U.S. patent application number 14/552949 was filed with the patent office on 2015-03-19 for methods for making foams using blowing agents comprising unsaturated fluorocarbons.
The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to Joseph Anthony Creazzo, Mario Joseph Nappa, Allen Capron Sievert, Ekaterina N Swearingen.
Application Number | 20150080485 14/552949 |
Document ID | / |
Family ID | 37881515 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150080485 |
Kind Code |
A1 |
Creazzo; Joseph Anthony ; et
al. |
March 19, 2015 |
METHODS FOR MAKING FOAMS USING BLOWING AGENTS COMPRISING
UNSATURATED FLUOROCARBONS
Abstract
Disclosed herein are blowing agents comprising fluorocarbons
and/or hydrofluorocarbons useful in foamable compositions. Also
disclosed are methods for forming a foam comprising the
aforementioned blowing agents.
Inventors: |
Creazzo; Joseph Anthony;
(Wilmington, DE) ; Nappa; Mario Joseph; (Newark,
DE) ; Sievert; Allen Capron; (Elkton, MD) ;
Swearingen; Ekaterina N; (Wilmington, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
Wilimington |
DE |
US |
|
|
Family ID: |
37881515 |
Appl. No.: |
14/552949 |
Filed: |
November 25, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
13949569 |
Jul 24, 2013 |
|
|
|
14552949 |
|
|
|
|
11591349 |
Nov 1, 2006 |
8558040 |
|
|
13949569 |
|
|
|
|
60732771 |
Nov 1, 2005 |
|
|
|
Current U.S.
Class: |
521/131 ;
252/182.15; 516/12 |
Current CPC
Class: |
C11D 11/0029 20130101;
G11B 5/8408 20130101; C08J 2205/052 20130101; C08J 2325/06
20130101; C10M 169/04 20130101; C23G 5/02825 20130101; C10N 2030/06
20130101; C03C 23/0075 20130101; C10M 2213/06 20130101; C10N
2030/22 20200501; C11D 7/5018 20130101; C10M 2211/06 20130101; G11B
5/71 20130101; C07C 21/18 20130101; C08J 2375/08 20130101; C10M
177/00 20130101; G11B 5/725 20130101; B01F 17/0085 20130101; C10M
147/04 20130101; C08J 9/0019 20130101; C10M 169/041 20130101; C08J
9/146 20130101; C08G 2101/0025 20130101; C10M 2211/022 20130101;
C10N 2040/14 20130101; C10N 2050/02 20130101; C08J 9/144 20130101;
C08J 2375/06 20130101; C10M 107/38 20130101; G11B 23/505 20130101;
C08G 18/4883 20130101; C11D 3/43 20130101; C10M 105/52 20130101;
C11D 3/245 20130101; C08J 2205/05 20130101; C10N 2040/18 20130101;
C10M 2213/04 20130101; C11D 11/0047 20130101; C10N 2070/00
20130101; C11D 11/0035 20130101; C08G 18/4208 20130101; C11D
11/0023 20130101; C23G 5/02803 20130101 |
Class at
Publication: |
521/131 ; 516/12;
252/182.15 |
International
Class: |
C08J 9/14 20060101
C08J009/14; B01F 17/00 20060101 B01F017/00 |
Claims
1-26. (canceled)
27. A method of producing thermoset foams, comprising the steps of
blending at least one active hydrogen containing compound and at
least one blowing agent to form a premix, wherein said blowing
agent comprises Z--CF3CH.dbd.CHCF3, and reacting said premix with
an A side mixture, said A side mixture comprising at least one
organic polyisocyanate.
28. The method of claim 27, wherein the at least one organic
polyisocyanate, the at least one active hydrogen-containing
compound, and the blowing agent of claim 27 are blended
simultaneously.
29. The method of claim 27, wherein the reacting step is performed
in the presence of at least one catalyst.
30. The method of claim 28, wherein the B side further comprises at
least one auxiliary component, said auxiliary component selected
from the group consisting of a surfactant, a flame retardant, a
preservative, a colorant, an antioxidant, a reinforcing agent, a
filler, an antistatic agent, or a combination thereof.
31. The method of claim 30, wherein the at least surfactant is
present in a range of from about 0.2 to about 5 parts surfactant
per 100 parts by weight polyol.
32. The method of claim 31, wherein the at least one surfactant is
a liquid or solid organosilicone compound, a glycol ether, a
tertiary amine or alkanolamine salt of a long chain alkyl acid
sulfate ester, an alkyl sulfonic ester, or an alkyl arylsulfonic
acid.
33. The method of claim 30, wherein the at least one catalyst is
present in a range of from about 0.1 to about 5 parts catalyst per
100 parts by weight of polyol.
34. The method of claim 27, wherein the thermoset foam is a spray
foam.
35. A composition comprising a fluoroolefin selected from the group
consisting of Z--CF3CH.dbd.CHCF3 and E-CF3CH.dbd.CHCF3, and carbon
dioxide.
36. A foam premix comprising: a polyol and a blowing agent, wherein
the blowing agent agent comprises a fluoroolefin selected from the
group consisting of E-CF3CH.dbd.CHCF3, Z--CF3CH.dbd.CHCF3, and
mixtures thereof.
37. The foam premix of claim 36, further comprising an additional
component, wherein the additional component is a surfactant or a
catalyst.
38. The foam premix of claim 37, wherein the surfactant is a
silicone based surfactant or a glycol ether.
39. The foam premix of claim 37, wherein the catalyst is an amine
or an organometallic catalyst
40. The foam premix of claim 36, further comprising wherein the
premix is shelf stable and capable of reacting and foaming under
the proper conditions of forming a foam under proper
conditions.
41. The foam premix of claim 37, wherein the surfactant is a liquid
or solid organosilicone compound, a glycol ether, a tertiary amine
or alkanolamine salt of a long chain alkyl acid sulfate ester, an
alkyl sulfonic ester, or an alkyl arylsulfonic acid.
42. The method of claim 37, wherein the at least one catalyst is
present in a range of from about 0.1 to about 5 parts catalyst per
100 parts by weight of polyol.
Description
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of priority of U.S.
Provisional Application 60/732,771, filed Nov. 1, 2005, and
incorporated herein by reference, and is further related to
co-filed and jointly owned application titled Blowing Agents for
Forming Foam Comprising Unsaturated Fluorocarbons, (Attorney Docket
No. FL1184 US NA) and further related to co-filed and jointly owned
application also titled Blowing Agents for Forming Foam Comprising
Unsaturated Fluorocarbons (Attorney Docket No. FL1318 US NA), both
of which are also incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The disclosure herein relates to blowing agent compositions
comprising unsaturated fluorocarbons and/or unsaturated
hydrofluorocarbons. The disclosure herein further relates to the
use of the blowing agent compositions in the process for
manufacturing plastic foams.
