
12 . 60
36.00
1-pentyne
40.00
13 . 60
0 .12
12 .70
37.00
73
(Continued)
-------
Table 12. (continued)
1,2-difluorobutane
methyl formate
methylcyclobutane
perfluoropentane
1,2-difluoro-2-methylpropane
2-fluorobutane
8 .56
31.50
35.50
13 . 00
13 . 90
15.00
0.11
0 . 58
0 . 65
12.80
13.30
14.17
3-methyl-l-butene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
28.50	9.36	0.35
36.00	11.20	0.12
24.50	13.00	0.25
36.00
24.00
36.00
14.00
20.00
Mixture Data
Mixture TC
(mW/m-K)
12.42
13.65
13.70
Mixture BP
(°C)
6. 00
20.00
19.00
perfluoropentane
o

H,C	CH.
3-methylcyclopentene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
10.20
78.00
Mixture Data
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
28.50	9.36	0.74
Mixture TC
(mW/m-K)
10.18
Mixture BP
(°C)
26.00
acetone
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
11.25
56.00
Mixture Data





Fraction
Mixture1
TC
Mixture BP

BP ('
3C)
TC (mW/m-K) in mixture (%)
(mW/m-
K)
(°C)
cyclopentene
44
.00
. 10
.80
0
.74
10
.91
41.00
1,3-cyclopentadiene
42
. 00
13
.10
0
.81
11
. 62
42.00
1 -methylcyclobutene
41
.50
11
.90
0
.70
11
.72
36.00
methylcyclopentane
71.
. 50
13
.10
0
.35
12 .
.02
51.00
1-butene, 3,3-dimethyl
41.
.00
12
.40
0,
.75
12.
.18
39.00
2-pentene
37.
. 00
12
.70
0 ,
. 80
12 ,
.44
35.00
cyclohexane
6 .
.50
13
. 90
0 .
.39
12.
.44
51.00
methyl t-butyl ether
55 .
.00
14.
. 40
0 .
. 60
13 .
.31
51.00
1,1,2-trimethylcyclopr opane
53.
, 00
15'
. 20
0.
. 57
13 .
.70
42.00
methylcyclobutane
35 .
. 50
15.
.00
0 .
.77
14.
.19
32.00
isopentane
28 .
00
14.
.80
0 .
.84
14.
29
26.00
ethylcyclopropane
34.
50
15.
. 60
0 .
77
14.
66
32.00
tetramethyl silane
26 .
00
15.
, 50
0 .
83
14.
92
26.00
(Continued)
74
-------
Table 12. (continued)
~
l-buten-3-yne
acetone
o
perfluoropentane
perfluorohexane
methyl acetate
1,1 -dimethoxyethane
methyl t-butyl ether
1,2-difluorobutane
methyl formate
o
perfluorohexane
perfluoropentane
acetone
1.1-difluorobutane
ethyl formate
1,1 -dimethoxyethane
1.2-difluoro-2-methylpropane
cyclobutane
Vapor Thermal Conductivity (TC) in mW/m-K:	14.80
Boiling Point (BP) in °C:	12.50
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
5.10 13.80 0.68 14.50	4.00
cyclohexane
Vapor Thermal Conductivity (TC) in mW/m-K:	13.90
Boiling Point (BP) in °C:	6.50
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
56.00 11.25 0.61 12.44	51.00
cyclopentane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.10
50.00
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
28.50
9.36
0 . 65
10 .44
28.00
56.30
8 .42
0.34
10.88
40 .00
56. 50
12.20
0.37
12.10
43 .00
o
o
in
CO
11.98
0.28
12.10
45.00
55.00
14.40
0.25
12 .74
48.00
8.56
13 . 00
0 .47
13 .00
47.00
31.50
13 . 90
0 . 67
13.20
27.00
cyclopentene
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
10.80
44.00
Mixture Data


Fraction
Mixture TC
Mixture BP
BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
56.30
8 .42
0.30
10.30
33 . 00
28 . 50
9.36
0.54
10.35
22 . 00
56. 00
11.25
0.26
10.91
41.00
8.56
13 .00
0 . 60
10.96
39 . 00
54. 50
11.80
0 .28
11.08
40.00
85.00
11.98
0 .18
11.10
42 .00
36.00
11.20
0 .75
11.13
34.00
75
(Continued)
-------
Table 12. (continued)
methyl acetate
56.
. 50
12
.20
0
.25
11
.15
42
.00
1,2-difluorobutane
8 .
.56
13
.00
0
.38
12
.10
42
.00
methyl formate
31.
.50
13 ,
.90
0 ,
. 65
12 ,
.67
26,
.00
dimethoxymethane
41.
, 00
14.
. 90
0 .
.47
13 .
.10
33 .
.00
vinyl formate
29.
,00
13 .
.26
0.
.44
13 .
.26
35.
.00
CH,
CH,
dimethoxymethane
Vapor Thennal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
14.90
41.00
Mixture Data





Fraction
Mixture TC
Mixture BP

BP ('
BC)
TC (mW/m-K) in mixture (%)
(mW/m-
•K)
(°C)
cyclopentene
44
.00
10
.80
0.53
13
.10
33.00
1 -methylcyclobutene
41
.50
11
.90
0.53
13
.75
28.00
1,4-pentadiene-3-methyl
55
.00
12
.70
0.35
13
.80
37.00
2,2-dimethylbutane
50.
.00
13
.20
0.43
14
.94
31.00
2,3-dimethylbutane
58,
.00
12 ,
.40
0.35
14,
.97
35.00
neopentane
9.
.50
15 .
.00
0.84
15.
.29
7.00
tetramethyl silane
26.
, 00
15.
. 50
0 . 60
15.
. 60
20.00
ethyl vinyl ether
34.
50
14.
, 60
0.76
15.
, 60
34.00
ethylcyclopropane
34.
50
15 .
60
0. 60
15.
68
26. 00
vinyl formate
29 .
00
15 .
90
0.13
15.
90
42.00
HjCv.
3 CH,
I 2
0^ .0
CH
ethyl formate
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
11.80
54.50
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
cyclopentene
44.00
O
00
o
0.72
11.08
40.00
1 -methylcyclobutene
41.50
11.90
0 .70
11.87
37.00
pentane
36.10
14.80
0 .71
14.00
33 .00
methylcyclobutane
35.50
15 .00
0.77
14.27
33 .00
ethylcyclopropane
34.50
15 . 60
0.77
14.73
33.00

dimethoxymethane
ethyl vinyl ether
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
14.60
34.50
Mixture Data
Fraction'
BP (°C) TC (mW/m-K) in mixture (%)
41.00	14,90	0.24
Mixture TC
(mW/m-K)
15.60
Mixture BP
(°C)
34.00
76
(Continued)
-------
Table 12. (continued)
.CH,
ethylcyclopropane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
15.60
34.50
Mixture Data




Fraction
Mixture TC
Mixture BP

BP (
°C)
TC (mW/m-K) in mixture (%)
(mW/m-
K)
(°C)
perfluoropentane
28
.50
9.36
0 . 50
12
.28
23.00
fluorobutane
32
. 50
12. 50
0 . 82
13
.08
32 .00
1,1 -difluoro-2-methylpropane
33
.00
12 .30
0 .75
13
.09
32 .00
1,2-difluoro-2-methylpropane
36
.00
11.20
0.53
13
.18
33 .00
perfluorohexane
56.
.30
8.42
0.22
13,
.72
30.00
acetone
56,
.00
11.25
0.23
14,
.66
32.00
ethyl formate
54.
.50
11.80
0.23
14.
.73
33 .00
methyl formate
31.
,50
13.90
0 . 52
14.
.77
22 .00
methyl acetate
56.
50
12 . 20
0.20
14.
92
34.00
1,1 -dimethoxyethane
85.
00
11.98
0.15
15.
00
34.00
1-pentyne
40.
00
13 . 60
0.25
15.
10
35.00
dimethoxymethane
41.
00
14.90
0.40
15.
68
26.00
H3C
fluorobutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.50
32.50
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
1,3-cyclopentadiene
42.00
13 .10
0.39
12.20
30 .00
1,3-pentadiene
42 .00
12 .10
0.20
12.41
31.00
2-pentene
37.00
12.70
0.20
12.53
32 .00
1,4-pentadiene
26.00
12.60
0 . 67
12.56
23 .00
2-methyl-1 -butene
31.00
12 . 90
0 . 60
12 .73
29 .00
isoprene
34.00
14.40
0 . 50
12.75
28. 00
methylcyclobutane
35.50
15.00
0 .15
12.89
32.00
ethylcyclopropane
34.50
15.60
0 .18
13 .08
32.00
9*3
h3c-
CH,
2-fluorobutane
perfluorohexane
acetone
isopentane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
24.50	13.00	0.90
56.30	8.42	0.19
56.00	11.25	0.16
14.80
28.00
Mixture Data
Mixture TC
(mW/m-K)
13.20
13.46
14.29
Mixture BP
(°C)
2 5 . 00
25.00
26.00
77
(Continued)
-------
Table 12. (continued)
methyl formate
31 -
.50
13 .
.90
0
.52
14.
.30
17,
.00
1,2-difluoro-2-methylpr opane
36.
. 00
11
.20
0
. 10
14.
.43
28 ,
.00
1,1 -dimethoxyethane
85.
.00
11.
.98
0 .
.05
14.
. 60
27.
.00
methyl acetate
56.
.50
12 .
.20
0 .
.07
14.
. 62
27.
,00
trimethyl orthoformate
100.
,50
12.
.40
0.
.05
14.
70
27.
.00
9^
h2c=-
CH„
isoprene
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
14.40
34.00
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
2,2-difluorobutane
31.00
11.40
0 .55
12 .12
27.00
1,2-difluoro-2-methylpropane
36.00
11.20
0 .44
12 .20
26.00
1,1-difluorobutane
8 . 56
13 . 00
0.31
12.36
31.00
1,1 -difluoro-2-methylpropane
33 .00
12.30
0.48
12.69
27.00
fluorobutane
32.50
12.50
0 . 50
12.75
28.00
1 -methylcyclobutene
41.50
11.90
0.10
12 .89
34. 00
1,1,1-trifluorobutane
0.38
12.00
0.86
12.96
17.00
2-fluorobutane
24. 50
13 .00
0 .70
13.00
24.00
1,2-difluorobutane
8.56
13 .00
0 .25
13 .30
30.00
methyl formate
31.50
13 . 90
0. 53
13.40
23 .00
-CH,
U
A.
methyl acetate
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
12.20
56.50
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
cyclopentene
44. 00
10 . 80
0.75
11.15
42 .00
1 -methylcyclobutene
41.50
11.90
0 .72
11.99
38.00
cyclopentane
50.00
12 .10
0 . 63
12.10
43 .00
methylcyclobutane
35.50
15 .00
0 . 79
14.41
34.00
methylcyclobutane
35 . 50
15 .00
0 . 80
14.44
34.00
isopentane
28.00
14. 80
0 . 93
14. 62
27.00
ethylcyclopropane
34.50
15 . 60
0 . 80
14.92
34. 00
CH,
0<5. -O
CH
methyl formate
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
13.90
31.50
Mixture Data
Fraction	Mixture TC Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
78
(Continued)
-------
Table 12. (continued)
cyclopentene
44
.00
10
.80
0
.35
12
. 67
26
.00
1 -methylcyclobutene
41
.50
11
.90
0
.42
12
.97
24
.00
cyclopentane
50,
.00
12
. 10
0
.33
13
.20
27
.00
2-pentene
37.
.00
12
.70
0
.42
13
.30
24
.00
isoprene
34.
. 00
14
.40
0
.47
13
.40
23
.00
2,3-dimethylbutane
58.
, 00
12 ,
.40
0.
.11
13 ,
.90
31,
.00
2,2-dimethylbutane
50 .
.00
13 .
.20
0 .
.30
13 ,
.91
•26.
.00
isopentane
28 .
00
14.
.80
0.
,48
14.
.30
17.
, 00
pentane
36.
10
14.
.80
0 .
,42
14.
.30
22.
,00
methylcyclobutane
35.
50
15.
,00
0 .
,47
14.
,45
22 .
,00
methylcyclobutane
35 .
50
15.
00
0 .
48
14.
46
22.
00
ethylcyclopropane
34.
50
15.
60
0 .
48
14.
77
22.
00
H3C
?*?
,CH
,CH„
1 -methylcyclobutene
methylcyclobutane
tetramethyl silane
methyl isopropyl ether
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
41.50	11.90	0.13
35.50	15.00	0.28
26.00	15.50	0.58
15.20
31.00
Mixture Data
Mixture TC
(mW/m-K)
14.79
15.15
15.40
Mixture BP
(°C)
31.00
29.00
26.00
CH,
CH,
CH,
1,4-pentadiene-3-methyl
cyclopentane
acetone
methyl t-butyl ether
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
55.00	12.70	0.45
50.00	12.10	0.75
56.00	11.25	0.40
14.40
55.00
Mixture Data
Mixture TC
(mW/m-K)
12.66
12.74
13 .31
Mixture BP
(°C)
52 . 00'
48 .00
51.00
\
perfluoroisopentane
perfluoropentane
1,1 -difluoro-2-methy lpropane
1,2-difluoro-2-methylpropane
methylcyclobutane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
29.50	9.27	0.50
28.50	9.36	0.50
33.00	12.30	0.80
36.00	11.20	0.55
15.00
35.50
Mixture Data
Mixture TC
(mW/m-K)
11.98
12.04
12 . 82
12 . 84
Mixture BP
(°C)
21. 00
20.00
32.00
32.00
79
(Continued)
-------
Table 12. (continued)
fluorobutane
32
.50
12
. 50
0'
.85
12
. 89
32
. 00
2-pentene
37
.00
12
.70
0
.35
14
.17
36
.00
acetone
56
. 00
11
.25
0
.23
14
.19
32
.00
ethyl formate
54
.50
11
.80
0
.23
14
.27
33
.00
methyl acetate
56
. 50
12
.20
0
.20
14
.44
34
.00
methyl formate
31.
.50
13
. 90
0
.52
14
.46
22
.00
1,1 -dimethoxyethane
85 ,
. 00
11,
.98
0.
.15
14.
.50
35 ,
.00
1,3-cyclopentadiene
42 .
.00
13.
. 10
0.
. 14
14.
.56
36.
.00
1-pentyne
40 .
.00
13 .
. 60
0 .
.27
14.
. 60
35 .
.00
1,1-difluorobutane
8.
.56
13 .
.00
0.
.05
14.
.78
36.
.00
2-methyl-2-butene
35.
00
14.
.10
0 .
.15
14.
86
36.
00
pentane
36.
10
14.
80
0 .
.58
14.
88
36.
00
methyl isopropyl ether
31.
00
15.
20
0.
72
15.
15
29.
00
1 -methylcyclobutene
41.
50
11.
90
0.
40
15.
32
26.
00
vinyl formate
29.
00
15.
63
0 .
37
15.
63
27.
00
I	methylcyclopentane
A. Vapor Thermal Conductivity (TC) in mW/m-K:	13.10
\	/ Boiling Point (BP) in °C:	71.50
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
acetone 56.00 11.25 0.65 .12.02	51.00
A	methylcyclopropane
„ r-" Vapor Thermal Conductivity (TC) in mW/m-K:	13.50
Boiling Point (BP) in °C:	4.00
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
l-buten-3-yne 5.10 13.80 0.42 13.60	1.00
neopentane
Vapor Thermal Conductivity (TC) in mW/m-K:	15.00
Boiling Point (BP) in °C:	9.50
	Mixture Data	
Fraction Mixture TC	Mixture BP
BP (°C) TC (mW/m-K) in mixture (%) (mW/m-K)	(°C)
perfluoropentane 28.50 9.3 6 0 .27 13.58	5.00
l-buten-3-yne 5.10 13.80 0.58 14.50	2.00
dimethoxymethane 41.00 14.90 0.16 . 15.29	7.00
80
(Continued)
-------
Table 12. (continued)
H3C"
pentane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
14.80
36.10
Mixture Data