BACKGROUND OF THE INVENTION
[0003] Closed-cell polyisocyanate-based foams are widely used for
insulation purposes, for example, in building construction and in
the manufacture of energy efficient electrical appliances. In the
construction industry, polyurethane (polyisocyanurate) board stock
is used in roofing and siding for its insulation and load-carrying
capabilities. Poured and sprayed polyurethane foams are widely used
for a variety of applications including insulating roofs,
insulating large structures such as storage tanks, insulating
appliances such as refrigerators and freezers, insulating
refrigerated trucks and railcars, etc.
[0004] All of these various types of polyurethane foams require
blowing (expansion) agents for their manufacture. Insulating foams
depend on the use of halocarbon blowing agents, not only to foam
the polymer, but primarily for their low vapor thermal
conductivity, a very important characteristic for insulation value.
Historically, polyurethane foams used CFCs (chlorofluorocarbons,
for example CFC-11, trichlorofluoromethane) and HCFCs
(hydrochlorofluorocarbons, for example HCFC-141b,
1,1-dichloro-1-fluoroethane) as the primary blowing agent. However,
due to the implication of chlorine-containing molecules such as the
CFCs and HCFCs in the destruction of stratospheric ozone, the
production and use of CFCs and HCFCs has been restricted by the
Montreal Protocol. More recently, hydrofluorocarbons (HFCs), which
do not contribute to the destruction of stratospheric ozone, have
been employed as blowing agents for polyurethane foams. An example
of an HFC employed in this application is HFC-245fa
(1,1,1,3,3-pentafluoropropane).
[0005] A second type of insulating foam is thermoplastic foam,
primarily polystyrene foam. Polyolefin foams (polystyrene,
polyethylene, and polypropylene) are widely used in insulation and
packaging applications. These thermoplastic foams were generally
made with CFC-12 (dichlorodifluoromethane) as the blowing agent.
More recently HCFCs (HCFC-22, chlorodifluoromethane) or blends of
HCFCs (HCFC-22/HCFC-142b) or HFCs (HFC-152a) have been employed as
blowing agents for polystyrene.
[0006] A third important type of insulating foam is phenolic foam.
These foams, which have very attractive flammability
characteristics, were generally made with CFC-11
(trichlorofluoromethane) and CFC-113
(1,1,2-trichloro-1,2,2-trifluoroethane) blowing agents
[0007] In addition to closed-cell foams, open-cell foams are also
of commercial interest, for example in the production of
fluid-absorbent articles. U.S. Pat. No. 6,703,431 (Dietzen, et.
al.) describes open-cell foams based on thermoplastics polymers
that are useful for fluid-absorbent hygiene articles such as wound
contact materials. U.S. Pat. No. 6,071,580 (Bland, et. al.)
describes absorbent extruded thermoplastic foams which can be
employed in various absorbency applications. Open-cell foams have
also found application in evacuated or vacuum panel technologies,
for example in the production of evacuated insulation panels as
described in U.S. Pat. No. 5,977,271 (Malone). Using open-cell
foams in evacuated insulation panels, it has been possible to
obtain R values of 10 to 15 per inch of thickness depending upon
the evacuation or vacuum level, polymer type, cell size, density,
and open cell content of the foam. These open-cell foams have
traditionally been produced employing CFCs, HCFCs, or more
recently, HFCs as blowing agents.
[0008] Multimodal foams are also of commercial interest, and are
described, for example, in U.S. Pat. No. 6,787,580 (Chonde, et.
al.) and U.S. Pat. No. 5,332,761 (Paquet, et. al.). A multimodal
foam is a foam having a multimodal cell size distribution, and such
foams have particular utility in thermally insulating articles
since they often have higher insulating values (R-values) than
analogous foams having a generally uniform cell size distribution.
These foams have been produced employing CFCs, HCFCs, and, more
recently, HFCs as the blowing agent.
[0009] As discussed above, the production of various types of foams
historically employed CFCs as the blowing agent. In general, the
CFCs produce foams exhibiting good thermal insulation, low
flammability and excellent dimensional stability. However, despite
these advantages the CFCs have fallen into disfavor due to their
implication in the destruction of stratospheric ozone, as well as
their implication in contributing to global warming.
[0010] HCFCs have been proposed as CFC substitutes, and are
currently employed as foam blowing agents. However, the HCFCs have
also been shown to contribute to the depletion of stratospheric
ozone, and as a result their use has come under scrutiny, and the
widespread use of HCFCs is scheduled for eventual phase out under
the Montreal Protocol.
[0011] More recently HFCs have been proposed and employed as foam
blowing agents. The HFCs do not contribute to the destruction of
stratospheric ozone, but are of concern due to their contribution
to the "greenhouse effect", i.e., they contribute to global
warming. As a result of their contribution to global warming, the
HFCs have come under scrutiny, and their widespread use may also be
limited in the future.
[0012] Hydrocarbons have also been proposed as foam blowing agents.
However, these compounds are flammable, and many are
photochemically reactive, and as a result contribute to the
production of ground level ozone (i.e., smog). Such compounds are
typically referred to as volatile organic compounds (VOCs), and are
subject to environmental regulations.
[0013] There is need for producing foams that provide low
flammability, good thermal insulation and high dimensional
stability by using a blowing agent that has substantially no ozone
depletion potential (ODP) and no or very low global warming
potential (GWP).
[0014] There is also need to provide a process for producing
plastic foams employing a blowing agent which has significantly
less photochemical reactivity than the hydrocarbons, and hence does
not contribute to the formation of ambient ozone and ground level
smog.
SUMMARY OF THE INVENTION
[0015] One aspect is for a blowing agent comprising at least one
fluorocarbon or hydrofluorocarbon selected from the group
consisting of: [0016] (i) a hydrofluorocarbon having the formula E-
or Z--R.sup.1CH.dbd.CHR.sup.2, wherein R.sup.1 and R.sup.2 are,
independently, C.sub.1 to C.sub.6 perfluoroalkyl groups; and [0017]
(ii) a fluorocarbon or hydrofluorocarbon selected from the group
consisting of CF.sub.3CF.dbd.CHF, CF.sub.3CH.dbd.CF.sub.2,
CHF.sub.2CF.dbd.CF.sub.2, CHF.sub.2CH.dbd.CHF,
CF.sub.3CF.dbd.CH.sub.2, CF.sub.3CH.dbd.CHF,
CH.sub.2FCF.dbd.CF.sub.2, CHF.sub.2CH.dbd.CF.sub.2,
CHF.sub.2CF.dbd.CHF, CHF.sub.2CF.dbd.CH.sub.2,
CF.sub.3CH.dbd.CH.sub.2, CH.sub.3CF.dbd.CF.sub.2,
CH.sub.2FCHCF.sub.2, CH.sub.2FCF.dbd.CHF, CHF.sub.2CH.dbd.CHF,
CF.sub.3CF.dbd.CFCF.sub.3, CF.sub.3CF.sub.2CF.dbd.CF.sub.2,
CF.sub.3CF.dbd.CHCF.sub.3, CF.sub.3CF.sub.2CF.dbd.CH.sub.2,
CF.sub.3CH.dbd.CHCF.sub.3, CF.sub.3CF.sub.2CH.dbd.CH.sub.2,
CF.sub.2.dbd.CHCF.sub.2CF.sub.3, CF.sub.2.dbd.CFCHFCF.sub.3,
CF.sub.2.dbd.CFCF.sub.2CHF.sub.2, CHF.sub.2CH.dbd.CHCF.sub.3,
(CF.sub.3).sub.2C.dbd.CHCF.sub.3,
CF.sub.3CF.dbd.CHCF.sub.2CF.sub.3,
CF.sub.3CH.dbd.CFCF.sub.2CF.sub.3,
(CF.sub.3).sub.2CFCH.dbd.CH.sub.2,
CF.sub.3CF.sub.2CF.sub.2CH.dbd.CH.sub.2,
CF.sub.3(CF.sub.2).sub.3CF.dbd.CF.sub.2,
CF.sub.3CF.sub.2CF.dbd.CFCF.sub.2CF.sub.3,
(CF.sub.3).sub.2C.dbd.C(CF.sub.3).sub.2,
(CF.sub.3).sub.2CFCF.dbd.CHCF.sub.3,
CF.sub.2.dbd.CFCF.sub.2CH.sub.2F, CF.sub.2.dbd.CFCHFCHF.sub.2,
CH.sub.2.dbd.C(CF.sub.3).sub.2, CH.sub.2CF.sub.2CF.dbd.CF.sub.2,
CH.sub.2FCF.dbd.CFCHF.sub.2, CH.sub.2FCF.sub.2CF.dbd.CF.sub.2,
CF.sub.2.dbd.C(CF.sub.3)(CH.sub.3),
CH.sub.2.dbd.C(CHF.sub.2)(CF.sub.3),
CH.sub.2.dbd.CHCF.sub.2CHF.sub.2,
CF.sub.2.dbd.C(CHF.sub.2)(CH.sub.3), CHF.dbd.C(CF.sub.3)(CH.sub.3),
CH.sub.2.dbd.C(CHF.sub.2).sub.2, CF.sub.3CF.dbd.CFCH.sub.3,
CH.sub.3CF.dbd.CHCF.sub.3, CF.sub.2.dbd.CFCF.sub.2CF.sub.2CF.sub.3,
CHF.dbd.CFCF.sub.2CF.sub.2CF.sub.3,
CF.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.3,
CF.sub.2.dbd.CFCF.sub.2CF.sub.2CHF.sub.2,
CHF.sub.2CF.dbd.CFCF.sub.2CF.sub.3,
CF.sub.3CF.dbd.CFCF.sub.2CHF.sub.2, CF.sub.3CF.dbd.CFCHFCF.sub.3,
CHF.dbd.CFCF(CF.sub.3).sub.2, CF.sub.2.dbd.CFCH(CF.sub.3).sub.2,
CF.sub.3CH.dbd.C(CF.sub.3).sub.2,
CF.sub.2.dbd.CHCF(CF.sub.3).sub.2,
CH.sub.2.dbd.CFCF.sub.2CF.sub.2CF.sub.3,
CHF.dbd.CFCF.sub.2CF.sub.2CHF.sub.2,
CH.sub.2.dbd.C(CF.sub.3)CF.sub.2CF.sub.3,
CF.sub.2.dbd.CHCH(CF.sub.3).sub.2, CHF.dbd.CHCF(CF.sub.3).sub.2,
CF.sub.2.dbd.C(CF.sub.3)CH.sub.2CF.sub.3,
CH.sub.2.dbd.CFCF.sub.2CF.sub.2CHF.sub.2,
CF.sub.2.dbd.CHCF.sub.2CH.sub.2CF.sub.3,
CF.sub.3CF.dbd.C(CF.sub.3)(CH.sub.3),
CH.sub.2.dbd.CFCH(CF.sub.3).sub.2, CHF.dbd.CHCH(CF.sub.3).sub.2,
CH.sub.2FCH.dbd.C(CF.sub.3).sub.2,
CH.sub.3CF.dbd.C(CF.sub.3).sub.2,
CH.sub.2.dbd.CHCF.sub.2CHFCF.sub.3,
CH.sub.2C(CF.sub.3)CH.sub.2CF.sub.3,
(CF.sub.3).sub.2C.dbd.CHC.sub.2F.sub.5,
(CF.sub.3).sub.2CFCF.dbd.CHCF.sub.3,
CH.sub.2.dbd.CHC(CF.sub.3).sub.3,
(CF.sub.3).sub.2C.dbd.C(CH.sub.3)(CF.sub.3),
CH.sub.2.dbd.CFCF.sub.2CH(CF.sub.3).sub.2,
CF.sub.3CF.dbd.C(CH.sub.3)CF.sub.2CF.sub.3,
CF.sub.3CH.dbd.CHCH(CF.sub.3).sub.2,
CH.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.2CHF.sub.2,
(CF.sub.3).sub.2C.dbd.CHCF.sub.2CH.sub.3,
CH.sub.2.dbd.C(CF.sub.3)CH.sub.2C.sub.2F.sub.5,
CH.sub.2.dbd.CHCH.sub.2CF.sub.2C.sub.2F.sub.5,
CH.sub.2.dbd.CHCH.sub.2CF.sub.2C.sub.2F.sub.5,
CF.sub.3CF.sub.2CF.dbd.CFC.sub.2H.sub.5,
CH.sub.2.dbd.CHCH.sub.2CF(CF.sub.3).sub.2,
CF.sub.3CF.dbd.CHCH(CF.sub.3)(CH.sub.3),
(CF.sub.3).sub.2C.dbd.CFC.sub.2H.sub.5,
cyclo-CF.sub.2CF.sub.2CF.sub.2CH.dbd.CH--,
cyclo-CF.sub.2CF.sub.2CH.dbd.CH--,
CF.sub.3CF.sub.2CF.sub.2C(CH.sub.3).dbd.CH.sub.2,
CF.sub.3CF.sub.2CF.sub.2CH.dbd.CHCH.sub.3,