Fraction
Mixture'
TC
Mixture BP

BP ('
BC)
TC (mW/m-K) in mixture (%)
(mW/m-
K)
(°C)
perfluoropentane
28
.50
9.36
0.52
11
.93
20.00
1,1 -difluoro-2-methylpropane
33
.00
12.30
0.90
12
.55
33 .00
l,2-difluoro-2-methylpropane
36
.00
11.20
0.58
12,
. 69
33 .00
perfluorohexane
56
.30
8 .42
0.25
13.
.05
31.00
ethyl formate
54,
.50
11.80
0.29
14.
. 00
33.00
methyl formate
31.
.50
13 .90
0.58
14.
.30
22.00
1,1 -dimethoxyethane
85.
.00
11.98
0.16.
14.
,30
34.00
1-pentyne
40.
.00
13 . 60
0 .20
14.
50
35.00
trimethyl orthoformate
100 .
.50
12 .40
0.08
14.
60
35.00
1,2-difluorobutane
8 .
56
13 .00
0 .27
14.
60
35.00
methylcyclobutane
35 .
50
15.00
0.42
14.
88
36.00
F \ F
F F
F>^;
F F
perfluorohexane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
8.42
56.30
Mixture Data



Fraction
Mixture TC
Mixture BP

BP (°C)
TC (mW/m-K) in mixture (%)
(mW/m-K)
(°C)
cyclopentene
44.00
10 .80
0 .70
10 .30
33.00
cyclopentane
50.00
12 .10
0 . 66
10.88
40.00
2-pentene
37 .00
12.70
0.73
11. 60
28.00
2-methyl-2-butene
35.00
14.10
0 .72
12.41
30.00
pentane
36.10
14.80
0.75
13 .05
31.00
isopentane
28 .00
14.80
0 . 81
13 .46
25.00
ethylcyclopropane
34.50
15 . 60
0.78
13 .72
30.00
-F
F F
I
F F
methylcyclobutane
perfluoroisopentane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
9.27
29.50
Mixture Data
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
35.50	15.00	0.50
Mixture TC
(mW/m-K)
11.98
Mixture BP
(°C)
21.00
(Continued)
81
-------
Table 12. (continued)
F F
F F
F F
perfluoropentane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
9.36
28.50
Mixture Data




Fraction
Mixture TC
Mixture BP

BP ('
3C)
TC (mW/m-K) in mixture (%)
(mW/m-
K)
(°C)
3-methylcyclopentene
78
.00
10.20
0
.26
10
.18
26.00
cyclopentene
44
.00
10 .80
0
.46
10
.35
22.00
cyclopentane
50
.00
12.10
0
.35
10
.44
28.00
1-pentene
29 .
. 90
13 . 60
0 .
.56
11.
.82
13 . 00
pentane
36.
. 10
14. 80
0 .
.48
11.
.93
20 . 00
methylcyclobutane
35.
.50
15.00
0.
.50
12.
.04
20.00
ethylcyclopropane
34.
,50
15 . 60
0 .
,50
12.
,28
23 .00
3-methyl-l-butene
20.
00
14.00
0 .
, 65
12.
,42
6.00
2-fluoro-2-methylpropane
-5 .
02
13 .80
0 .
82
12.
87
10.00
neopentane
9.
50
15.00
0.
73
13 .
58
5 .00
f,
CHj-Si-CHj
CH.
acetone
1,1 -dimethoxyethane
trimethyl orthoformate
methyl isopropyl ether
dimethoxymethane
tetramethyl silane
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
55.00	11.25	0.17
85.00	11.98	0.15
100.50	12.40	0.13
31.00	15.20	0.42
41.00	14.90	0.40
15.50
26.00
Mixture Data
Mixture TC
(mW/m-K)
14.92
15.00
15.10
15.40
15.60
Mixture BP
CO
26.00
26. 00
26 . 00
26.00
20 . 00
0
1
^CH x'CH,
0	'O ^
1
CH3
pentane
isopentane
tetramethyl silane
trimethyl orthoformate
Vapor Thermal Conductivity (TC) in mW/m-K:
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
36.10	14.80	0.92
28.00	14.80	0.95
26.00	15.50	0.87
12.40
100.50
Mixture Data
Mixture TC
(mW/m-K)
14.60
14.70
15.10
Mixture BP
(°C)
35 . 00
27.00
26.00
(Continued)
82
-------
Table 12. (continued)
f
CU. -o
CH
cyclopentene
methylcyclobutane
dimethoxymethane
vinyl formate
Vapor Thermal Conductivity (TC) in mW/m-K;
Boiling Point (BP) in °C:
Fraction
BP (°C) TC (mW/m-K) in mixture (%)
44.00	10.80	0.56
35.50	15.00	0.63
41'. 00	14.90	0.87
16.90
29.00
Mixture Data
Mixture TC
(mW/m-K)
13 .26
15.63
15.90
Mixture BP
(°C)
35.00
27.00
42.00
83
-------
Table 13. Estimated Azeotropes with Vapor Thermal Conductivity Less Than Either Component
Name	Name	Azeotrope
(mole fraction percent)
TC*
(mole fraction percent)
TC*
r
methyl formate (53%)
13.9
isoprene (47%)
14.4
13.4
2-fluorobutane (92%)
13
1,3-cyclopentadiene (8%)
13.1
12.9
2-methyl-l-butene (66%)
12.9
1,1 -difluorobutane (34%)
13
12.12
1,4-pentadiene (81 %)
12.6
1,1 -difluorobutane (19%)
13
12.3
2-pentene (73%)
12.7
1,1 -difluorobutane (27 %)
13
12.24
1,2-difluorobutane (30%)
13
1,3-cyclopentadiene (70%)
13.1
12.5
l,4-pentadiene-3-methyl (45%)
12.7
methyl t-butyl ether (55%)
14.4
12.66
1-methylcyclobutene (40%)
11.9
1,3-cyclopentadiene (60%)
13.1
11.78
methylcyclobutene (45%)
11.9
1,1 -difluorobutane (55 %)
13
11.41
1,3-pentadiene (48%)
12.1
1,1-difluorobutane (52%)
13
11.54
1,1 -difluorobutane (31 %)
13
isoprene (69%)
14.4
12.36
1,1-difluorobutane (40%)
13
1,3-cyclopentadiene (60%)
13.1
11.42
fluorobutane (61%)
12.5
1,3-cyclopentadiene (39%)
13.1
12.2
1,1 -difluoro-2-methylpropane (61%)
12.3
1,3-cyclopentadiene (39%)
13.1
12.12
* TC = Vapor thermal conductivity in mW/m-K
84
-------
Initial analysis of the azeotrope estimations also indicated that there are a number of limitations
that needed to be addressed. Among these:
•	Only 86 of the binary pairs used an HFC or a PFC as one component (10 HFC and
3 PFCs);
•	HFCs 134a, 245ca, and 245fa were not considered in the initial set of estimations;
•	Non-fluorocarbon mixtures, in general, did not have vapor thermal conductivities
less than 12 mW/m - K; Hydrocarbon/HFC mixtures were not considered
(e.g., cyclopentane/HFC-245ca or HFC-245fa might make good mixtures - the
HFC would lower the vapor thermal conductivity and flammability and
cyclopentane would lower the GWP); and
•	Identifying azeotropic mixtures was an intensive process. Typically, estimations
on approximately 25-50 component pairs were required before an azeotropic
mixture was found.
These observations were considered in order to determine the types of azeotropic mixtures that
should be investigated next. The results indicated that a small amount of one component in an
azeotrope could significantly lower the vapor thermal conductivity of the other. This result was
revealed from the initial estimates with perfluorpentane and perfluorohexane. From a realistic
standpoint, PFCs would not make reasonable third-generation blowing agents because of their
high GWPs. Fluorinated HFCs and HFEs were chosen for further investigation because they
were expected to mimic the behavior of the PFCs and were likely to form azeotropes. Fluoro-
iodocompounds were also expected to mimic the azeotropic behavior of PFCs since they were
fully halogentated. Unlike PFCs, however, they are not expected to contribute to global warming
due to their short atmospheric lifetimes resulting from photolysis of the carbon-iodine bond.
These compounds also have the lowest vapor thermal conductivities of any of the chemical
groups considered in this project. Azeotropes tend to form from mixtures of dissimilar chemicals
85
-------
(Stichilmair, 1988). Based on our initial work on blowing agent substitutes, the most likely
chemicals to form azeotropes with HFC, HFE, and fluoro-iodo compounds that could be used in
rigid polyurethane foams are hydrocarbons, olefins, ethers, and carbonyl compounds (including
fluorinated carbonyl compounds). Chemicals from these latter groups were chosen for further
investigation by referring to the list of 105 blowing agent substitutes and selecting those with
favorable vapor thermal conductivity commercial availability (or expected ease of synthesis), and
expected ability to form azeotropic mixtures. A total of 47 chemicals were chosen for further
investigation as likely components in a mixed polyurethane foam blowing agent substitute (Table
14).
Initiating work on this next step in the project revealed a severe data limitation. In order
to utilize the UNIFAC method to estimate azeotropic boiling points, two values are required. The
first is the interaction or UNIFAC parameter. As indicated above, UNIFAC parameters were
successfully derived for CHF2, CH2F, and CHF earlier in this project. To perform the estimation
on all 47 chemicals in Table 14, interaction parameters would also have to be derived for
fluoroethers, fluoroacetones, and fluoroiodocarbons. Interaction parameters with a high degree
of confidence were successfully derived for the iodofluorocarbon (CF2-I) group. There was not
sufficient experimental data, however, to derive interaction parameters for fluoroethers and
fluoroacetones. Given the potential use of fluoroethers as third-generation blowing agents,
consideration of these compounds was kept active in hopes that the required data could ultimately
be obtained.
86
-------
Table 14. Azeo trope Candidates
Vapor Thermal
Chemical
BP (°C)
Conductivity (mW/m-K)
Acetone*
56
11.25
Methane, difiuoro-*
-51.65
11
Butane, 2-methyl-*
28
14.8
Butane, 2,3-dimethyl-*
58
12.4
Pentane*
36.1
14.8
2-Pentene*
37
12.7
Cyclopentene*
44
10.8
Cyclopentane*
50
12.1
Bis-2,2,2-trifluoroethyl ether
9.5
9.93
Ethane, pentafluoroiodo-
12
8.3
1,4-Difiuorobutane
28.82
13
Methane, iodofluoro-
53.4
5.11
1,1,2,3,3,3-Pentafluoropropyl methyl ether
-7.07
11
1,1,1,4,4,4-Hexafluorobutane
24.9
9.5
Propane, 1,1,1-trifluoro-*
-13
11
1 -Methoxy-1,1,2,2-tetrafluoroethane
-12.54
12
1,1-Difluoroacetone
34.13
11
1,1,1,2,3-Pentafluoropropane
22.7
8.92
Methyl trifluoroacetate
43
10.9
1,1,1 -Trifluorobutane
0.38
12
1 -Methoxy-2,2,2-trifluoroethane
1.45
12.5
1,1,1,3,3-Pentafluoropropane
15.3
9.39
Difluoromethyl fluoromethyl ether
29.9
10.3
1,1,2,2-Tetrafluoroethyl ethyl ether
14.95
12.2
87	(Continued)
-------
Table 14. (continued)
Chemical
1,1,1,2,2,3-Hexafluoropropane
Propane, 1,1,1,2,3,3,3-heptafluoro-2-iodo-
1,1,2,2,3-Pentafluoropropane
1,1,2,2,3,3-Hexafluoropropane
Trifluoromethyl ethyl ether
1-Pentene, 4-methyl-*
Propane, 1,1,1,2,2,3,3-heptafluoro-3-iodo-
Ethane, 1,1,1,2-tetrafluoro-
1 -T rifluoromethoxy-2-fluoroethane
Methane, iododifluoro-
t-Butyl methyl ether*
Difluoromethyl ether
1.1.1.2.2-Pentafluoropropane
1,1,1,2,2,3,3-Heptafluoropropane
Methane, trifluoroiodo-
1,1 -Difluorobutane
Butane, 1-fluoro-
Ethane, 1 -iodo-1,1,2,2-tetrafluoro-
1.1.2.3.3-Pentafluoropropane
1 -Difluoromethoxy-1,1,2,2-tetrafluoroethane
1.1.2.2-Tetrafluoropropane
1,2-Difluorocyclobutane
1.1.3.3-Tetrafluorooxetane
* = Antoine coefficient available
Vapor Thermal
BP (°C) Conductivity (mW/m-K)
-1.2
10
38
8.54
25.1
8.81
10
9.27
1.45
12.5
53
11.7
40
8.06
-26.5
9.1
4.14
12.1
21.6
6.25
55
14.4
4.7
12.5
-17.6
11.5
-17.7
11
-22.5
8.06
8.56
13
32.5
12.5
41
7.45
39.3
8.19
-3.1
11.5
-1.6
10.7
24.07
12.7
21.2
12.2
88
-------
The second values that are required to estimate azeotropic boiling points are Antoine
coefficients. Antoine coefficients describe the shape of a compound's vapor pressure curve as a
function of temperature. Extensive compilations of Antoine coefficients are available in the
literature (especially for hydrocarbons) or they can be calculated from vapor pressure
measurements obtained at different temperatures. Even though Antoine coefficients were thought
to be widely available, searches of the readily available compilations produced Antoine
coefficients for only 11 of the 47 chemicals chosen for investigation (7 hydrocarbons, 1 ether, 1
carbonyl compound, and 2 HFCs). These chemicals are marked with an asterisk in Table 14.
Considerable effort was expended to obtain Antoine coefficients for HFCs, HFEs, and
iodoflurocarbons because of the relatively high vapor thermal conductivity and low flammability
of these groups. SRC performed extensive searches of CAS Online and other general indices for
citations to the open literature, on-line thermodynamic databases from commercial vendors
(including DETHERM, DIPPR, and TRCTHERMO), PC-based databases (such as the ARTI's
refrigerants database), proceedings of meetings, the patent literature, the Internet (e.g., NIST's
web site [NIST, 1997]), published compendia, and books. SRC also searched for vapor pressure
vs. temperature data; information that could be used to calculate an Antoine coefficient. This
extensive search produced usable Antoine coefficients or vapor pressure data for only a limited
number of chemicals slated for investigation (Table 15). Experimental data was also obtained for
difluoromethyl ether (HFE 134) (Defibaugh et al., 1992) and a number of other HFEs not on the
list of chemicals for further investigation (Wang et al., 1991). Antoine coefficients were also
located for a number of perfluoroalkylamines (Varouchtchenko and Droujinina, 1995), a class of
-------
Table 15. Antoine Coefficients Located in the Literature
Name
1,1,1,2-tetrafluoroethane (HFC 134a)
1.1.1.2.2-pentafluoropropane	(HFC 245cb)
1.1.1.3.3-pentafluoropropane	(HFC 245fa)
1,1,2,2,3-pentafluoropropane (HFC 245ca)
1,1,1,2,3,3-hexafluoropropane (HFC 236ea)
1-fluorobutane
1,1 -difluorobutane
1,1,1 -trifluorobutane
difluoroidodomethane
trifluoroiodomethane
pentafluoroiodoethane
Reference
(DIPPR, 1997)
(DETHERM, 1997)
(Bogdan et al., 1996)
(Defibaugh et al., 1996)
(Defibaugh et al., 1996a)
(TRCTHERMO, 1997)
(TRCTHERMO, 1997)
(DETHERM, 1997)
(Kudachadker et al., 1979)
(DETHERM, 1997)
(DETHERM, 1997)
90
-------
compounds that has appeared in the literature as potential refrigerant and/or blowing agent
substitute (Sekiya and Misaki, 1996). Unfortunately, UNIFAC interaction coefficients and vapor
thermal conductivities are not available or cannot be estimated for these amines and they could
not be examined further. Less than half of the 47 chemicals initially chosen for the final
investigation could be pursued because of the lack of required data. Once again, another route to
the desired result was required.
Analysis of the collected data indicated that except for the HFEs, Antoine coefficients
were available for at least one member of the chemical classes frequently considered as blowing
agent substitutes: alkanes, HFCs, and iodofluorocompounds. With the major classes represented,
it seemed reasonable that a simple predictive tool could be developed to identify useful trends in
azeotropic boiling point, vapor thermal conductivity, and composition. With these trends
identified, potential azeotropic blowing agent substitutes could be selected based on the
consideration of any number of specific concerns, such as flammability, global warming potential,
ozone depletion potential, solubility, molecular weight, or toxicity as well as the performance
characteristics desired in the resulting foam.
In order to identify trends in azeotrope formation, representative chemicals from the
alkane and HFC groups were chosen based on a combination of factors. For the alkanes, the
chemicals showing the highest potential to be blowing agent substitutes were chosen
(cyclopentante, pentane, and isopentane). The HFCs were expected to be the largest group, and
the choice of chemicals for further study was driven by the availability of Antoine coefficients and
-------
UNIFAC interaction coefficients as well as the degree of fluorination. Also considered was the
length of the carbon backbone (i.e., methanes, ethanes, propanes, and butanes were all included),
vapor thermal conductivity, flammability, and boiling point. A total of 13 HFCs were selected.
Also included for further study were representative chemicals from the alkenes group (alkenes
display lower vapor thermal conductivity relative to their saturated analogs), and two
representative fluoroiodocarbons. Two miscellaneous oxygenated chemicals (methyl formate and
t-butyl methyl ether) that were found to readily form azeotropes in our initial studies were also
added to the mix bringing the total to 23 chemicals (Table 16). The objective was to investigate
the azeotrope forming potential of each of these 23 chemicals with every other chemical to
establish if any trends could be identified.
Determining if the 23 representative chemicals formed azeotropes with one another
resulted in the investigation of 276 binary mixtures. The results are summarized in a series of
matrices for mole fraction (Table 17), vapor thermal conductivity (Table 18), and boiling point
(Table 19) of the binary azeotropes. The 23 chemicals are represented by a row or a column in
these matrices. Next to each chemical name is the pure component vapor thermal conductivity
and boiling point data, as appropriate. The intersection of a row and column represents a binary
mixture. The square at the intersection of a row and column contains the estimated property
value of the azeotrope if one was formed; a blank square indicates that an azeotrope was not
formed. In the matrix for mole fraction (Table 17), a numeric value indicates the percent
composition of the component on the X (diagonal) axis. A summary of these data for the
azeotropes that were formed is also provided in Table 20.
-------
Table 16. Chemicals in Azeotrope Matrix
Cyclopentane
Isopentane
Pentane
Difluoromethane
1,1,1,2-Tetrafluoroethane (HFC 32)
1.1.1.2.2-Pentafluoropropane	(HFC 134a)
1.1.1.3.3-Pentafluoropropane	(HFC 245cb)
1,1,2,2,3-Pentafluoropropane (HFC 245ca)
1,1,1,2,3,3-Hexafluoropropane (HFC 236ea)
1-Fluorobutane
1,1 -Difluorobutane
1,1,1-Trifluorobutane
1,2-Difluorobutane
2,2-Difluorobutane
1,1 -Difluoro-2-methylpropane
1,2-Difluoro-2-methylpropane
Isoprene
cis-2-Pentene
Cyclopentene
Pentafluoroiodoethane
Difluoroiodomethane
Methyl formate
93
-------
Table 17. Estimated Mole Fraction of Azeotropes (percent X axis component)
Alkanes
1>
§
g
cu
. o
u x
HFCs
cs
rr
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p
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DC
i
cn
CO
CN
§ §
9
X>
2
0
1
X)
2
o
s
s
Q
3
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s
O
J3
X>
2
o
s
iS
Q
3
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i
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cs
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2
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I
c
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g
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&
U
Fluoro-
Iodo
Other
>>
£
a>
u
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(L>
"?>
5
u
S
(9
Cyclopentane
Isopentane
Pentane
43
18
33
23
13
O
O
o
53
73
O
o
36
O
o
34
35
33
75
48
42
Difluoromethane
1,1,1,2-Tetrafluoroethane
1,1,1,2,2-Pentafluoropropane
1,1,1,3,3-Pentafluoropropane
1,1,2,2,3-Pentafluoropropane
72
19
66
72
88
63
68
29
1,1,1,2,3,3-Hexafluoropropane
85
82
O
1-Fluorobutane
1,1 -Difluorobutane
O
50
80
O
31
27
60
1,1,1 -Trifluorobutane
86
35
1,2-Difluorobutane
25
11
38
2,2 -Difluorobutane
O
o
55
O
1,1 -Difluoro-2-methylpropane
O
1,2-Difluoro-2-methylpropane
Isoprene |Q
cis-2-Pentene
30
47
23
42
_C^clo£entene
12
35
Ethane, pentafluoroiodo-
Difluoroiodomethane
Methyl formate
O = near ideal mixture
94
-------
Table 18. Estimated Vapor Thermal Conductivities of Azeotropes (mW/m-K)
Alkanes