cyclo-CF.sub.2CF.sub.2CF.dbd.CF--,
cyclo-CF.sub.2CF.dbd.CFCF.sub.2CF.sub.2--,
cyclo-CF.sub.2CF.dbd.CFCF.sub.2CF.sub.2CF.sub.2,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.dbd.CH.sub.2,
CF.sub.3CH.dbd.CHCF.sub.2CF.sub.3,
CF.sub.3CF.sub.2CH.dbd.CHCF.sub.2CF.sub.3,
CF.sub.3CH.dbd.CHCF.sub.2CF.sub.2CF.sub.3,
CF.sub.3CF.dbd.CFC.sub.2F.sub.5,
CF.sub.3CF.dbd.CFCF.sub.2CF.sub.2C.sub.2F.sub.5,
CF.sub.3CF.sub.2CF.dbd.CFCF.sub.2C.sub.2F.sub.5,
CF.sub.3CH.dbd.CFCF.sub.2CF.sub.2C.sub.2F.sub.5,
CF.sub.3CF.dbd.CHCF.sub.2CF.sub.2C.sub.2F.sub.5,
CF.sub.3CF.sub.2CH.dbd.CFCF.sub.2C.sub.2F.sub.5,
CF.sub.3CF.sub.2CF.dbd.CHCF.sub.2C.sub.2F.sub.5,
C.sub.2F.sub.5CF.sub.2CF.dbd.CHCH.sub.3,
C.sub.2F.sub.5CF.dbd.CHCH.sub.3, (CF.sub.3).sub.2C.dbd.CHCH.sub.3,
CF.sub.3C(CH.sub.3).dbd.CHCF.sub.3, CHF.dbd.CFC.sub.2F.sub.5,
CHF.sub.2CF.dbd.CFCF.sub.3, (CF.sub.3).sub.2C.dbd.CHF,
CH.sub.2FCF.dbd.CFCF.sub.3, CHF.dbd.CHCF.sub.2CF.sub.3,
CHF.sub.2CH.dbd.CFCF.sub.3, CHF.dbd.CFCHFCF.sub.3,
CF.sub.3CH.dbd.CFCHF.sub.2, CHF.dbd.CFCF.sub.2CHF.sub.2,
CHF.sub.2CF.dbd.CFCHF.sub.2, CH.sub.2CF.dbd.CFCF.sub.3,
CH.sub.2FCH.dbd.CFCF.sub.3, CH.sub.2.dbd.CFCHFCF.sub.3,
CH.sub.2.dbd.CFCF.sub.2CHF.sub.2, CF.sub.3CH.dbd.CFCH.sub.2F,
CHF.dbd.CFCH.sub.2CF.sub.3, CHF.dbd.CHCHFCF.sub.3,
CHF.dbd.CHCF.sub.2CHF.sub.2, CHF.sub.2CF.dbd.CHCHF.sub.2,
CHF.dbd.CFCHFCHF.sub.2, CF.sub.3CF.dbd.CHCH.sub.3,
CF.sub.2.dbd.CHCF.sub.2Br, CHF.dbd.CBrCHF.sub.2,
CHBr.dbd.CHCF.sub.3, CF.sub.3CBr.dbd.CFCF.sub.3,
CH.sub.2.dbd.CBrCF.sub.2CF.sub.3, CHBr.dbd.CHCF.sub.2CF.sub.3,
CH.sub.2.dbd.CHCF.sub.2CF.sub.2Br, CH.sub.2.dbd.CHCBrFCF.sub.3,
CH.sub.3CBr.dbd.CHCF.sub.3, CF.sub.3CBr.dbd.CHCH.sub.3,
(CF.sub.3).sub.2C.dbd.CHBr, CF.sub.3CF.dbd.CBrCF.sub.2CF.sub.3,
E-CHF.sub.2CBr.dbd.CFC.sub.2F.sub.5,
Z--CHF.sub.2CBr.dbd.CFC.sub.2F.sub.5,
CF.sub.2.dbd.CBrCHFC.sub.2F.sub.5,
(CF.sub.3).sub.2CFCBr.dbd.CH.sub.2,
CHBr.dbd.CF(CF.sub.2).sub.2CHF.sub.2,
CH.sub.2.dbd.CBrCF.sub.2C.sub.2F.sub.5,
CF.sub.2.dbd.C(CH.sub.2Br)CF.sub.3,
CH.sub.2.dbd.C(CBrF.sub.2)CF.sub.3, (CF.sub.3).sub.2CHCH.dbd.CHBr,
(CF.sub.3).sub.2C.dbd.CHCH.sub.2Br,
CH.sub.2.dbd.CHCF(CF.sub.3)CBrF.sub.2,
CF.sub.2.dbd.CHCF.sub.2CH.sub.2CBrF.sub.2, CFBr.dbd.CHCF.sub.3,
CFBr.dbd.CFCF.sub.3, CF.sub.3CF.sub.2CF.sub.2CBr.dbd.CH.sub.2, and
CF.sub.3(CF.sub.2).sub.3CBr.dbd.CH.sub.2.
[0018] Another aspect is for a closed cell foam prepared by foaming
a foamable composition in the presence of a blowing agent described
above.
[0019] A further aspect is for a foamable composition comprising a
polyol and a blowing agent described above.
[0020] Another aspect is for a foam premix composition comprising a
polyol and a blowing agent described above.
[0021] Additionally, one aspect is for a method of forming a foam
comprising: [0022] (a) adding to a foamable composition a blowing
agent described above; and [0023] (b) reacting the foamable
composition under conditions effective to form a foam.
[0024] A further aspect is for a method of forming a
polyisocyanate-based foam comprising reacting at least one organic
polyisocyanate with at least one active hydrogen-containing
compound in the presence of a blowing agent described above.
Another aspect is for a polyisocyanate foam produced by said
method.
[0025] Other objects and advantages will become apparent to those
skilled in the art upon reference to the detailed description that
hereinafter follows.
DETAILED DESCRIPTION OF THE INVENTION
[0026] Applicants specifically incorporate the entire content of
all cited references in this disclosure. Applicants also
incorporate by reference the co-owned and concurrently filed
applications entitled "Solvent Compositions Comprising Unsaturated
Fluorinated Hydrocarbons" (Attorney Docket # FL 1181 US PRV, U.S.
Application No. 60/732,771), "Blowing Agents for Forming Foam
Comprising Unsaturated Fluorocarbons" (Attorney Docket # FL 1184 US
PRV, U.S. Application No. 60/732,090), "Aerosol Propellants
Comprising Unsaturated Fluorocarbons" (Attorney Docket # FL 1185 US
PRV, U.S. Application No. 60/732,791), and "Compositions Comprising
Fluoroolefins and Uses Thereof" (Attorney docket # FL 1159, U.S.
Application No. 60/732,581). Further, when an amount,
concentration, or other value or parameter is given as either a
range, preferred range, or a list of upper preferable values and
lower preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of any upper range limit
or preferred value and any lower range limit or preferred value,
regardless of whether ranges are separately disclosed. Where a
range of numerical values is recited herein, unless otherwise
stated, the range is intended to include the endpoints thereof, and
all integers and fractions within the range. It is not intended
that the scope of the invention be limited to the specific values
recited when defining a range.
[0027] One aspect provides blowing agents having the formula E- or
Z--R.sup.1CH.dbd.CHR.sup.2 (Formula I), wherein R.sup.1 and R.sup.2
are, independently, C.sub.1 to C.sub.6 perfluoroalkyl groups.
Examples of R.sup.1 and R.sup.2 groups include, but are not limited
to, CF.sub.3, C.sub.2F.sub.5, CF.sub.2CF.sub.2CF.sub.3,
CF(CF.sub.3).sub.2, CF.sub.2CF.sub.2CF.sub.2CF.sub.3,
CF(CF.sub.3)CF.sub.2CF.sub.3, CF.sub.2CF(CF.sub.3).sub.2,
C(CF.sub.3).sub.3, CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3,
CF.sub.2CF.sub.2CF(CF.sub.3).sub.2,
C(CF.sub.3).sub.2C.sub.2F.sub.5,
CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3, CF(CF.sub.3)
CF.sub.2CF.sub.2C.sub.2F.sub.5, and
C(CF.sub.3).sub.2CF.sub.2C.sub.2F.sub.5. Exemplary, non-limiting
Formula I compounds are presented in Table 1.
TABLE-US-00001 TABLE 1 Code Structure Chemical Name F11E
CF.sub.3CH.dbd.CHCF.sub.3 1,1,1,4,4,4-hexafluorobut-2-ene F12E
CF.sub.3CH.dbd.CHC.sub.2F.sub.5
1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E
CF.sub.3CH.dbd.CHCF.sub.2C.sub.2F.sub.5
1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE
CF.sub.3CH.dbd.CHCF(CF.sub.3).sub.2
1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22E
C.sub.2F.sub.5CH.dbd.CHC.sub.2F.sub.5
1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14E
CF.sub.3CH.dbd.CH(CF.sub.2).sub.3CF.sub.3
1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iE
CF.sub.3CH.dbd.CHCF.sub.2CF--(CF.sub.3).sub.2
1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sE
CF.sub.3CH.dbd.CHCF(CF.sub.3)--C.sub.2F.sub.5
1,1,1,4,5,5,6,6,6-nonafluoro-4-(trifluoromethyl)hex-2-ene F14tE
CF.sub.3CH.dbd.CHC(CF.sub.3).sub.3
1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23E
C.sub.2F.sub.5CH.dbd.CHCF.sub.2C.sub.2F.sub.5
1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iE
C.sub.2F.sub.5CH.dbd.CHCF(CF.sub.3).sub.2
1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15E
CF.sub.3CH.dbd.CH(CF.sub.2).sub.4CF.sub.3
1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene
1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6- F15iE
CF.sub.3CH.dbd.CH--CF.sub.2CF.sub.2CF(CF.sub.3).sub.2
(trifluoromethyl)hept-2-ene F15tE
CF.sub.3CH.dbd.CH--C(CF.sub.3).sub.2C.sub.2F.sub.5
1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl) hex-2-ene F24E
C.sub.2F.sub.5CH.dbd.CH(CF.sub.2).sub.3CF.sub.3
1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene F24iE
C.sub.2F.sub.5CH.dbd.CHCF.sub.2CF--(CF.sub.3).sub.2
1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6- (trifluoromethyl)hept-3-ene
F24sE C.sub.2F.sub.5CH.dbd.CHCF(CF.sub.3)--C.sub.2F.sub.5
1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5- (trifluoromethyl)hept-3-ene
F24tE C.sub.2F.sub.5CH.dbd.CHC(CF.sub.3).sub.3
1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl) hex-3-ene F33E
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF.sub.2C.sub.2F.sub.5
1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE
(CF.sub.3).sub.2CFCH.dbd.CH--CF(CF.sub.3).sub.2
1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl) hex-3-ene F33iE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF(CF.sub.3).sub.2
1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2- (trifluoromethyl)hept-3-ene
F16E CF.sub.3CH.dbd.CH(CF.sub.2).sub.5CF.sub.3
1,1,1,4,4,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-2-ene F16sE
CF.sub.3CH.dbd.CHCF(CF.sub.3)--(CF.sub.2).sub.2C.sub.2F.sub.5
1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-
(trifluoromethyl)hept-2-ene F16tE
CF.sub.3CH.dbd.CHC(CF.sub.3).sub.2--CF.sub.2C.sub.2F.sub.5
1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25E
C.sub.2F.sub.5CH.dbd.CH(CF.sub.2).sub.4CF.sub.3
1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iE
C.sub.2F.sub.5CH.dbd.CH--CF.sub.2CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-
(trifluoromethyl)oct-3-ene F25tE
C.sub.2F.sub.5CH.dbd.CH--C(CF.sub.3).sub.2C.sub.2F.sub.5
1,1,1,2,2,6,6,7,7,7-decafluoro-5,5- bis(trifluoromethyl)hept-3-ene
F34E C.sub.2F.sub.5CF.sub.2CH.dbd.CH--(CF.sub.2).sub.3CF.sub.3
1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-
(trifluoromethyl)oct-4-ene F34sE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF(CF.sub.3)C.sub.2F.sub.5
1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-
(trifluoromethyl)oct-4-ene F34tE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--C(CF.sub.3).sub.3
1,1,1,5,5,6,6,7,7,7-decafluoro-2,2- bis(trifluoromethyl)hept-3-ene
F3i4E (CF.sub.3).sub.2CFCH.dbd.CH--(CF.sub.2).sub.3CF.sub.3
1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-
2(trifluoromethyl)oct-3-ene F3i4iE
(CF.sub.3).sub.2CFCH.dbd.CH--CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,5,5,6,7,7,7-decafluoro-2,6- bis(trifluoromethyl)hept-3-ene
F3i4sE (CF.sub.3).sub.2CFCH.dbd.CH--CF(CF.sub.3)C.sub.2F.sub.5
1,1,1,2,5,6,6,7,7,7-decafluoro-2,5- bis(trifluoromethyl)hept-3-ene
F3i4tE (CF.sub.3).sub.2CFCH.dbd.CH--C(CF.sub.3).sub.3
1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl) hex-3-ene