f
&
U 49
HFCs
X)
o
a,
p
§
Oh
§ §
3
_D
s
0
1
Q
x>
2
o
a
3
X>
e
o
s
P s
3
£
s
o
Q
I4
>»
£
o
B
S iS
Q Q
Alkenes
g
a-
Q>
§
g
&
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V
Fluoro-
Iodo
Other
o
*5
o
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a>
B
1Z-L1
il
12
10
12
11
12
13
11
12
11
14
a
ii
14
14
c-Pentane 11
10
13
11
13
13
Isopentane 15
12
11
14
13
14
Pentane 15
11
11
14
13
15
13
14
14
14
Difluoromethane 11
1,1,1,2-Tetrafluoroethane 9
1,1,1,2,2-Pentafluoropropane 12
1,1,1,3,3-Pentafluoropropane 9
1,1,2,2,3-Pentafluoropropane 9
1,1,1,2,3,3-Hexafluoropropane 10
10
12
10
10
10
10
12
11
11
1-Fluorobutane 12
1,1 -Difluorobutane 13
12
13
12
12
12
12
11
1,1,1 -Trifluorobutane 12
13
11
1,2-Difluorobutane 13
13
13
12
2,2-Difluorobutane 11
12
11
12
12
l,l-Difluoro-2-rnethylpropane 12
12
1,2-Difluoro-2-methylpropane 11
Isoprene 14|l3
cis-2-Pentene 13
13
13
^C^clo£enteneJJ
13
Ethane, pentafluoroiodo- 8
Difluoroiodomethane 6
Methyl formate 14
95
-------
Table 19. Estimated Boiling Points of Azeotropic Blowing Agents (°C)
Alkanes
u
c
aS
e
o
a
&
V
HFCs

2
o
f*
Q
3
2
o
_3
=J
X>
2
0
1
Q
x>
2
0
1
a
ci
¦I*
0
£
1
2
0
1
Q
o-
2
o?
>>
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(U
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i
CN
i
2
0
1
Q
Alkenes
a>
c
B
c

Oh
_o
&
U
Fluoro-
Iodo
2 °
Other
a>
!
a>
s
2^


18
11
25
2mm
QA
21
21
21
34
38
44
12
32
55
c-Pentane 50
25
47
46
27
48
Isopentane 28
17
29
28
17
Pentane 36
21
34
37
35
33
14
36
22
Difluoromethane -51
1,1,1,2-Tetrafluoroethane -26
1,1,1,2,2-Pentafluoropropane -17
1,1,1,3,3-Pentafluoropropane 15
1,1,2,2,3-Pentafluoropropane 25
25
27
23
25
25
21
21
34
1,1,1,2,3,3-Hexafluoropropane 6
1-Fluorobutane 32
1,1-Difluorobutane 8
33
28
32
38
31
36
39
1,1,1-Trifluorobutane 0.4
17
1,2-Difluorobutane 9
2,2-Difluorobutane 31
30
36
42
32
l,l-Difluoro-2-methylpropane 33
33
27
33
34
1,2-Difluoro-2-methylpropane 36
Isoprene 34[36
cis-2-Pentene 38
23
24
Cyclopentene 44
10
26
Pentafluoroiodoethane 12
Difluoroiodomethane 6
Methyl formate 32
96
-------
Table 20. Azeotrope Matrix Summary
Mixture Chemicals
Cyclopentane
1,1,2,2,3-Pentafluoropropane
1,2-Difluoro butane
Cyclopentene
Methyl formate
t-Butyl methyl ether
Isopentane
1,1,2,2,3-Pentafluoropropane
1,1,1,2,3,3-Hexafluoropropane
1-Fluorobutane
2,2-Difluorobutane
Ethane, pentafluoroiodo-
Methyl formate
Pentane
1,1,2,2,3-Pentafluoropropane
1,1,1,2,3,3-Hexafluoropropane
1-Fluorobutane
1,1 -Difluorobutane
1,2-Difluorobutane
2,2-Difluorobutane
Isoprene
cis-2-Pentene
Ethane, pentafluoroiodo-
Methyl formate
1-Fluorobutane
Mole Fraction
(%)
72
47
O
67
25
57
77
O
O
66
52
67
87
O
O
27
O
64
O
65
58
28
97
Vapor Thermal Boiling
Conductivity	Point
(mW/m-K)	(°C)
9.71	25
13	47
11.4	46
13.2	27
12.7	48
11.6	17
11.3	4
13.7	29
13.1	28
9.16	4
14.3	17
11.0	21
10.8	6
13.7	34
12.9	37
14.6	35
13.1	33
13.7	14
13.8	36
9.26	6
14.3	22
11.5	25
(Continued)
-------
Table 20. (continued)
Mixture Chemicals
1,1,1 -Trifluorobutane
2,2-Difluorobutane
1,1 -Difluoro-2-methylpropane
1,2-Difluoro-2-methylpropane
cis-2-Pentene
Cyclopentene
Methyl formate
1,1,1,2,3,3-Hexafluoropropane
1,1,1-Trifluorobutane
cis-2-Pentene
Ethane, pentafluoroiodo-
1-Fluorobutane
1,1 -Difluoro-2-raethylpropane
Isoprene
cis-2-Pentene
1,1 -Difluoro butane
1,2-Difluoro-2-methylpropane
Isoprene
cis-2-Pentene
Cyclopentene
1,1,1-T rifluorobutane
Isoprene
Ethane, pentafluoroiodo-
1,2-Difluorobutane
Isoprene
Vapor Thermal Boiling
Fraction Conductivity	Point
(%)	(mW/m-K)	(°C)
12.2	27
9.91	23
10.0	25
9.41	25
10.5	21
9.76	21
12.4	34
10.6	6
10.7	5
8.3	8
11.8	33
12	28
12.8	32
11.6	38
12.4	31
12.2	36
11.0	39
13.0	17
10.5	8
13.3	30
Mole
81
34
28
12
37
32
71
15
18
O
o
50
20
O
69
33
40
14
65
75
98
(Continued)
-------
Table 20. (continued)
Mixture Chemicals
cis-2-Pentene
Cyclopentene
2,2-Difluorobutane
1,1 -Difluoro-2-methylpropane
1,2-Difluoro-2-methylpropane
Isoprene
cis-2-Pentene
1,1 -Difluoro-2-methylpropane
1,2-Difluoro-2-methylpropane
Isoprene
cis-2-Pentene
Ethane, pentafluoroiodo-
Methyl formate
cis-2-Pentene
Ethane, pentafluoroiodo-
Methyl formate
Cyclopentene
Ethane, pentafluoroiodo-
Methyl formate
O = non-ideal mixture
Vapor Thermal Boiling
Mole Fraction Conductivity	Point
(%)	(mW/m-K)	(°C)
89	12.8	36
62	12.1	42
O	11.8	32
O	11.3	33
45	12.1	27
O	12.1	33
O	11.7	34
O	12.8	36
70	8.3	6
53	13.4	23
77	7.81	9
58	13.3	24
88	6.89	10
65	12.7	26
99
-------
If a shaded circle (O) appears in Table 17 for mole fractions, a near ideal mixture was
formed by the two chemicals. As indicated earlier, the boiling point of an ideal mixture remains
constant over the entire composition range. However, a 50/50 mixture of the two components
would behave differently than a 90/10 mixture. Since the vapor thermal conductivity would
change as a function of the blend ratio, the data in Table 17 were estimated for a 50/50 ratio of
the two components. In theory, an ideal mixture blowing agent could be specifically blended to
achieve the desired vapor thermal conductivity for a specific application. In reality, however, it is
more likely that the blend ratio would be close to 50/50. These near ideal mixtures were included
in this analysis because they represent another type of mixture that has the potential to be used as
a blowing agent substitute.
Analysis of Tables 17, 18, and 19 revealed a number of interesting and unexpected results:
•	Of the 276 mixtures investigated, 42 formed azeotropes and 14 formed near ideal
mixtures. Even though the chemicals were chosen, in part, based on their ability to
form azeotropes, it was still surprising that such a high number were identified
given the general lack of data available in the literature;
•	HFCs are capable of forming azeotropes or ideal mixtures with other HFCs. The
general rule of thumb is that azeotropes are formed from dissimilar chemicals.
Azeotropes formed from two different HFCs were not expected and represent a
particularly interesting opportunity for blowing agent substitutes;
•	General trends that can predict what chemicals are likely to form azeotropes could
not be identified. For example, HFC 245ca (1,1,2,2,3-pentafluoropropane) formed
azeotropic mixtures with a wide variety of other chemicals, while HFC 245fa
(1,1,1,3,3-pentafluorpropane) and HFC 245cb (1,1,1,2,2-pentafluorpropane) did
not; and
•	Azeotropic compositions can not be predicted based on systematic changes to
molecular structure. For example, 1-fluoro-, 1,1-difluoro-, and 1,1,1-
trifluorobutane formed azeotropes with isoprene. The estimated mole fraction of
the HFCs was 50%, 31%, and 86%, respectively. The mole fraction did not follow
an incremental change with increasing fluorine content.
100
-------
These results indicate that predicting whether two chemicals will form an azeotrope requires the
use of the estimation methodology discussed in this section and cannot be made by comparison of
structural similarities between groups of compounds. That is, no readily identifiable trends were
observed. This point is reinforced using fluoroiodo compounds as an example.
The fluoroiodo compounds were examined closely because of their high vapor thermal
conductivity and some additional work was performed on difluoroiodomethane. Unlike
pentafluoroiododoethane which formed 7 azeotropes with matrix chemicals, difluoroiodomethane
did not form any. On further investigation, however, difluoroiodomethane was found to form
azeotropes with 1-fluoro- and 1,2-difluoropentane (Table 21), chemicals that have only one
carbon more than two of the matrix chemicals, 1-fluoro- and 1,2-difluorobutane.
Another interesting result of the matrix study was the propensity of HFC 245ca to form
azeotropes. This HFC formed 11 azeotropes with matrix chemicals. Because of the propensity of
HFC 245ca to form azeotropes, we investigated it further by performing azeotrope estimations
with other pairs. This process identified an additional 11 azeotropes formed by HFC 245ca which
are presented in Table 22. The total number of azeotropes found for HFC 245ca (22) far exceed
the number found for any of chemical studied in this project.
Kam (Kam, 1993) developed a method for calculating the vapor thermal conductivity of
azeotropic mixtures based only on the weight fraction and vapor thermal conductivity of each
component. An interesting aspect of this method is that it is designed with the expectation that
the vapor thermal conductivity of the mixture will be lower than that of either component. This
101
-------
Table 21. Azeotropes of Pentafluoroiodoethane and Difluoroiodomethane
Chemical
Pentafluoroiodoethane
3,3-dimethyl-1 -butene
2-pentene
isoprene
isopentane
1,1,1 -trifluoro butane
n-pentane
neopentane
Iododifluoromethane
1,1 -difluoropentane
1-fluoropentane
2-fluoropentane
Vapor Thermal Boiling
Mole Fraction Conductivity	Point
(%)	(mW/m-K)	(°C)
22	7.71	7
23	7.81	9
30	8.30	6
34	9	4
35	11	8
35	9.26	6
50	10.7	-5
45	8.08	8
60	9.55	3
67	10.3	-1
102
-------
Table 22. Azeotropes of HFC 245ca.
Binary Component with	Mole Fraction
HFC 245ca (%)
1.2-difluoro-2-methylpropane	12
cyclopentane	18
cyclopentene	32
2.3-dimethylbutane	13
2,2-difluorobutane	34
2,2-dimethylbutane	19
l,l-difluoro-2-methylpropane	28
1-methylcyclobutene	34
1-fluorobutane	28
2-pentene	37
2-methyl-l-butene	43
2-methyl-2-butene	34
pentane	33
1-pentene	45
methylcyclobutane	36
ethylcyclopropane	36
isopentane	43
3-methyl-1	-butene	55
1,1,1-trifluorobutane	81
methyl formate	71
2-fluoro-2-methylpropane	83
neopentane	70
Vapor Thermal Boiling
Conductivity	Point
(mW/m-K)	(°C)
9.41
26
9.71
25
9.76
21
9.78
24
9.94
23
10.0
23
10.0
24
10.1
20
10.1
25
10.5
21
10.8
16
10.9
20
11.0
20
11.2
15
11.2
21
11.4
20
11.6
17
11.8
9
12.2
27
12.4
34
12.4
13
13.4
7
103
-------
method is based on only 17 azeotropic mixtures, many of which included water as one
component. For an insulating foam blowing agent, a mixture vapor thermal conductivity that is
lower than that of either component is a very attractive factor. Our results indicate that it is
relatively rare for an azeotropic mixture to display this effect. Only three of the 48 matrix
azeotropes displayed this effect (1,1 -difluorobutane/isoprene, 1,1 -difluorobutane/2-pentene,
isoprene/methylformate). Of the approximately 500 azeotropic mixtures identified in this project,
14 mixtures were found that had vapor thermal conductivities lower than both components. For
the remainder, the vapor thermal conductivity generally followed a trend based on the mole
fraction and vapor thermal conductivity of each component.
Assigning GWPs to the Identified Azeotropic Blowing Agents
Azeotropic mixtures were studied in this project because they offer a number of potential
advantages over traditional single-substance blowing agents. One of the most significant areas
where azeotropic mixtures are likely to prove advantageous is in their potential reduction in the
anthropogenic contribution to global warming from the manufacture of insulating foams. There
were two major sets of estimations performed in the investigation of azeotropic blowing agents.
In the initial estimation set, 55 chemicals were found to form azeotropic mixtures. The literature
and estimated GWPs for these 55 chemicals are presented in Tables 23 and 24, respectively.
Table 24 also contains the hydroxyl radical reaction rate and atmospheric lifetime from which the
GWPs were estimated. The second estimation set was performed on a matrix of 23 chemicals.
The literature and estimated GWPs for these chemicals are provided in Tables 25 and 26,
respectively. The estimated GWP for the actual azeotropic mixture can be roughly estimated to
104
-------
Table 23. Literature GWPs for Initial Azeotrope Investigation Chemicals
CAS
Chemical Name
GWP
Reference
000067641
acetone
0 *C02
Ashida et al. (1994)
000075832
2,2-dimethylbutane
0 *C02
Ashida et al. (1994)
000078784
isopentane
.0004* CFC 11
Heilig and Wiederman (1993)
000078795
isoprene
0 *C02
Ashida et al. (1994)
000079209
methyl acetate
0 *C02
Ashida et al. (1994)
000079298
2,3 -dimethy lbutane
0 *C02
Ashida et al. (1994)
000107313
methyl formate
0 *C02
Ashida et al. (1994)
000109660
pentane
0 *C02
Ballhaus and Hahn (1993)
000109944
ethyl formate
0 *C02
Ashida et al. (1994)
000110827
cyclohexane
0 *C02
Ashida et al. (1994)
000142290
cyclopentene
0 *C02
Ashida et al. (1994)
000287923
cyclopentane
<0.001 *CFC 11
Heilig and Wiederman (1993)
000355420
perfluorohexane
5000(20),7400(100),
10700(500) *C02
IPCC (1996)
000678262
perfluoropentane
5100(2), 7500(100),
11000(500) *C02
IPCC (1996)
*CFC 11 = GWP relative to CFC 11 as the reference gas
*C02 = GWP relative to C02 as the reference gas. The time horizon is in parentheses
105
-------
Table 24. Estimated GWPs for Initial Azeotrope Investigation Chemicals
OH Rate Constant
Lifetime Estimated GWP
Name
(cm3/molecu!e-sec)
Exp?
(years)
(100 yc
1,3-cyclopentadiene
1.427472e-10