F26E C.sub.2F.sub.5CH.dbd.CH(CF.sub.2).sub.5CF.sub.3
1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10- octadecafluorodec-3-ene
F26sE
C.sub.2F.sub.5CH.dbd.CHCF(CF.sub.3)--(CF.sub.2).sub.2C.sub.2F.sub.5
1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-
(trifluoromethyl)non-3-ene F26tE
C.sub.2F.sub.5CH.dbd.CHC(CF.sub.3).sub.2--CF.sub.2C.sub.2F.sub.5
1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-
bis(trifluoromethyl)oct-3-ene F35E
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--(CF.sub.2).sub.4CF.sub.3
1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10- octadecafluorodec-4-ene
F35iE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF.sub.2CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-
(trifluoromethyl)non-4-ene F35tE
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--C(CF.sub.3).sub.2C.sub.2F.sub.5
1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-
bis(trifluoromethyl)oct-4-ene F3i5E
(CF.sub.3).sub.2CFCH.dbd.CH--(CF.sub.2).sub.4CF.sub.3
1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
(trifluoromethyl)non-3-ene F3i5iE
(CF.sub.3).sub.2CFCH.dbd.CH--CF.sub.2CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-
bis(trifluoromethyl)oct-3-ene F3i5tE
(CF.sub.3).sub.2CFCH.dbd.CH--C(CF.sub.3).sub.2C.sub.2F.sub.5
1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5- tris(trifluoromethyl)hept-3-ene
F44E CF.sub.3(CF.sub.2).sub.3CH.dbd.CH--(CF.sub.2).sub.3CF.sub.3
1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10- octadecafluorodec-5-ene
F44iE CF.sub.3(CF.sub.2).sub.3CH.dbd.CH--CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
(trifluoromethyl)non-4-ene F44sE
CF.sub.3(CF.sub.2).sub.3CH.dbd.CH--CF(CF.sub.3)C.sub.2F.sub.5
1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-
(trifluoromethyl)non-4-ene F44tE
CF.sub.3(CF.sub.2).sub.3CH.dbd.CH--C(CF.sub.3)
1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-
bis(trifluoromethyl)oct-3-ene F4i4iE
(CF.sub.3).sub.2CFCF.sub.2CH.dbd.CH--CF.sub.2CF(CF.sub.3).sub.2
1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-
bis(trifluoromethyl)oct-4-ene F4i4sE
(CF.sub.3).sub.2CFCF.sub.2CH.dbd.CH--CF(CF.sub.3)C.sub.2F.sub.5
1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-
bis(trifluoromethyl)oct-4-ene F4i4tE
(CF.sub.3).sub.2CFCF.sub.2CH.dbd.CH--C(CF.sub.3).sub.3
1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6- tris(trifluoromethyl)hept-3-ene
F4s4sE
C.sub.2F.sub.5CF(CF.sub.3)CH.dbd.CH--CF(CF.sub.3)C.sub.2F.sub.5
1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-
bis(trifluoromethyl)oct-4-ene F4s4tE
C.sub.2F.sub.5CF(CF.sub.3)CH.dbd.CH--C(CF.sub.3).sub.3
1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5- tris(trifluoromethyl)hept-3-ene
F4t4tE (CF.sub.3).sub.3CCH.dbd.CH--C(CF.sub.3).sub.3
1,1,1,6,6,6-hexafluoro-2,2,5,5-
tetrakis(trifluoromethyl)hex-3-ene
[0028] Compounds of Formula I may be prepared by contacting a
perfluoroalkyl iodide of the formula R.sup.1I with a
perfluoroalkyltrihydroolefin of the formula R.sup.2CH.dbd.CH.sub.2
to form a trihydroiodoperfluoroalkane of the formula
R.sup.1CH.sub.2CHIR.sup.2. This trihydroiodoperfluoroalkane can
then be dehydroiodinated to form R.sup.1CH.dbd.CHR.sup.2.
Alternatively, the olefin R.sup.1CH.dbd.CHR.sup.2 may be prepared
by dehydroiodination of a trihydroiodoperfluoroalkane of the
formula R.sup.1CHICH.sub.2R.sup.2 formed in turn by reacting a
perfluoroalkyl iodide of the formula R.sup.2I with a
perfluoroalkyltrihydroolefin of the formula
R.sup.1CH.dbd.CH.sub.2.
[0029] Said contacting of a perfluoroalkyl iodide with a
perfluoroalkyltrihydroolefin may take place in batch mode by
combining the reactants in a suitable reaction vessel capable of
operating under the autogenous pressure of the reactants and
products at reaction temperature. Suitable reaction vessels include
those fabricated from stainless steels, in particular of the
austenitic type, and the well-known high nickel alloys such as
Monel.RTM. nickel-copper alloys, Hastelloy.RTM. nickel based alloys
and Inconel.RTM. nickel-chromium alloys.
[0030] Alternatively, the reaction may be conducted in semi-batch
mode in which the perfluoroalkyltrihydroolefin reactant is added to
the perfluoroalkyl iodide reactant by means of a suitable addition
apparatus such as a pump at the reaction temperature.
[0031] The ratio of perfluoroalkyl iodide to
perfluoroalkyltrihydroolefin should be between about 1:1 to about
4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1
tend to result in large amounts of the 2:1 adduct as reported by
Jeanneaux, et al. in Journal of Fluorine Chemistry, Vol. 4, pages
261-270 (1974).
[0032] Preferred temperatures for contacting of said perfluoroalkyl
iodide with said perfluoroalkyltrihydroolefin are preferably within
the range of about 150.degree. C. to 300.degree. C., preferably
from about 170.degree. C. to about 250.degree. C., and most
preferably from about 180.degree. C. to about 230.degree. C.
[0033] Suitable contact times for the reaction of the
perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are
from about 0.5 hour to 18 hours, preferably from about 4 to about
12 hours.
[0034] The trihydroiodoperfluoroalkane prepared by reaction of the
perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be
used directly in the dehydroiodination step or may preferably be
recovered and purified by distilled prior to the dehydroiodination
step.
[0035] The dehydroiodination step is carried out by contacting the
trihydroiodoperfluoroalkane with a basic substance. Suitable basic
substances include alkali metal hydroxides (e.g., sodium hydroxide
or potassium hydroxide), alkali metal oxide (for example, sodium
oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide),
alkaline earth metal oxides (e.g., calcium oxide), alkali metal
alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous
ammonia, sodium amide, or mixtures of basic substances such as soda
lime. Preferred basic substances are sodium hydroxide and potassium
hydroxide.
[0036] Said contacting of the trihydroiodoperfluoroalkane with a
basic substance may take place in the liquid phase preferably in
the presence of a solvent capable of dissolving at least a portion
of both reactants. Solvents suitable for the dehydroiodination step
include one or more polar organic solvents such as alcohols (e.g.,
methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,
and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile,
butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide,
N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The
choice of solvent may depend on the boiling point of the product
and the ease of separation of traces of the solvent from the
product during purification. Typically, ethanol or isopropanol are
good solvents for the reaction.
[0037] Typically, the dehydroiodination reaction may be carried out
by addition of one of the reactants (either the basic substance or
the trihydroiodoperfluoroalkane) to the other reactant in a
suitable reaction vessel. Said reaction vessel may be fabricated
from glass, ceramic, or metal and is preferably agitated with an
impellor or stirring mechanism.
[0038] Temperatures suitable for the dehydroiodination reaction are
from about 10.degree. C. to about 100.degree. C., preferably from
about 20.degree. C. to about 70.degree. C. The dehydroiodination
reaction may be carried out at ambient pressure or at reduced or
elevated pressure. Of note are dehydroiodination reactions in which
the compound of Formula I is distilled out of the reaction vessel
as it is formed.
[0039] Alternatively, the dehydroiodination reaction may be
conducted by contacting an aqueous solution of said basic substance
with a solution of the trihydroiodoperfluoroalkane in one or more
organic solvents of lower polarity such as an alkane (e.g., hexane,
heptane, or octane), aromatic hydrocarbon (e.g., toluene),
halogenated hydrocarbon (e.g., methylene chloride, ethylene
dichloride, chloroform, carbon tetrachloride, or
perchloroethylene), or ether (e.g., diethyl ether, methyl
tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran,
dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence
of a phase transfer catalyst. Suitable phase transfer catalysts
include quaternary ammonium halides (e.g., tetrabutylammonium
bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium
chloride, dodecyltrimethylammonium chloride, and
tricaprylylmethylammonium chloride), quaternary phosphonium halides
(e.g., triphenylmethylphosphonium bromide and
tetraphenylphosphonium chloride), and cyclic ether compounds known
in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).
[0040] Alternatively, the dehydroiodination reaction may be
conducted in the absence of solvent by adding the
trihydroiodoperfluoroalkane to a solid or liquid basic
substance.
[0041] Suitable reaction times for the dehydroiodination reactions
are from about 15 minutes to about six hours or more depending on
the solubility of the reactants. Typically the dehydroiodination
reaction is rapid and requires about 30 minutes to about three
hours for completion.
[0042] The compound of formula I may be recovered from the
dehydroiodination reaction mixture by phase separation after
addition of water, by distillation, or by a combination
thereof.
[0043] The compositions disclosed herein may comprise a single
compound of Formula I, for example, one of the compounds in Table
1, or may comprise a combination of compounds of Formula I.
[0044] In addition to the inventive compounds described above,
compounds presented in Table 2 can be used as blowing agents.
TABLE-US-00002 TABLE 2 Name Structure Chemical name HFC-1225s
C.sub.3HF.sub.5 HFC-1225ye CF.sub.3CF.dbd.CHF
1,2,3,3,3-pentafluoro-1- propene HFC-1225zc CF.sub.3CH.dbd.CF.sub.2
1,1,3,3,3-pentafluoro-1- propene HFC-1225yc
CHF.sub.2CF.dbd.CF.sub.2 1,1,2,3,3-pentafluoro-1- propene HFC-1234s
C.sub.3H.sub.2F.sub.4 HFC-1234ye CHF.sub.2CF.dbd.CHF
1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF.sub.3CF.dbd.CH.sub.2
2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF.sub.3CH.dbd.CHF
1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH.sub.2FCF.dbd.CF.sub.2
1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF.sub.2CH.dbd.CF.sub.2
1,1,3,3-tetrafluoro-1-propene HFC-1234ye CHF.sub.2CF.dbd.CHF
1,2,3,3-tetrafluoro-1-propene HFC-1243s C.sub.3H.sub.3F.sub.3
HFC-1243yf CHF.sub.2CF.dbd.CH.sub.2 2,3,3-trifluoro-1-propene
HFC-1243zf CF.sub.3CH.dbd.CH.sub.2 3,3,3-trifluoro-1-propene