2.85e-04
Zero to
isoprene
1.08e-10
V
3.76e-04
Zero to
1,3-pentadiene
1.01e-10
/
4.02e-04
Zero to
1 -methylcyclobutene
8.756e-ll

4.64e-04
Zero to
2-methyl-2-butene
8.69e-ll
V
4.68e-04
Zero to
2-pentene
6.5e-ll
/
6.25e-04
Zero to
2-butene
6.4e-ll
V
6.35e-04
Zero to
2-methyl-1 -butene
6-le-ll
/
6.66e-04
Zero to
3-methylcyclopentene
6.052e-ll

6.72e-04
Zero to
1,4-pentadiene-3-methyl
5.470728e-ll

7.43e-04
Zero to
1,4-pentadiene
5.3e-ll
V
7.67e-04
Zero to
trimethyl orthoformate
4.580125e-ll

8.87e-04
Zero to
ethyl vinyl ether
4.03634e-ll

1.01e-03
Zero to
l-buten-3-yne
4.014e-ll

1.01e-03
Zero to
1-pentene
3.19e-l1
V
1.27e-03
Zero to
3-methyl-1 -butene
3.18e-ll
V
1.28e-03
Zero to
1-butene, 3,3-dimethyl
2.85e-ll
/
1.43e-03
Zero to
vinyl formate
2.63e-ll

1.55e-03
Zero to
methyl isopropyl ether
1.3e-ll

3.13e-03
Zero to
1-pentyne
1.12e-ll
/
3.63e-03
Zero to
1,1 -dimethoxyethane
8.89e-12
V
4.57e-03
Zero to
methylcyclopentane
7.03706e-12

5.78e-03
Zero to
dimethoxymethane
5.07764e-12

8.'00e-03
Zero to
methyl t-butyl ether
2.94e-12
V
1.38e-02
Zero to
methylcyclobutane
2.17605e-12

1.87e-02
Zero to
106
(Continued)
-------
Table 24. (continued)
Name
OH Rate Constant
(cm3/molecule-sec)
Exp?
Lifetime
(years)
Estimated GWP
(100 year horizon)
fluorobutane
2.12487e-12

1.91e-02
Zero to 1
2-fluorobutane
2.12e-12

1.92e-02
Zero to 1
cyclobutane
1.5e-12
/
2.71e-02
Zero to 1
1,1-difluorobutane
1.49e-12

2.73e-02
Zero to 1
ethylcyclopropane
1.44482e-12

2.81e-02
Zero to 1
1,1,1 -trifluorobutane
1.4e-12

2.90e-02
Zero to 1
tetramethyl silane
le-12
/
4.06e-02
Zero to 1
neopentane
8.49e-13
/
4.79e-02
Zero to 1
l,l-difluoro-2-
methylpropane
6.1e-13

6.66e-02
Zero to 1
1,1,2-
trimethylcyclopropane
5.888e-13

6.90e-02
Zero to 1
1,2-difluorobutane
5.2e-13

7.82e-02
Zero to 1
2-fluoro-2-
methylpropane
4.08e-13

9.96e-02
Zero to 1
l,2-difluoro-2-
methylpropane
3.6e-13

1.13e-01
Zero to 1
methylcyclopropane
2.825e-13

1.44e-01
Zero to 1
2,2-difluorobutane
1.8654e-13

2.18e-01
Zero to 1
/ - Experimentally determined.
107
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Table 25. Literature GWPs for Matrix Chemicals
CAS
Name
000811972	1,1,1,2-
T etrafluoroethane
000287923	Cyclopentane
000142290	Cyclopentene
000075105	Difluoromethane
000078784	Isopentane
000078795	Isoprene
000107313	Methyl formate
000109660	Pentane
GWP
3300(20), 1300(100),420
(500) *C02
<0.001 *CFC 11
0 *C02
1800(20),580(100),180
(500) *C02
0.0004 *CFC 11
0 *C02
0 *C02
0
Reference
Albritton et al. (1995)
Heilig and Wiederman (1993)
Ashida et al. (1994)
Albritton et al. (1995)
Heilig and Wiederman (1993)
Ashida et al. (1994)
Ashida et al. (1994)
Ballhaus and Hahn (1993)
*CFC 11 = GWP relative to CFC 11 as the reference gas
*C02 = GWP relative to C02 as the reference gas. The time horizon is in parentheses
108
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Table 26. Estimated GWPs for Matrix Chemicals
Name
OH Rate Contant
(cm3/molecule-sec)
Exp ?
Lifetime
(years)
Estimated GWP
(100 year horizon)
cis-2-Pentene
6.5e-ll
/
6.25e-04
Zero to 1
2,2-Difluorobutane
1.8654e-13

2.18e-01
Zero to 1
1,1 -Difluorobutane
1.48e-12

2.75e-02
Zero to 1
1,1,1,2,3,3-
Hexafluoropropane
8.51e-15
V
4.78e+00
200 - 1,000
1,1,1 -Trifluorobutane
1.4e-12

2.90e-02
Zero to 1
1,1,1,3,3-
Pentafluoropropane
2.97 le-14

1.37e+00
200 - 1,000
Neopentane
8.49e-13
/
4.79e-02
Zero to 1
3,3-Dimethyl-1 -butene
2.85e-ll
V
1.43e-03
Zero to 1
1,1,2,2,3-
Pentafluoropropane
1.09e-14
/
3.73e+00
200 - 1,000
1,2-Difluorobutane
5.2e-13

7.82e-02
Zero to 1
1,1,1,2,2-
Pentafluoropropane
2.45e-15

1.66e+01
2,000 - 3,500
1-Fluorobutane
2.12487e-12

1.91e-02
Zero to 1
l,l-Difluoro-2-
methylpropane
6.1e-13

6.66e-02
Zero to 1
l,2-Difluoro-2-
methylpropane
3.6e-13

1.13e-01
Zero to 1
/ - Experimentally determined.
109
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be the sum of the molar ratio of each component multiplied by its GWP. This process is
illustrated for the combined GWP for the azeotropes formed by the matrix chemicals (Table 27).
For those matrix chemicals with estimated GWPs, the lowest value in the estimated range was
used for these calculations. Evaluation of the data in Table 27 indicates that most of the
individual components of azeotropic mixtures identified possessed relatively low GWPs to begin
with, an expected result given the goals of this project. The data demonstrate, however, that
large reductions in the GWP can potentially be achieved if an azeotropic mixture is chosen over
one of its components. For example, the azeotropic mixture of 1,1,1,2,3,3-hexafluoropropane
and pentafluoroiodoethane results in an estimated 50% decrease in overall GWP compared to the
use of the HFC alone.
110
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Table 27. Approximate GWP of Azeotropic Blowing Agents
Overall
Component 1
%
GWP
Component 2
%
GWP
GWP

85
200
1,1,1 -Trifluorobutane
15
0
170
1,1,1,2,3,3-Hexafluoropropane
50
200
Ethane, pentafluoroiodo-
50
0
100
1,1,1,2,3,3-Hexafluoropropane
82
200
cis-2-Pentene
18
0
164
1,1,1 -Trifluorobutane
35
0
Ethane, pentafluoroiodo-
65
0
0
1,1,1 -Trifluorobutane
86
0
Isoprene
14
0
0
1,1 -Difluorobutane
50
0
1,2-Difluoro-2-methylpropane
50
0
0
1,1 -Difluorobutane
60
0
Cyclopentene
40
0
0
1,1 -Difluorobutane
31
0
Isoprene
69
0
0
1,1 -Difluorobutane
67
0
cis-2-Pentene
33
0
0
1,2-Difluorobutane
38
0
Cyclopentene
62
0
0
1,2-Difluorobutane
25
0
Isoprene
75
0
0
1,2-Difluorobutane
11
0
cis-2-Pentene
89
0
0
1 -Fluorobutane
50
0
1,1 -Difluoro-2-methylpropane
50
0
0
1-Fluorobutane
50
0
Isoprene
50
0
0
1-Fluorobutane
80
0
cis-2-Pentene
20
0
0
2,2-Difluorobutane
50
0
1,1 -Difluoro-2-methylpropane
50
0
0
2,2-Difluorobutane
50
0
1,2-Difluoro-2-methylpropane
50
0
0
2,2 -Difluorobutane
55
0
Isoprene
45
0
0
2,2-Difluorobutane
50
0
cis-2-Pentene
50
0
0
Cyclopentane
28
0
1,1,2,2,3-Pentafluoropropane
72
200
144
Cyclopentane
53
0
1,2-Difluorobutane
47
0
0
Cyclopentane
50
0
Cyclopentene
50
0
0
Cyclopentane
33
0
Methyl formate
67
0
0
Cyclopentane
75
0
t-Butyl methyl ether
25
0
0
Cyclopentene
12
0
Ethane, pentafluoroiodo-
88
0
0
Cyclopentene
35
0
Methyl formate
65
0
0
Isopentane
23
0
1,1,1,2,3,3-Hexafluoropropane
77
200
154
Isopentane
43
0
1,1,2,2,3-Pentafluoropropane
57
200
114
(Continued)
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Table 27. (continued)
Overall
Component 1
%
GWP
Component 2
%
GWP
GWP
Isopentane
50
0
1 -Fluorobutane
50
0
0
Isopentane
50
0
2,2-Difluorobutane
50
0
0
Isopentane
34
0
Ethane, pentafluoroiodo-
66
0
0
Isopentane
48
0
Methyl formate
52
0
0
Isoprene
30
0
Ethane, pentafluoroiodo-
70
0
0
Isoprene
47
0
Methyl formate
53
0
0
Isoprene
50
0
cis-2-Pentene
50
0
0
Pentane
13
0
1,1,1,2,3,3-Hexafluoropropane
87
200
174
Pentane
19
0
1,1,1 -Trifluorobutane
81
0
0
Pentane
33
0
1,1,2,2,3-Pentafluoropropane
67
200
134
Pentane
72
0
1,1 -Difluoro-2-methylpropane
28
0
0
Pentane
50
0
1,1 -Difluorobutane
50
0
0
Pentane
88
0
1,2-Difluoro-2-methylpropane
12
0
0
Pentane
73
0
1,2-Difluorobutane
27
0
0
Pentane
72
0
1 -Fluorobutane
28
0
0
Pentane
50
0
1 -Fluorobutane
50
0
0
Pentane
66
0
2,2-Difluorobutane
34
0
0
Pentane
50
0
2,2-Difluorobutane
50
0
0
Pentane
68
0
Cyclopentene
32
0
0
Pentane
35
0
Ethane, pentafluoroiodo-
65
0
0
Pentane
36
0
Isoprene
64
0
0
Pentane
42
0
Methyl formate
58
0
0
Pentane
29
0
Methyl formate
71
0
0
Pentane
63
0
cis-2-Pentene
37
0
0
Pentane
50
0
cis-2-Pentene
50
0
0
cis-2-Pentene
23
0
Ethane, pentafluoroiodo-
77
0
0
cis-2-Pentene
42
0
Methyl formate
58
0
0
112
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Conclusion
Flammability of Blowing Agent Substitutes
The flammability of blowing agent substitutes can be used to address important safety
factors that may arise during the manufacture, distribution, use, and disposal of insulating
polyurethane foams. There is an abundance of flammability data available for hydrocarbons,
ketones, ethers, and other similar commercially important chemicals but there is a dearth of data
available for HFC, HFEs, and other classes of potential third-generation blowing agents.
Literature methodology for estimating the LFL and UFL of organic chemicals has been available
for some time. This project established that these methods work reasonably well for chemicals
that are expected to form flammable mixtures in air, but they are incapable of predicting if a
chemical will be non-flammable. All else being equal, a non-flammable blowing agent substitute is
advantageous from both a safety and cost standpoint.
A relatively simple method for determining if a third-generation blowing agent substitute
will be non-flammable was developed based on the halo gen: hydro gen index of the chemical under
consideration. By using either the chemical structure or the molecular formula, the number of
hydrogens and the number of halogen atoms (F, CI, or Br) can be readily determined. For
saturated (no double or triple bonds) compounds that do not contain iodine, the halogen:hydrogen
index is equal to (# of halogens + # of hydrogens) / # of halogens. If the halogen:hydrogen index
is 1.2 or less, the compound is expected to be non-flammable. If all the halogen atoms are
fluorine, then the compound is expected to be non-flammable if the halo gen: hydro gen index is 1.3
113
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or less. For compounds with a halogen:hydrogen index greater than 1.2, the LFL and UFL can be
determined with reasonable accuracy using the flammability estimation methods available in the
open literature.
Third-Generation Azeotropic Blowing Agents
The investigation of azeotropic mixtures as potential third-generation blowing agents
substantially increases the number of alternatives that can be considered for the production of
insulating foams. Azeotropic blowing agents can be blended to obtain a variety of physical,
performance, and safety properties. There have been a number of strong efforts over the past few
years to find CFC and HCFC substitutes. This project has utilized much of this work to further
expand the selection of suitable alternatives. As the list of suitable alternatives grows, so does the
potential for identifying blowing agents that are better than current industry solutions.
One of the areas where azeotropic blowing agents offer the highest potential as
replacements is in the reduction of global warming. Azeotropic blowing agents hold the potential
to reduce the anthropogenic contribution to global warming from polyurethane foam manufacture
in two areas. The first is the potential to blend two substances with low GWPs into a blowing
agent mixture that performs better than a chemical with a relatively high GWP. The second area
where azeotropes can reduce the anthropogenic contribution to global warming is to reduce the
total quantity of a chemical used in the production of foams. The lower the amount of a chemical
used, the less that it can contribute to radiative forcing. For example, HFC 245ca (vapor thermal
conductivity 9 mW/m-k, estimated GWP 1-10, boiling point 25 °C) is a likely blowing agent
114
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substitute for insulating foams. Blending this substitute with 2-pentene (estimated GWP 0) does
not have a significant effect on the boiling point, raises the vapor thermal conductivity slightly to
10 mW/m-k, and reduces the amount of HFC 245ca in the foam by 37%. Use of this azeotrope
would, therefore, reduce the amount of HFC 245ca that could contribute to global warming
through its use in the manufacture of insulating polyurethane foams by 37% relative to the use of
the pure HFC as a blowing agent.
Blowing agent azeotropes could also be blended to achieve a blowing agent with the
required boiling point or vapor thermal conductivity. An azeotropic blowing agent could also be
blended to reduce toxicity and flammability concerns. Although the flammability limits of an
individual chemical will not decrease in a mixture, the amount of a flammable chemical used in the
manufacture of the foam will. If the azeotrope is chosen such that the flammable component is
not present in sufficient quantity to exceed its LFL during manufacture, its explosion hazard is
greatly reduced. Similarly, the quantity of a flammable component present in the foam will also be
decreased, reducing the explosion hazard at the use level. It is also possible to reduce toxicity
concerns of a blowing agent substitute through the use of azeotropic mixture. Of course, the
toxicity of an individual component cannot be reduced. If this componment is only a small
percentage of the blowing agent mixture, then is it possible that levels of exposure during
production and use of the foam may be sufficiently low that adverse health or environmental
effects are not expressed.
The above concepts on blowing agent mixtures should encourage interested parties to
investigate the use of azeotropes in laboratory foaming trials on insulating polyurethane foams.
115
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Many of the azeotropes formed by the matrix chemicals have relatively low vapor thermal
conductivities and appropriate boiling points. Initial foaming trials initiated using the matrix
chemicals would serve to both validate the azeotrope estimation technique and reinforce the
usefulness of azeotropic blowing agents. There are limited data on azeotropic blowing agents in
the available literature. Ashida and coworkers (Ashida et al. 1994, 1995) studied azeotrope
blowing agents for isocyanate-based foams. The best insulating foams were formed when the
blend ratio of the blowing agent mixture was the same as the azeotropic vapor composition. This
is consistent with data published by Kam (Kam, 1993) where the vapor thermal conductivity of a
number of mixtures or of a blown foam was lowest when the two components were present at
their azeotropic ratios. The patent literature contains a number of citations on azeotropic blowing
agents and, even though they are short on experimental details, they provide additional
justification for further study in this area. Laboratory experiments are the next step required to
demonstrate that the development and blending of azeotropic blowing agents for rigid
polyurethane foams will meet required performance characteristics, reduce the anthropogenic
contribution to global warming, and satisfy health and safety requirements.
116
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Werner, J., S.A., Kane, H.P. Doerge, and E.F. Boonstra. Azeotropic Compositions of
Perfluorohexane, or 1,1,1,4,4,4-Hexafluorobutane, or 1,3-Dioxolane and Hydrocarbons Having 5
or 6 Carbon Atoms. International Application Published Under the Patent Cooperation Treaty.
WO 96/3043 (1996a)
Wuebbles, D.J. and J. Edmonds. Primer on Greenhouse Gases. Lewis Publishers, Chelsea, MI.
(1991)
121
-------
Appendix A. Flammability Limits Collected from the Literature


CAS
Number
Name
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
000011111
OCTAFLUORO-M-DIODOBUTANE
*

NF**

Tapscott et al. (1995)
000012121
4-BROMO-3-CHLORO-3,4,4-
TRIFLUORO-1-BUTENE
NF
NF
NF

Tapscott et al. (1995)
000013131
4-BROMO-3,3,4,4-TETRAFLUORO-l-
BUTENE
NF
NF
NF

Tapscott et al. (1995)
000022222
TRIDEC AFLUORO-1 -IODOHEXANE
NF
NF
NF

Tapscott et al. (1995)
000033333
HEPTADECAFLUORO-l-lODOOCTANE
NF
NF
NF

Tapscott et al. (1995)
000044444
2-BROMO-3,3.3-TRIFLUOROPROPENE
NF
NF
NF

Tapscott et al. (1995)
000050000
FORMALDEHYDE

7.0
73.0
703.15
Daubert and Danner (1996)
000055555
3-BROMO-3,3-DIFLUOROPROPENE
NF
NF
NF

Tapscott et al. (1995)
000056235
CARBON TETRACHLORIDE
NF
NF
NF
NF
ARTI (1997)
000057556
1,2-PROPANEDIOL
372.04
2.6
12.5
694.26
Daubert and Danner (1996)
000057578
BETA-PROPIOLACTONE
347.04
2.9


Daubert and Danner (1996)
000060242
2-MERCAPTOETHANOL
340.15
2.3
18.0
568.15
Daubert and Danner (1996)
000060297
DIETHYL ETHER
228.15
1.9
48.0
433.15
Daubert and Danner (1996)
000060344
METHYLHYDRAZINE
343.15
2.5
97

Merck (1996)
000062533
ANILINE
343.15
1.3
11.0
890.37
Daubert and Danner (1996)
000064175
ETHANOL
286.00
4.3
19.0
696
Daubert and Danner (1996)
000064186
FORMIC ACID
321.15

38.0
753.15
Daubert and Danner (1996)
000064197
ACETIC ACID
316.00
5.4
16.0
700
Daubert and Danner (1996)
000067561
METHANOL
284.00
7.3
36
737
Daubert and Danner (1996)
000067630
ISOPROPANOL
284.82
2.0
12.0
672.04
Daubert and Danner (1996)
000067641
ACETONE
255.37
2.6
12.8
810.93
Daubert and Danner (1996)
000067663
CHLOROFORM
NF
NF
NF

ARTI (1997)
000067685
DIMETHYL SULFOXIDE
360.93
2.6
28.5
488.15
Daubert and Danner (1996)
000067721
HEXACHLOROETHANE
NF
NF
NF

ARTI (1997)
000068122
N,N'-DIMETHYLFORMAMIDE
330.93
2.2
15.2

Daubert and Danner (1996)
000071238
1-PROPANOL
288.15
2.0
12.0

Daubert and Danner (1996)
000071363
1-BUTANOL
302.00
1.4
11.2
616.00
Daubert and Danner (1996)
000071410
1-PENTANOL
305.93
1.2
10.0
573.15
Daubert and Danner (1996)
122
-------
Appendix A. (continued)
CAS
Number	Name
000071432	BENZENE
000071556	1,1,1 -TRICHLOROETHANE
000074828	METHANE
000074839	METHYL BROMIDE
000074840	ETHANE
000074851	ETHYLENE
000074862	ACETYLENE
000074873	METHYL CHLORIDE
000074884	METHYL IODIDE
000074895	METHYLAMINE
000074908	HYDROCYANIC ACID
000074931	METHANETHIOL
000074964	BROMOETHANE
000074975	CHLOROBROMOMETHANE
000074986	PROPANE
000074997	PROPYNE
000075003	CHLOROETHANE
000075014	VINYLCHLORIDE
000075025	VINYLFLUORIDE
000075036	IODOETHANE
000075047	ETHYLAMINE
000075058	ACETONITRILE
000075070	ACETALDEHYDE
000075081	ETHYL MERCAPTAN
000075092	DICHLOROMETHANE
000075105	DIFLUOROMETHANE
000075150	CARBON DISULFIDE
000075183	DIMETHYLS ULFIDE
000075194	CYCLOPROPANE
Flash
Point
(°C)
262.00
NF-T
255.37
<273.15
NF
273.15
255.37
NF
223.15
195.00
NF
278.71
235.00
225.00
NF-T
NF-T
243.15
239.26
LFL
(%)
1.2
7.4
5.0
10.0
2.9
2.7
2.5
8.1
NF
4.9
6.0
3.9
6.7
NF
2.0
1.7
3.8
3.6
2.6
NF
3.5
4.4
4.0
2.8
15.9
12.7
1.3
2.2
2.4
UFL
(%)
8.0
16.5
15.0
16.0
13.0
36.0
80.0
17.2
NF
20.7
41.0
21.8
11.3
NF
9.5
15.4
33
21.7
NF
14.0
16.0
60.0
18.0
19.1
33.5
50.0
19.7
10.4
Autoig
Temp
CC)
833.15
810
810.37
745
723.15
578.15
905.00
703.15
810.93
784.26
723
792
745
658.15
NF
657
797.04
403.15
572
888.15
921
363.15
479.26
770.93
Reference
Daubert and Danner (1996)
ARTI (1997)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
ARTI (1997)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
ARTI (1997)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
ARTI (1997)
Daubert and Danner
Daubert and Danner
Daubert and Danner
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
123
-------
Appendix A. (continued)
CAS
Number
Name
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
000075218
ETHYLENE OXIDE

3.0
100
702.04
Daubert and Danner (1996)
000075252
BROMOFORM
NF
NF
NF

ARTI (1997)
000075285
2-METHYLPROPANE

1.8
8.4
733.15
Daubert and Danner (1996)
000075296
2-CHLOROPROPANE
238.15
2.8
10.7
866
Daubert and Danner (1996)
000075310
ISOPROPYLAMINE
236.15
2.0
10.4
675.15
Daubert and Danner (1996)
000075343
1,1-DICHLOROETHANE
261.15
5.4
11.4
731.15
Daubert and Danner (1996)
000075354
1,1 -DICHLOROETHENE
255.00
7.3
16.0
843.00
Daubert and Danner (1996)
000075376
1,1 -DIFLUOROETHANE

4.4
17.5

Barthelemy et al. (1993)
000075387
1,1 -DIFLUOROETHENE

5.5
21.3
913
Daubert and Danner (1996)
000075434
DICHLOROFLUOROMETHANE
NF
NF
NF
827
ARTI (1997)
000075456
CHLORODIFLUOROMETHANE
NF
NF
NF
905
ARTI (1997)
000075467
TRIFLUOROMETHANE
NF
NF
NF
1038
ARTI (1997)
000075478
IODOFORM
NF
NF
NF

ARTI (1997)
000075503
TRIMETHYLAMINE
266.48
2.0
11.6
463.15
Daubert and Danner (1996)
000075525
NITROMETHANE
308.15
7.3

652.15
Daubert and Danner (1996)
000075569
PROPYLENE OXIDE
235.93
2.1
21.5
738.15
Daubert and Danner (1996)
000075616
DIBROMODIFLUOROMETHANE
NF
NF
NF

ARTI (1997)
000075638
BROMOTRIFLUOROMETHANE
NF
NF
NF

ARTI (1997)
000075649
T-BUTYLAMINE
264.15
1.7
8.9

Daubert and Danner (1996)
000075650
T-BUTANOL
284.26
2.4
8.0
751.00
Daubert and Danner (1996)
000075683
1 -CHLORO-1,1 -DIFLUOROETHANE

6.2
17.9
905
Daubert and Danner (1996)
000075694
TRICHLOROFLUOROMETHANE
NF
NF
NF
>750
ARTI (1997)
000075718
DICHLORODIFLUOROMETHANE
NF
NF
NF
>750
ARTI (1997)
000075729
CHLOROTRIFLUOROMETHANE
NF
NF
NF

ARTI (1997)
000075730
TETRAFLUOROMETHANE
NF
NF
NF

ARTI (1997)
000075763
TETRAMETHYLSILANE
246.15
1.5

450.00
Daubert and Danner (1996)
000075774
CHLOROTRIMETHYLS1LANE
245.00
1.8

668.15
Daubert and Danner (1996)
000075785
DICHLORODIMETHYLSILANE
257.15
3.4


Daubert and Danner (1996)
000075796
METHYLTRICHLOROSILANE
258.15
5.1


Daubert and Danner (1996)
124
-------
Appendix	A. (continued)
CAS
Number	Name
000075832	2,2-DIMETHYLBUTANE
000075854	2-METH YL-2-BUT ANOL
000075865	ACETONE CYANOHYDRIN
000075887	1,1,1 -TRIFLUORO-2-CHLOROETHANE
000076017	PENTACHLOROETHANE
000076028	TRICHLORACETYLCHLORIDE
000076119	1,1,1,2-TETRACHLORO-2,2-
DIFLUOROETHANE
000076120	1,1,2,2,-
TETRACHLORODIFLUOROETHANE
000076131	1,1,2-TRICHLOROTRIFLUOROETHANE
000076142	1,2-
DICHLOROTETRAFLUOROETHANE
000076153	CHLOROPENTAFLUOROETHANE
000076164	HEXAFLUOROETHANE
000076197	OCTAFLUOROPROPANE
000076222	CAMPHOR
000077474	HEXACHLOROCYCLOPENTAD1ENE
000077736	DIC Y CLOPENT ADIENE
000078002	TETRAETHYL LEAD
000078400	TRIETHYL PHOSPHATE
000078591	1SOPHORONE
000078784	ISOPENTANE
000078795	2-METHYL-1.3-BUTADIENE
000078831	ISOBUTYL ALCOHOL
000078842	1SOBUTYRALDEHYDE
000078875	1,2-DICHLOROPROPANE
000078886	2,3-DICHLOROPROPENE
000078922	2-BUTANOL
000078933	2-BUTANONE
Flash
Point
CQ
LFL
(%)
UFL
(%)
Autoig
Temp
CO
Reference
255.37
1.2
7.0
698.15
Daubert and Danner (1996)
313.71
1.2
9.0
710.37
Daubert and Danner (1996)
347.04
2.2
12.0
960.93
Daubert and Danner (1996)
NF
NF
NF

ARTI (1997)
NF
NF
NF

Daubert and Danner (1996)

NF
NF

Daubert and Danner (1996)
NF
NF
NF

ARTI (1997)
NF
NF
NF

ARTI (1997)
NF
NF
NF
953
ARTI (1997)
NF
NF
NF
>750
ARTI (1997)
NF
NF
NF
1153
ARTI (1997)
NF
NF
NF
1153
ARTI (1997)
NF
NF
NF

ARTI (1997)
338.70
0.6
3.5
739.26
Daubert and Danner (1996)
NF
NF
NF

Daubert and Danner (1996)
305.37
1.0

783.15
Daubert and Danner (1996)
366.15
1.8

400.15
Daubert and Danner (1996)
372.00
1.7
10.0
728.00
Daubert and Danner (1996)
357.15
0.8
3.8
733.15
Daubert and Danner (1996)

1.4
7.6
693.15
Daubert and Danner (1996)
219.26
2.0
9.0
493.15
Daubert and Danner (1996)
301.00
1.7
10.9
681.15
Daubert and Danner (1996)
265.93
1.6
10.6
527.59
Daubert and Danner (1996)
286.15
3.4
14.5
830
Daubert and Danner (1996)
283.15
2.6
7.8

Daubert and Danner (1996)
297.00
1.7
9.8
679.00
Daubert and Danner (1996)
267.04
1.8
10.0
788.71
Daubert and Danner (1996)
125
-------
Appendix A. (continued)
Flash
CAS	Point
Number	Name	(°C)
000078999	1,1-DICHLOROPROPANE	294.15
000079005	1,1,2-TRICHLOROETHANE
000079016	TRICHLOROETHENE
000079049	CHLOROACETYLCHLORIDE	NF
000079094	PROPIONIC ACID	328.00
000079107	ACRYLIC ACID	323.71
000079118	CHLOROACETIC ACID	NF
000079209	METHYL ACETATE	263.15
000079221	METHYL CHLOROFORMATE	285.15
000079243	NITROETHANE	301.00
000079298	2,3-DIMETHYLBUTANE	244.26
000079312	ISOBUTYRIC ACID	349.82
000079345	1,1,2,2-TETRACHLOROETHANE	NF
000079389	CHLOROTRIFLU OROETHYLENE
000079414	METHACRYLIC ACID	350.37
000079469	2-NITROPROPANE	297.15
000080159	CUMENE HYDROPEROXIDE	322.04
000080626	METHYL METHACRYLATE	284.15
000084662	DIETHYL PHTHALATE	434.15
000084695	DI-ISOBUTYLPHTHALATE	434.15
000084742	DIBUTYL PHTHALATE	430.15
000085449	PHTHALIC ANHYDRIDE	424.82
000088722	2-NITROTOLUENE	379.00
000091203	NAPHTHALENE	352.00
000091667	N,N-DIETHYLANILINE	358.15
000092513	DIC Y CLOHEXYL	347.15
000092524	BIPHENYL	386.00
.000095476	O-XYLENE	290.00
000095487	O-CRESOL	354.26
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
3.1
6
14.5
15.5
830
Daubert and Danner (1996)
ARTI (1997)
8.0
10.5
683.15
Daubert and Danner (1996)
NF
NF
NF
Daubert and Danner (1996)
2.9
14.8
748.15
Daubert and Danner (1996)
2.4

711.15
Daubert and Danner (1996)
NF
NF
NF
Daubert and Danner (1996)
3.1
16.0
775
Daubert and Danner (1996)
6.7

777.15
Daubert and Danner (1996)
3.4

633.15
Daubert and Danner (1996)
1.2
7.0
693.15
Daubert and Danner (1996)
2.0
9.2
774.82
Daubert and Danner (1996)
NF
NF

ARTI (1997)
8.4
38.7

Daubert and Danner (1996)
1.6
8.7

Daubert and Danner (1996)
2.6
11.0
701
Daubert and Danner (1996)
0.9
6.5
422.04
Daubert and Danner (1996)
2.1
12.5

Daubert and Danner (1996)
0.7

730.15
Daubert and Danner (1996)
0.4

705.15
Daubert and Danner (1996)
0.5

675.15
Daubert and Danner (1996)
1.7
10.5
857.04
Daubert and Danner (1996)
2.2

578.15
Daubert and Danner (1996)
0.9
5.9
799.15
Daubert and Danner (1996)
1.6
9.5
605.15
Daubert and Danner (1996)
0.7
5.1
518.15
Daubert and Danner (1996)
0.6
5.8
813.15
Daubert and Danner (1996)
0.9
6.7
736.15
Daubert and Danner (1996)
1.4

872.04
Daubert and Danner (1996)
126
-------
Appendix	A. (continued)
CAS
Number	Name
000095501	1,2-DICHLOROBENZENE
000095545	1,2-BENZENEDIAMINE
000095636	1,2,4-TRIMETHYLBENZENE
000095761	3,4-DICHLORO ANILINE
000096140	3-METHYLPENTANE
000096184	1,2,3-TRICHLOROPROPANE
000096220	3-PENTANONE
000096333	METHYL ACRYLATE
000096377	METHYLCYCLOPENTANE
000096480	GAMMA-BUTYROLACTONE
000097007	2,4-DINITROCHLOROBENZENE
000097632	ETHYL METHACRYLATE
000097643	ETHYL LACTATE
000097858	ISOBUTYLISOBUTYRATE
000097881	METHACRYLIC ACID, N-BUTYL
ESTER
000097994	TETRAHYDROFURFURYL ALCOHOL
000098000	2-HYDROXYMETHYLFURAN
000098011	FUFURAL
000098066	T-BUTYLBENZENE
000098828	CUMENE
000098839	ALPHA-METHYLSTYRENE
000098884	BENZOYL CHLORIDE
000098953	NITROBENZENE
000099092	3-NITROANILINE
000099876	P-CYMENE
000099990	P-NITROTOLUENE
000100378	2-DIETHYLAMINOETHANOL
000100414	ETHYLBENZENE
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
339.00
2.2
9.2
921.00
Daubert and Danner (1996)
429.15
1.5


Daubert and Danner (1996)
318.65
0.9

788.15
Daubert and Danner (1996)
439.00
2.8
7.2
538.15
Daubert and Danner (1996)

1.2
7.7
551.15
Daubert and Danner (1996)
347.04
3.2
12.6
577.04
Daubert and Danner (1996)
285.93
1.5
8.0
725.37
Daubert and Danner (1996)
269.82
2.8
25.0
741.15
Daubert and Danner (1996)
245.93
1.2
8.4
602.04
Daubert and Danner (1996)
371.48
2.0


Daubert and Danner (1996)
467.00
2.0
22.0
705.15
Daubert and Danner (1996)
294.15
1.8


Daubert and Danner (1996)
319.15
1.5

673.15
Daubert and Danner (1996)
311.15
1.0
7.6
705.15
Daubert and Danner (1996)
325.37
2.0
8.0

Daubert and Danner (1996)
343.15
1.5
9.7
553.15
Daubert and Danner (1996)
338.15
1.8
16.3
663.15
Daubert and Danner (1996)
333.15
2.1
19.3
588.71
Daubert and Danner (1996)
333.15
0.7
5.7
723.15
Daubert and Danner (1996)
304.15
0.9
6.5
697.00
Daubert and Danner (1996)
327.04
1.9
6.1
847.59
Daubert and Danner (1996)
345.37
1.2
4.9
358.15
Daubert and Danner (1996)
361.00
1.8

755.00
Daubert and Danner (1996)
472.15
1.7


Daubert and Danner (1996)
320.00
0.7
5.6
708.15
Daubert and Danner (1996)
379.00
1.6

663.15
Daubert and Danner (1996)
52.00
6.7
11.7

SRC (1993)
288.15
1.0
6.7
703.15
Daubert and Danner (1996)
127
-------
Appendix A. (continued)
Flash
CAS	Point LFL
Number Name	(°C) (%)
000100425	STYRENE	305.37	1.1
000100447	ALPHA-CHLOROTOLUENE	333.15	1.1
000100801	M-METHYLSTYRENE	324.15	0.7
000101848	DIPHENYLETHER	388.15	0.8
000102363	1,2-DICHLORO-4-	415.15	1.6
ISOCYANATOBENZENE
000102716	TRIETHANOLAMINE	179.00	1.20
000102761	TRIACETIN	411.00	1.0
000103093	2-ETHYLHEXYLACET ATE	344.15	0.8
000103117	2-ETHYLHEXYL ACRYLATE	344.15	0.7
000103651	N-PROPYLBENZENE	303.15	0.9
000103695	N-ETHYLANILINE	358.15	1.6
000104518	N-BUTYLBENZENE	323.15	0.8
000104767	2-ETHYL-l-HEXANOL	346.48	0.9
000105055	P-DIETHYLBENZENE	329.15	0.8
000105306	2-METHYL-1 -PENTANOL	324.26	1.0
000105373	ETHYL PROPIONATE	285.00	1.9
000105464	S-BUTYLACETATE	255.15	1.3
000105577	1,1 -DIETHOXYETHANE	252.59	1.6
000105599	N-METHYLDIETHANOLAMINE	399.82	1.4
000105602	CAPROLACTAM	412.00	1.4
000106310	BUTYRIC ANHYDRIDE	355.37	1.1
000106423	P-XYLENE	298.15	1.1
000106445	P-CRESOL	367.59	1.1
000106638	ISOBUTYL ACRYLATE	304.26	2.0
000106887	1,2-BUTYLENEOXIDE	258.15	1.5
000106898	1 -CHLORO-2,3-EPOXYPROPANE	304.26	3.8
000106934	1,2-DIB ROMOETHANE	NF	NF
000106978	N-BUTANE	1.5
UFL
(%)
6.1
11.0
1.5
8.6
Autoig
Temp
(°C)
763.15
858.15
762.15
891.15
8.1
8.2
6.0
9.5
5.8
9.7
6.1
7.7
11.0
7.5
10.4
8.0
7.6
7.0
8.0
18.3
21.0
NF
9.0
706.00
530.93
729.15
752.15
683.15
560.93
703.15
750.00
503.15
648.15
552.59
801.15
832.04
613.15
712.04
689.15
NF
561.00
Reference
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
SRC (1993)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996).
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
996)
128
-------
Appendix A. (continued)
CAS
Number	Name
000106989	1-BUTENE
000106990	1,3-BUTADIENE
000107028	ACROLEIN
000107051	3-CHLOROPROPYLENE
000107062	1,2-DICHLOROETHANE
000107073	2-CHLOROETHANOL
000107108	PROPYLAMINE
000107119	ALL YL AMINE
000107120	PROPIONITRILE
000107131	ACRYLONITRILE
000107153	1,2-DIAMINOETHANE
000107186	ALL YL ALCOHOL
000107197	PROPARGYL ALCOHOL
000107211	ETHYLENE GLYCOL
000107255	METHYL VINYLETHER
000107313	METHYLFORMATE
000107460	HEXAMETHYLDISILOXANE
000107517	OCTAMETHYLTRISILOXANE
000107835	2-METHYLPENTANE
000107879	2-PENTANONE
000107926	BUTYRIC ACID
000107937	CROTONIC ACID
000107982	1 -METHOXY-2-PROPANOL
000108032	1 -NITROPROP ANE
000108054	VINYL ACETATE
000108101	4-METHYL-2-PENTANONE
000108112	4-METH YL-2-PENT ANOL
000108189	DIISOPROPYLAMINE
000108203	DI-ISOPROPYL ETHER
Flash
Point
(°C)
247.15
241.15
286.00
313.71
261.00
244.26
275.37
273.15
307.04
294.26
309.26
384.26
217.15
254.26
271.15
238.00
280.37
345.00
367.59
32.00
306.15
265.00
288.71
314.26
266.15
245.00
LFL
(%)
2.0
2.8
2.9
6.2
4.9
2.0
2.2
3.1
2.4
4.2
2.5
2.4
3.2
2.6
5.9
1.3
0.9
1.2
1.5
2.2
2.2
3
2.2
2.6
1.4
1.0
0.8
1.4
UFL
(%)
9.3
11.5
31.0
11.3
16.0
15.9
10.4
22.0
17.3
14.4
18.0
39.0
20.0
18.6
13.8
7.0
8.2
13.4
15.1
12
13.4
7.5
5.5
7.1
21.0
Autoig
Temp
(°Q
657.04
702.04
507.04
758.15
686
698.15
591.00
647.04
754.26
658.15
651.48
388.15
673.15
560.15
729.26
614.15
623.15
579.26
725.15
723.15
669.26
694.15
700.00
732.04
588.71
716.00
Reference
Daubert and Dannei
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Moore et al. (1995)
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
129
-------
Appendix A. (continued)
Flash	Autoig
CAS	Point LFL UFL	Temp
Number Name	(°C) (%) (%)	(°C)
000108214	ISOPROPYL ACETATE	275.00	1.8	7.2	733.15
000108247	ACETIC ANHYDRIDE	327.00	2.9	10.3	607.15
000108316 MALEIC ANHYDRIDE	375.15	1.4	7.1	750.00
000108383	M-XYLENE	298.15	1.1	7.0	738.15
000108394	M-CRESOL	367.59	1.1	832.04
000108463	RESORCINOL	400.00	1.4	9.8	880.00
000108576	M-DIETHENYLBENZENE	0.3
000108656	PROPYLENE GLYCOL ME ETHER	316.00	1.3	13.1	627.15
ACETATE
000108678	1,3,5-TRIMETHYLBENZENE	317.55	0.9	7.3	823.15
000108838	2,6-DIMETH YL-4-HEPT ANONE	322.15	0.8	6.2	669.15
000108872	1 -METHYLCYCLOHEXANE	269.26	1.2	558.15
000108883	TOLUENE	277.15	1.2	7.1	753.15
000108907	CHLOROBENZENE	305.37	1.3	7.1	910.93
000108930	CYCLOHEXANOL	340.93	1.2	573.15
000108941	CYCLOHEXANONE	317.04	1.0	693.15
000108952	PHENOL	352.59	1.5	988.15
000109433	DIBUTYL SEBACATE	451.15	0.4	638.15
000109604	N-PROPYL ACETATE	288.00	2.0	8.0	723.00
000109659	1 -BROMOBUT ANE	291.15	2.6	6.6	538.15
000109660	N-PENTANE	233.15	1.3	8.0	516.00
000109671	1-PENTENE	255.37	1.5	8.7	545.93
000109693	1 -CHLOROBUT ANE	245.00	1.8	10.1	513.15
000109739	N-BUTYLAMINE	261.00	1.7	9.8	585.00
000109740	BUTYRONITRILE	299.26	1.6	774.82
000109784	ETHYLENE CYANOHYDRIN	402.59	2.3	12.1	767.59
000109864	2-METHOXYETHANOL	312.00	1.8	14.0	558.15
000109875	DIMETHOXYMETHANE	255.37	1.6	17.6	510.35
000109897	DIETHYLAMINE	247.04	1.8	10.1	585.15
Reference
Daubert and Dannei
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
130
-------
Appendix A. (continued)
Flash	Autoig
CAS	Point	LFL	UFL	Temp
Number Name	(°C) (%)	(%)	(°C)
000109922	ETHYL VINYL ETHER	<228	1.7	28.0	474.82
000109933	DIVINYL ETHER	226.15	1.7	27.0	633.15
000109944	ETHYL FORMATE	269.15	2.7	13.5	728.15
000109977	PYRROLE	312.04	2.0	12.0
000109999	TETRAHYDROFURAN	258.71	2.0	11.8	594.26
000110009	FURAN	237.59	2.3	14.3
000110010	TETRAHYDROTHIOPHENE	291.48	1.5	9.0
000110123	5-METHYL-2-HEXANONE	309.15	1.0	8.2	464.15
000110167	MALEIC ACID	NF	NF	NF	NF
000110190	SEC-BUTYLACETATE	291.00	1.3	10.5	696.00
000110430	2-HEPTANONE	312.15	1.1	7.9	666.15
000110543	N-HEXANE	251.50	1.1	7.7	498.00
000110576	1,4-DICHLORO-2-BUTENE(TRANS)	326.15	1.5	4.0
000110805	2-ETHOXYETHANOL	316.00	1.7	15.6	508.15
000110827	CYCLOHEXANE	253.15	1.3	8.0	533.15
000110838	CYCLOHEXENE	266.48	1.2	583.15
000110861	PYRIDINE	293.15	1.8	12.4	755.37
000110883	1,3,5-TRIOXANE	318.15	3.6	29.0	687
000110918	MORPHOLINE	310.93	1.8	10.8	583.15
000111159	ETHOXYETHYLACETATE	327.59	1.7	12.7	652.59
000111400	DIETHYLENETRI AMINE	372.00	1.0	10.0	631.00
000111411	2-(2-AMINOETHYLAMINO)ETHANOL 375.00	1.0	8.0	641.00
000111466	DIETHYLENE GLYCOL	116.00	1.7	10.6
000111499	HEXAMETHYLENEIMINE	310.37	1.6	2.3	603.15
000111557	ETHYLENE GLYCOL DIACETATE	361.15	1.6	8.4	755.15
000111659	OCTANE	286.00	0.8	6.5	479.00
000111660	1-OCTENE	294.26	0.9	503.15
000111693	ADIPONITRILE	366.15	1.7	5.0	823.15
000111762	2-BUTOXYETHANOL	333.50	1.1	12.7	511.15
Reference
Daubert and Danne:
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
SRC (1993)
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
Daubert and Danne
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
131
-------
Appendix A. (continued)
Flash	Autoig
CAS	Point	LFL	UFL	Temp
Number Name	(°C)	(%)	(%)	(°C)
000111773	DIETHYLENE GLYCOL	357.04	1.4	22.7	466.00
MONOMETHYL ETHER
000111842	N-NONANE	304.00	0.7	5.6	478.00
000111864	N-OCTYL AMINE	333.00	0.7	9.6
000111900	DIETHYLENE GLYCOL MONOETHYL 356.45	1.2	16.0	477.15
ETHER
000111922	DIBUTYLAMINE	320.15	1.1
000112152	CARBITOL ACETATE	380.00	1.0	19.4	633.15
000112209	N-NONYL AMINE	335.15	0.6	8.6
000112276	TRIETHYLENE GLYCOL	450.00	0.9	9.2	644.00
000112345	DIETHYLENE GLYCOL MONO-N-	351.00	0.9	24.6	478.00
BUTYL ETHER
000112403	DODECANE	347.00	0.6	476.00
000112572	TETRAETHYLENEPENT AMINE	436.00	4.6	573.15
000112607	TETRAETHYLENE GLYCOL	182.00	1
000115071	PROPENE	165.37	2.0	11.0	728.15
000115106	DIMETHYL ETHER	232.00	3.3	27.3	623.15
000115117	ISOBUTENE	1.8	8.8	738.15
000115253	PERFLUOROCYCLOBUTANE	NF	NF	NF
000116143	TETRAFLUOROETHYLENE	11.0	60.0	473.15
000116154	HEXAFLUOROPROPENE	NF	NF	NF	NF
000117817	BIS(2-ETHYLHEXYL)PHTHALATE	489.00	0.3	664.15
000119642	TETRALIN	344.00	0.8	5.0	657.00
000120127	ANTHRACENE	394.26	0.6	813.15
000120616	DIMETHYLTEREPHTHALATE	429.15	0.0	843.15
000120821	1,2,4-TRICHLOROBENZENE	378.71	2.5	6.6	844.26
000121448	TRIETHYLAMINE	260.95	1.2	8.0
000123057	2-ETHYLHEXANAL	317.15	0.9	7.2	463.15
000123386	PROPIONALDEHYDE	243.15	2.6	16.1	480.37
000123422	4-H YDROXY-4-METH YL-2-	320.00	1.8	6.9	876.48
PENTANONE
Reference
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
SRC (1993)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
ARTI (1997)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
Daubert and Danner (1996)
132
-------
Appendix A. (continued)
CAS
Number
Name
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
000123513
ISOPENTANOL
315.93
1.2
9.0
623.15
Daubert and Danner (1996)
000123546
2,4-PENTANEDIONE
307.04
2.4
11.6
613.15
Daubert and Danner (1996)
000123626
PROPIONIC ANHYDRIDE
336.00
1.5
11.9
558.00
Daubert and Danner (1996)
000123637
PARALDEHYDE
308.71
1.3

510.93
Daubert and Danner (1996)
000123728
BUTYRALDEHYDE
266.48
2.5
12.5
503.15
Daubert and Danner (1996)
000123739
TRANS-CROTONALDEHYDE
285.93
2.1
15.5
505.37
Daubert and Danner (1996)
000123864
N-BUTYL ACETATE
295.00
1.7
7.6
694.00
Daubert and Danner (1996)
000123911
1,4-DIOXANE
285.37
2.0
22.0
453.15
Daubert and Danner (1996)
000123922
ISOAMYL ACETATE
298.15
1.0
7.5
633.15
Daubert and Danner (1996)
000123966
2-OCTANOL
333.15
0.8


Daubert and Danner (1996)
000124027
N-2-PROPENYL-2-PROPEN-1 -AMINE
284.15

10.8

Daubert and Danner (1996)
000124049
HEXANEDIOIC ACID
436.00
1.6

693.15
Daubert and Danner (1996)
000124094
HEXAMETHYLENE DIAMINE
366.48
0.7
6.3

Daubert and Danner (1996)
000124118
ISONONENE

0.8


Daubert and Danner (1996)
000124174
DIETHYLENE GLYCOL MONOBUTYL
110.00
0.8


SRC (1993)
ETHER ACETATE
000124185
N-DECANE
319.00
0.7
5.4
474.00
Daubert and Danner (1996)
000124403
DIMETHYLAMINE
223.15
2.8
14.4
673.15
Daubert and Danner (1996)
000126307
2,2-DIMETHYL-1,3 -PROPANEDIOL
402.00
1.4
22.0
672.00
Daubert and Danner (1996)
000126998
CHLOROPRENE
253.15
2.1
20.0
593.15
Daubert and Danner (1996)
000127184
TETRACHLOROETHENE
NF
NF
NF
NF
Daubert and Danner (1996)
000127195
N,N'-DIMETHYLACET AMIDE
336.15
1.8
13.8
627.15
Daubert and Danner (1996)
000131113
DIMETHYL PHTHALATE
419.00
0.9

829.00
Daubert and Danner (1996)
000135988
SEC-BUTYLBENZENE
325.00
0.8
6.9
691.00
Daubert and Danner (1996)
000137326
2-METHYL-1 -BUTANOL
323.15
1.4
9.0
658.15
Daubert and Danner (1996)
000138227
LACTIC ACID, BUTYL ESTER
71.00
1.0
7.9

SRC (1993)
000140885
ETHYL ACRYLATE
288.71
1.8
9.5
655.93
Daubert and Danner (1996)
000141322
BUTYL ACRYLATE
312.04
1.5
9.9
565.93
Daubert and Danner (1996)
000141537
SODIUM FORMATE
NF
NF
NF
NF
Daubert and Danner (1996)
133
-------
Appendix A. (continued)





CAS
Number
Name
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
CC)
Reference
000141628
DECAMETHYLTETRASILOXANE

0.9
3.6
623.15
Moore etal. (1995)
000141786
ETHYL ACETATE
269.00
2.2
11.4
700.00
Daubert and Danner (1996)
000141797
MESITYL OXIDE
301.48
1.3
8.8
617.59
Daubert and Danner (1996)
000141979
ACETOACETIC ESTER
330.37
1.4
9.5
568.15
Daubert and Danner (1996)
000142289
1,3-DICHLOROPROPANE
294.15
3.4
14.5

Daubert and Danner (1996)
000142290
CYCLOPENTENE
244.26
1.5

668.15
Daubert and Danner (1996)
000142825
N-HEPTANE
269.00
1.0
7.0
477.00
Daubert and Danner (1996)
000142961
DI-N-BUTYL ETHER
298.15
1.5
7.6
467.59
Daubert and Danner (1996)
000143088
1-NONANOL
347.00
0.8
6.1

Daubert and Danner (1996)
000151564
AZIRIDINE
262.04
3.3
54.8
593.15
Daubert and Danner (1996)
000151677
HALOTHANE
NF
NF
NF

ARTI (1997)
000156592
1,2-DICHLOROETHENE (CIS)
277.00
9.7
12.8

Daubert and Danner (1996)
000156605
1,2-DICHLOROETHENE (TRANS)
275
5.6
12.8
733.00
Daubert and Danner (1996)
000287230
CYCLOBUTANE

1.7


Daubert and Danner (1996)
000287923
CYCLOPENTANE
233.15
1.4
9.4
634.15
Daubert and Danner (1996)
000302012
HYDRAZINE
310.93
4.7
99.9
543.15
Daubert and Danner (1996)
000306832
1,1,1 -TRIFLUORO-2,2-
DICHLOROETHANE
NF
NF
NF
1003
ARTI (1997)
000344070
BENZENE, CHLOROPENTAFLUORO-
NF
NF
NF

Tapscottetal. (1995)
000353366
FLUOROETHANE

3.8
18.0

ARTI (1997)
000353593
BROMOCHLORODIFLUOROMETHAN
E
NF
NF
NF

ARTI (1997)
000354041
1,2-DIBROMO-1,1,2-
TRIFLUOROETHANE
NF



ARTI (1997)
000354234
1,2-DICHLORO-1,1,2-
TRIFLUOROETHANE
NF
NF
NF
NF
Daubert and Danner (1996)
000354256
l-CHLORO-1,1,2,2-
TETRAFLUOROETHANE
NF
NF
NF

ARTI (1997)
000354336
1,1,1,2,2-PENT AFLUOROETHANE
NF
NF
NF
1006
ARTI (1997)
000354643
PENT AFLU OROIODOETHANE
NF
NF
NF

Tapscott et al. (1995)
000355259
DECAFLUOROBUTANE
NF
NF
NF
NF
Daubert and Danner (1996)
134
-------
Appendix A. (continued)
CAS
Number	Name
0003 59159 METHYL DIFLUOROMETHYL ETHER
000359353	1,1,2,2-TETRAFLUOROETHANE
000360894 OCTAFLUORO-2-BUTENE
000374072	l,l-DICHLORO-l,2,2,2-
TETRAFLUOROETHANE
000420462 1,1,1 -TRIFLUOROETHANE
000423392	BUTANE, 1,1,1,2,2,3,3,4,4-
NONAFLUORO-4-IODO-
000430660	1,1,2-TRIFLUOROETHANE
000431312	1,1,1,2,3 -PENTAFLUOROPROPANE
000431630	1,1,1,2,3,3-HEXAFLUOROPROPANE
000431890	1,1,1,2,3,3,3-HEPTAFLUOROPROPANE
000460195	CYANOGEN
000460435	2-(METHOXY)-1,1,1 -
TRIFLUOROETHANE
000460731	1,1,1,3,3-PENTAFLUOROPROPANE
000463490	1,2-PROPADlENE
000463581	CARBONYL SULFIDE
000463821	2,2-DIMETHYLPROPANE
000493 016	C1S-BICYCLO[4.4.0]DECANE
000493027	TRANS-BICYCLO[4.4.0]DECANE
000503300	TRIMETHYLENEOXIDE
000504632	1,3-PROPANEDlOL
000513359	2-METHYL-2-BUTENE
000526738	1,2,3-TRlMETH YLBENZENE
000538932	ISOBUTYLBENZENE
000540476	METHOXYCYCLOPROPANE
000540545	1-CHLOROPROPANE
000540670	ETHYL METHYL ETHER
000540841	2,2,4-TRIMETHYLPENTANE
Flash
Point
(•Q
LFL
(%)
UFL
(%)
Autoig
Temp
<°C)
Reference
ARTI (1997)
NF
NF
NF
903
ARTI (1997)
NF
NF
NF
NF
Daubert and Danner (1996)
NF
NF
NF
NF
Daubert and Danner (1996)

9.2
18.4

Daubert and Danner (1996)
NF
NF
NF

Tapscottetal. (1995)

5.8
24.4

ARTI (1997)

9.6
10.7

ARTI (1997)
NF
NF
NF

ARTI (1997)
NF
NF
NF

ARTI (1997)

6.0
32.0

Daubert and Danner (1996)
257.15
4.5
14.3

ARTI (1997)
NF-T
8,9
2,1
11.2

ARTI (1997)
Daubert and Danner (1996)

12.0
29.0

Daubert and Danner (1996)

1.4
7.5
723.15
Daubert and Danner (1996)
330.95
0.7
4.9
523.15
Daubert and Danner (1996)
330.95
0.7
4.9
523.15
Daubert and Danner (1996)

2.8
37.0

Daubert and Danner (1996)

2.6

651
Daubert and Danner (1996)
266.48
1.4


Daubert and Danner (1996)
317,15
0.8
6.6
743.15
Daubert and Danner (1996)
325.15
0.8
2.0
6.0
701.00
Daubert and Danner (1996)
Merck (1996)
<255
2.6
11.1
793.15
Daubert and Danner (1996)
236.00
2.0
10.1
463.15
Daubert and Danner (1996)
260.93
1.1
6.0
690.93
Daubert and Danner (1996)
135
-------
Appendix A. (continued)
CAS
Number	Name
000542109 1,1 -ETHANEDIOL DIACETATE
000542552 ISOBUTYL FORMATE
000543599	1 -CHLOROPENT ANE
000547648	LACTIC ACID, METHYL ESTER
000554121	METHYL PROPIONATE
000556672	OCT AMETH YLTETRASILOXANE
000557175	METHYL PROPYL ETHER
000557982	2-CHLOROPROPENE
000558305	2,2-DIMETHYLOXIRANE
000560214	2,3,3-TRIMETHYLPENTANE
000562492	3,3-DIMETHYLPENTANE
000563451	3-METH YL-1 -BUTENE
000563462	2-METHYL-l-BUTENE
000564023	2,2,3-TRIMETHYLPENTANE
000565593	2,3 -DIMETH YLPENT ANE
000565753	2,3,4-TRIMETHYLPENTANE
000576261	2,6-DIMETHYLPHENOL
000584021	3-PENTANOL
000584849	2,4-TOLUENEDIISOCYANATE
000589344	3-METHYLHEXANE
000589537	4-METHYLHEPT ANE'
000589811	3-METHYLHEPTANE
000590181	CIS-2-BUTENE
000590192	1,2-BUTADIENE
000590670	1 -METHYLCYCLOHEXANOL
000591764	2-METHYLHEXANE
000591786	2-HEXANONE
000592278	2-METHYLHEPT ANE
000592416	1-HEXENE
Flash
Point
CQ
284.15
55.00
271.00
330.15
239.15
258.15
266.48
346.15
313.71
127.00
269.26
279.15
338.15
<255
298.15
277.15
LFL
(%)
1.7
1.6
1.1
2.5
0.8
2.0
4.5
1.5
1.0
1.0
1.5
1.4
1.0
1.1
1.0
1.4
1.2
0.9
1.0
0.9
0.9
1.6
2.0
1.0
1.0
1.2
0.9
1.2
UFL
(%)
8.5
8.0
8.6
3.6
13.0
7.4
14.8
16.0
18.3
7.0
9.1
6.7
9.0
9.5
7.0
9.7
12.0
6.0
8.0
9.2
Autoig
Temp
CC)
593.15
533.15
742.00
673.00
712.15
703.15
638.15
703.15
610.37
872.00
708.15
553.15
598.15
568.15
553.15
697.04
526.15
Reference
Daubert and Danner
Daubert and Danner
Daubert and Danner
SRC (1993)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
SRC (1993)
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
Daubert and Danner
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
1996)
136
-------
Appendix A. (continued)
CAS
Number	Name
000592450	1,4-HEXADIENE
000592767	1-HEPTENE
000592847	N-BUTYLFORMATE
000617787	3 -ETH YLPENT ANE
000622979	P-METHYLSTYRENE
000624646	TRANS-2-BUTENE
000624726	1,2-DIFLUOROETHANE
000624839	METHYLISOCYANATE
000627203	CIS-2-PENTENE
000628320	ETHYL PROPYL ETHER
000628637	N-AMYL ACETATE
000629594	TETRADECANE
000630080	CARBON MONOXIDE
000638493	FORMIC ACID, PENTYL ESTER
000646048	TRANS-2-PENTENE
000661972	1,3-DICHLORO-l, 1,2,2,3,3-
HEXAFLUOROPROPANE
000674760	TRANS-4-METHYL-2-PENTENE
000677690	PROPANE, 1,1,1,2,3,3,3-
HEPTAFLUORO-2-IODO-
000679867	1,1,2,2,3-PENTAFLUOROPROPANE
000680319	HEXAMETHYLPHOSPHORAMIDE
000691383	4-METHYL-2-PENTENE (CIS)
000754347	HEPTAFLUORO-1 -IODOPROPANE
000763699	3-ETHOXYPROPANOIC ACID, ETHYL
ESTER
000811972	1,1,1,2-TETRAFLUOROETHANE
000814788	3-METHYL-3-BUTEN-2-ONE
000821556	2-NONANONE
000872059	1-DECENE
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
248.15
2.0
6.1

Daubert and Danner (1996)
273.15
1.0

563.15
Daubert and Danner (1996)
290.93
1.7
8.0
595.37
Daubert and Danner (1996)

1.0
7.0

Daubert and Danner (1996)
319.00
1.9
6.1
848.15
Daubert and Danner (1996)

1.8
9.7
597.04
Daubert and Danner (1996)

3.6
21.8

ARTI (1997)
266.15
5.3
26.0
807.15
Daubert and Danner (1996)
227.59
1.4


Daubert and Danner (1996)

1.7
9.0

Daubert and Danner (1996)
296.15
1.1
7.5
633.15
Daubert and Danner (1996)
373.15
0.5

473.00
Daubert and Danner (1996)

12.5
74.0
8.1
882.04
Daubert and Danner (1996)
Daubert and Danner (1996)

1.4


Daubert and Danner (1996)
NF
NF
1.2
NF

ARTI (1997)
Daubert and Danner (1996)
NF
NF
NF

Tapscott et al. (1995)
0
8.3
12.8

ARTI (1997)
378.71
NF
1.2


Daubert and Danner (1996)
Daubert and Danner (1996)
NF
NF
NF

Tapscott et al. (1995)
331.15
1.1

650.15
Daubert and Danner (1996)
NF
NF
NF
1016
ARTI (1997)
294.15
1.8
9.0

Daubert and Danner (1996)
337.15
0.9
5.9
633.15
Daubert and Danner (1996)
326.48
0.7

508.15
Daubert and Danner (1996)
137
-------
Appendix A. (continued)





CAS
Number
Name
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
000872504
N-METHYLPYRROLIDONE
368.71
2.2
12.2
619.15
Daubert and Danner (1996)
000931919
HEXAFLUOROCYCLOPROPANE
NF
NF
NF

ARTI (1997)
000999973
HEXAMETH YLD1SILIZ ANE
281.15
0.8
16.3

Daubert and Danner (1996)
001067205
3,3-DIETHYLPENTANE

0.7
5.7
563.15
Daubert and Danner (1996)
001070877
2,2,4,4-TETRAMETHYLPENT ANE

0.9


Daubert and Danner (1996)
001111746
DIMETHYL SILANE


83.0
503.15
Daubert and Danner (1996)
001186534
2,2,3,4-TETRAMETHYLPENTANE

0.9


Daubert and Danner (1996)
001198614
BENZENE, 1.3-DICHLORO-2,4,5,6-
TETRAFLUORO-
NF
NF
NF


001333740
HYDROGEN

4.0
75.0
673.15
Daubert and Danner (1996)
001511622
BROMODIFLUOROMETHANE
NF
NF
NF

ARTI (1997)
001634044
METHYL T-BUTYL ETHER
245.00
2.0
15.1
733.15
Daubert and Danner (1996)
001638262
1,1 -DIMETH YLC YCLOPENTANE

1.1


Daubert and Danner (1996)
001640897
ETHYLCYCLOPENTANE

1.1
6.7
533.15
Daubert and Danner (1996)
001678917
ETHYLCYCLOHEXANE
308.15
0.9
6.6
535.37
Daubert and Danner (1996)
001678928
N-PROPYLCYCLOHEXANE

0.9

521.15
Daubert and Danner (1996)
001678939
BUTYLCYCLOHEXANE

0.9

519.15
Daubert and Danner (1996)
001691174
BIS(DIFLUOROMETHYL) ETHER
NF
NF
NF

ARTI (1997)
001717006
1,1 -DICHLOROFLUOROETHANE
NF-T
5.8
17.7
598
ARTI (1997)
001759586
1,3-DIMETHYLCYCLOPENTANE
(TRANS)

1.1


Daubert and Danner (1996)
002040962
PROPYLCYCLOPENTANE

0.9

542.15
Daubert and Danner (1996)
002216333
3-METHYLOCT ANE

0.9

493.15
Daubert and Danner (1996)
002216344
4-METHYLOCT ANE

0.9

493.15
Daubert and Danner (1996)
002252848
1,1,1,2,2,3,3-HEPTAFLUOROPROPANE
NF
NF
NF

ARTI (1997)
002314978
TR1FLUOROIODOMETHANE
NF
NF
NF

ARTI (1997)
002532583
1,3-DIMETHYLCYCLOPENTANE (CIS)

1.1


Daubert and Danner (1996)
002807309
ETHYLENE GLYCOL MONOPROPYL
ETHER
322.15
1.3
15.8
508.15
Daubert and Danner (1996)
002837890
2-CHLORO-1,1,1,2-
TETRAFLUOROETHANE
NF
NF
NF
988
ARTI (1997)
138
-------
Appendix A. (continued)
CAS
Number	Name
003221612	2-METH YLOCT ANE
004109960	DICHLOROSILANE
0045 53 622	2-METH YLPENTANEDINITRILE
005989275	D-LIMONENE
007154792	2,2,3,3-TETRAMETHYLPENTANE
007664417	AMMONIA
007704349	SULFUR
007719097	THIONYL CHLORIDE
007727186	TRICHLOROOXO VANADIUM
007782414	FLUORINE
007783064	HYDROGEN SULFIDE
010025782	TRICHLOROSILANE
010025 873	PHOSPHOROUS OXYCHLORIDE
019287457	DIBORANE
025265718	DIPROPYLENE GLYCOL
026519915	1 -METHYL-1,3-CYCLOPENTADIENE
026761400	DIISODECYL PHTHALATE
026952216	ISOOCTYL ALCOHOL
028523866	SEVOFLUORANE
000111444	ETHANE, l,l'-OXYBIS[2-CHLORO-]
000407590	1,1,1,4,4,4-HEXAFLUOROBUTANE
000627134	N-PROPYL NITRATE
000106956	ALLYL BROMIDE
000626380	SEC-AMYL ACETATE
000097961	DIETHYL ACETALDEHYDE
000628375	DIETHYL PEROXIDE
000057147	1,1 -DIMETHYLH YDRAZINE
000505226	m-DIOXAN
004806615	ETHYL CYCLOBUTANE
Flash
Point
(°C)
LFL
(%)
UFL
(%)
Autoig
Temp
(°C)
Reference
296.00
0.9

493.15
Daubert and Danner (1996)
<255
4.0
96.0
331.15
Daubert and Danner (1996)
371.15
0.3
3.3

Daubert and Danner (1996)
318.15
0.7
6.1
510.00
Daubert and Danner (1996)

0.8
4.9
703.15
Daubert and Danner (1996)

16.0
25.0
924.26
Daubert and Danner (1996)
480.37
2.0

505.37
Daubert and Danner (1996)
NF
NF
NF
NF
Daubert and Danner (1996)
NF
NF
NF
NF
Daubert and Danner (1996)
NF
NF
NF
NF
Daubert and Danner (1996)

4.3
45.0
533.15
Daubert and Danner (1996)
245.37
1.2
90.5
377.59
Daubert and Danner (1996)
NF
NF
NF
NF
Daubert and Danner (1996)
183.15
0.9
98.0
325
Daubert and Danner (1996)
391.00
2.2


Daubert and Danner (1996)
322.04
1.3
7.6
719.00
Daubert and Danner (1996)
505.37
0.3

675.00
Daubert and Danner (1996)
82.00
0.9
11
5.7

SRC (1993)
Merck (1996)
55.00
2.7


SRC (1993)
NF-T
7.3
9.6

Knopeck et al. (1994)

2
100

Lewis (1994a)

4.4
7.3

Lewis (1994a)

1.1
7.5

Lewis (1994a)

1.2
7.7

Lewis (1994a)

2.3


Lewis (1994a)

2
95

Lewis (1994a)

2
22

Lewis (1994a)

1.2
7.7

Lewis (1994a)
139
-------
Appendix A. (continued)
CAS
Number	Name
000110496 ETHYLENE GLYCOL MONOMETHYL
ETHER ACETATE
000625581 ETHYL NITRATE
000108236 CARBONOCHLORIDIC ACID, 1-
METHYLETHYL ESTER
001712647 NITRIC ACID, 1 -METHYLETHYL
ESTER
000054115 PYRIDINE, 3 -(1 -METHYL-2-
PYRROLIDINYL)-, (S)-
019624227	PENTABORANE
007803512	PHOSPHINE
000075741	TETRAMETHYL LEAD
000594274	TETRAMETHYL STANNE
Flash
Point
(°C)
LFL
(%)
1.7
3.8
4
0.75
0.42
1.0
1.8
1.9
UFL
(%)
15
100
4.0
Autoig
Temp
(°C)
Reference
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
Lewis (1994a)
* Blank
**NF
***NF_T
= No data available
: Not flammable or does not support combustion
: Not flammable within the guidelines of the transportation industry (not
flammable below 100°C)
140
-------
Appendix B. Chemical Name and ASHRAE Standard Designation of Refrigerants Reference
CAS Registry
Number
ASHRAE
Designation
Chemical Name
000075694
CFC11
T richlorofluoromethane

CFC111
Pentachlorofluoroethane
000076120
CFC112
T etrachloro-1,2-dichloroethane
000076119
CFC112a
T etrachloro-1,1 -dichloroethane
000076131
CFC113
1,1,2-Trichloro- 1,2,2-trifluoroethane
000354585
CFC113a
1,1,1 -Trichloro-1,2,2-trifluoroethane
000076142
CFC114
1,2-Dichloro-1,1,2,2-tetrafluoroethane
000374072
CFC114a
1,1 -Dichloro-1,2,2,2-tetrafluoroethane
000076153
CFC115
Chloropentafluoroethane
000076164
CFC116
Perfluoroethane
000075718
CFC12
Dichlorodifluoromethane
000075729
CFC13
Chlorotrifluoromethane
000075434
CFC21
Dichlorofluoromethane

CFC211
Heptachlorofluoropropane

CFC217
Chloroheptafluoropropane
000075456
CFC22
Chlorodifluoromethane

FE115B1
Bromodifluoromethyl trifluoromethyl ether
001479498
FE116
Trifluoromethyl ether

FE216
1,1,2,2,3,3-Hexafluorooxetane

FEE216
2,2,4,4,5,5-Hexafluoro-l,3-dioxolane

FEE218
Bis(trifluoromethoxy)difluoromethane
000354212
HCFC122
1,1,2-Trichloro-2,2-difluoroethane
000306832
HCFC123
1,1 -Dichloro-2,2,2-trifluoroethane
002837890
HCFC124
1 -Chloro-1,2,2,2-tetrafluoroethane
141
-------
Appendix B. (continued)
CAS Registry ASHRAE
Number	Designation

HCFC131
001649087
HCFC132b
000075887
HCFC133a
001717006
HCFC141b
000075683
HCFC142b
000075003
HCFC160
000353366
HCFC161

HCFC21

HCFC22

HCFC225ba

HCFC225da

HCFC226da

HCFC226ea

HCFC234da

HCFC235ca

HCFC243da

HCFC244ca

HCFC31

HCFC326d
000075105
HFC32
000354336
HFC 125
000359353
HFC 134
000811972
HFC 134a
000420462
HFC 143a
Chemical Name
1,2-Dichloro-1,1 -difluoroethane
1 -Chloro-2,2,2-trifluoroethane
1.1-Dichloro-1-fluoroethane
1 -Chloro-1,1 -difluoroethane
Chloroethane
Fluoroethane
Dichlorofluoromethane
Chlorodifluoromethane
1.2-Dichloro-1,2,3,3,3-pentafluoropropane
1,2-Dichloro-1,1,3,3,3-pentafluoropropane
2-Chloro-1,1,1,3,3,3-hexafluoropropane
1 -Chloro-1,1,1,3,3,3 -hexafluoropropane
1,2-Dichloro-1,3,3,3-Tetrafluoropropane
1 -Chloro-2,2,3,3,3-pentafluoropropane
1,2-Dichloro-3,3,3-trifluoropropane
l-Chloro-2,2,3,3-tetrafluoropropane
Chlorofluoromethane
l-Chloro-2,2,3,3,4,4-hexafluorocyclobutane
Difluoromethane
Pentafluoroethane
1,1,2,2-Tetrafluoroethane
1,1,1,2-T etrafluoroethane
1,1,1 -Trifluoroethane
142
-------
Appendix B. (continued)
CAS Registry ASHRAE
Number	Designation
000075376
HFC152a
000076197
HFC218
002252848
HFC227ca
000431890
HFC227ea
000680002
HFC236ca
000677565
HFC236cb
000431630
HFC236ea
000690391
HFC236fa
000679867
HFC245ca
001814886
HFC245cb
000460731
HFC245fa
024270664
HFC245ea
000431312
HFC245eb
040723635
HFC254cb

HFC254ea

HFC254eb
000460731
HFC254fa

HFC254fb
000421078
HFC263fb

HFC272ca

HFC272ea

HFC329ccb

HFC338cca

HFC338ccb
Chemical Name
1,1 -Difluoroethane
Perfluoropropane
,1,1,2,2,3,3-Heptafluoropropane
,1,1,2,3,3,3-Heptafluoropropane
, 1,2,2,3,3-Hexafluoropropane
,1,1,2,2,3-Hexafluoropropane
,1,1,2,3,3-Hexafluoropropane
,1,1,3,3,3-Hexafluoropropane
, 1,2,2,3-Pentafluoropropane
,1,1,2,2-Pentafluoropropane
,1,1,3,3-Pentafluoropropane
, 1,2,3,3-Pentafluoropropane
,1,1,2,3-Pentafluoropropane
, 1,2,2-Tetrafluoropropane
, 1,2,3-Tetrafluoropropane
,1,1,2-Tetrafluoropropane
, 1,3,3-Tetrafluoropropane
,1,1,3-Tetrafluoropropane
,1,1 -Trifluorpropane
,2-Difluoropropane
,2-Difluoropropane
,1,1,2,2,3,3,4,4-Nonafluorobutane
, 1,2,2,3,3,4,4-Octafluorobutane
,1,1,2,2,3,3,4-Octafluorobutane
143
-------
Appendix B. (continued)
CAS Registry
Number
000407590
000460731
003822682
001691174
000461632
000421147
ASHRAE
Designation
HFC338eea
HFC347ccd
HFC356mmf
HFC365mfc
HFE124B1
HFE125
HFE134
HFE143
HFE143a
HFE225
HFE227ca
HFE234
HFE245cb
Chemical Name
1,1,1,2,3,4,4,4-Octafluorobutane
1,1,1,2,2,3,3-Heptafluorobutane
1,1,1,4,4,4-Hexafluorobutane
1,1,1,3,3-Pentafluorobutane
Bromodifluoromethyl difluoromethyl ether
Trifluoromethyl difluoromethyl ether
Difluoromethyl ether
Difluoromethyl fluoromethyl ether
Trifluoromethyl methyl ether
1,1,2,2,3,3-Tetrafluorooxetane
l-(Trifluoromethoxy)-1,1,2,2-tetrafluoroethane
1,1,3,3-Tetrafluorooxetane
Ethane, 2,2-difluoro, 2-difluoromethoxy-
144
-------