HFC-1243yc CH.sub.3CF.dbd.CF.sub.2 1,1,2-trifluoro-1-propene
HFC-1243zc CH.sub.2FCH.dbd.CF.sub.2 1,1,3-trifluoro-1-propene
HFC-1243ye CHF.sub.2CF.dbd.CHF 1,2,3-trifluoro-1-propene HFC-1243ze
CHF.sub.2CH.dbd.CHF 1,3,3-trifluoro-1-propene FC-1318s
C.sub.4F.sub.8 FC-1318my CF.sub.3CF.dbd.CFCF.sub.3
1,1,1,2,3,4,4,4-octafluoro-2- butene FC-1318cy
CF.sub.3CF.sub.2CF.dbd.CF.sub.2 1,1,2,3,3,4,4,4-octafluoro-1-
butene HFC-1327s C.sub.4HF.sub.7 HFC-1327my
CF.sub.3CF.dbd.CHCF.sub.3 1,1,1,2,4,4,4-heptafluoro-2- butene
HFC-1327ye CHF.dbd.CFCF.sub.2CF.sub.3 1,2,3,3,4,4,4-heptafluoro-1-
butene HFC-1327py CHF.sub.2CF.dbd.CFCF.sub.3
1,1,1,2,3,4,4-heptafluoro-2- butene HFC-1327et
(CF.sub.3).sub.2C.dbd.CHF 1,3,3,3-tetrafluoro-2-
(trifluoromethyl)-1-propene HFC-1327cz
CF.sub.2.dbd.CHCF.sub.2CF.sub.3 1,1,3,3,4,4,4-heptafluoro-1- butene
HFC-1327cye CF.sub.2.dbd.CFCHFCF.sub.3 1,1,2,3,4,4,4-heptafluoro-1-
butene HFC-1327cyc CF.sub.2.dbd.CFCF.sub.2CHF.sub.2
1,1,2,3,3,4,4-heptafluoro-1- butene HFC-1336s C.sub.4H.sub.2F.sub.6
HFC-1336yf CF.sub.3CF.sub.2CF.dbd.CH.sub.2
2,3,3,4,4,4-hexafluoro-1- butene HFC-1336ze
CHF.dbd.CHCF.sub.2CF.sub.3 1,3,3,4,4,4-hexafluoro-1- butene
HFC-1336eye CHF.dbd.CFCHFCF.sub.3 1,2,3,4,4,4-hexafluoro-1- butene
HFC-1336eyc CHF.dbd.CFCF.sub.2CHF.sub.2 1,2,3,3,4,4-hexafluoro-1-
butene HFC-1336pyy CHF.sub.2CF.dbd.CFCHF.sub.2
1,1,2,3,4,4-hexafluoro-2- butene HFC-1336qy
CH.sub.2FCF.dbd.CFCF.sub.3 1,1,1,2,3,4-hexafluoro-2- butene
HFC-1336pz CHF.sub.2CH.dbd.CFCF.sub.3 1,1,1,2,4,4-hexafluoro-2-
butene HFC-1336mzy CF.sub.3CH.dbd.CFCHF.sub.2
1,1,1,3,4,4-hexafluoro-2- butene HFC-1336qc
CF.sub.2.dbd.CFCF.sub.2CH.sub.2F 1,1,2,3,3,4-hexafluoro-1- butene
HFC-1336pe CF.sub.2.dbd.CFCHFCHF.sub.2 1,1,2,3,4,4-hexafluoro-1-
butene HFC-1336ft CH.sub.2.dbd.C(CF.sub.3).sub.2 3,3,3-trifluoro-2-
(trifluoromethyl)-1-propene HFC-1345s C.sub.4H.sub.3F.sub.5
HFC-1345qz CH.sub.2FCH.dbd.CFCF.sub.3 1,1,1,2,4-pentafluoro-2-
butene HFC-1345mzy CF.sub.3CH.dbd.CFCH.sub.2F
1,1,1,3,4-pentafluoro-2- butene HFC-1345fz
CF.sub.3CF.sub.2CH.dbd.CH.sub.2 3,3,4,4,4-pentafluoro-1- butene
HFC-1345mzz CHF.sub.2CH.dbd.CHCF.sub.3 1,1,1,4,4-pentafluoro-2-
butene HFC-1345sy CH.sub.3CF.dbd.CFCF.sub.3
1,1,1,2,3-pentafluoro-2- butene HFC-1345fyc
CH.sub.2.dbd.CFCF.sub.2CHF.sub.2 2,3,3,4,4-pentafluoro-1- butene
HFC-1345pyz CHF.sub.2CF.dbd.CHCHF.sub.2 1,1,2,4,4-pentafluoro-2-
butene HFC-1345cyc CH.sub.3CF.sub.2CF.dbd.CF.sub.2
1,1,2,3,3-pentafluoro-1- butene HFC-1345pyy
CH.sub.2FCF.dbd.CFCHF.sub.2 1,1,2,3,4-pentafluoro-2- butene
HFC-1345eyc CH.sub.2FCF.sub.2CF.dbd.CF.sub.2
1,2,3,3,4-pentafluoro-1- butene HFC-1345ctm
CF.sub.2.dbd.C(CF.sub.3)(CH.sub.3) 1,1,3,3,3-pentafluoro-2-
methy1-1-propene HFC-1345ftp CH.sub.2.dbd.C(CHF.sub.2)(CF.sub.3)
2-(difluoromethyl)-3,3,3- trifluoro-l-propene HFC-1354s
C.sub.4H.sub.4F.sub.4 HFC-1354fzc CH.sub.2.dbd.CHCF.sub.2CHF.sub.2
3,3,4,4-tetrafluoro-1-butene HFC-1354ctp
CF.sub.2.dbd.C(CHF.sub.2)(CH.sub.3) 1,1,3,3-tetrafluoro-2-methyl-
1-propene HFC-1354etm CHF.dbd.C(CF.sub.3)(CH.sub.3)
1,3,3,3-tetrafluoro-2-methyl- 1-propene HFC-1354tfp
CH.sub.2.dbd.C(CHF.sub.2).sub.2 2-(difluoromethyl)-3,3-
difluoro-1-propene HFC-1354my CF.sub.3CF.dbd.CFCH.sub.3
1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH.sub.3CF.dbd.CHCF.sub.3
1,1,1,3-tetrafluoro-2-butene FC-141-10s C.sub.5F.sub.10
FC-141-10myy CF.sub.3CF.dbd.CFCF.sub.2CF.sub.3 1,1,1,2,3,4,4,5,5,5-
decafluoro-2-pentene FC-141-10cy
CF.sub.2.dbd.CFCF.sub.2CF.sub.2CF.sub.3 1,1,2,3,3,4,4,5,5,5-
decafluoro-1-pentene HFC-1429s C.sub.5HF.sub.9 HFC-1429mzt
(CF.sub.3).sub.2C.dbd.CHCF.sub.3 1,1,1,4,4,4-hexafluoro-2-
(trifluoromethyl)-2-butene HFC-1429myz
CF.sub.3CF.dbd.CHCF.sub.2CF.sub.3 1,1,1,2,4,4,5,5,5-nonafluoro-
2-pentene HFC-1429mzy CF.sub.3CH.dbd.CFCF.sub.2CF.sub.3
1,1,1,3,4,4,5,5,5-nonafluoro- 2-pentene HFC-1429eyc
CHF.dbd.CFCF.sub.2CF.sub.2CF.sub.3 1,2,3,3,4,4,5,5,5-nonafluoro-
1-pentene HFC-1429czc CF.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.3
1,1,3,3,4,4,5,5,5-nonafluoro- 1-pentene HFC-1429cycc
CF.sub.2.dbd.CFCF.sub.2CF.sub.2CHF.sub.2
1,1,2,3,3,4,4,5,5-nonafluoro- 1-pentene HFC-1429pyy
CHF.sub.2CF.dbd.CFCF.sub.2CF.sub.3 1,1,2,3,4,4,5,5,5-nonafluoro-
2-pentene HFC- CF.sub.3CF.dbd.CFCF.sub.2CHF.sub.2
1,1,1,2,3,4,4,5,5-nonafluoro- 1429myyc 2-pentene HFC-
CF.sub.3CF.dbd.CFCHFCF.sub.3 1,1,1,2,3,4,5,5,5-nonafluoro- 1429myye
2-pentene HFC- CHF.dbd.CFCF(CF.sub.3).sub.2
1,2,3,4,4,4-hexafluoro-3- 1429eyym (trifluoromethyl)-1-butene HFC-
CF.sub.2.dbd.CFCH(CF.sub.3).sub.2 1,1,2,4,4,4-hexafluoro-3-
1429cyzm (trifluoromethyl)-1-butene HFC-1429mzt
CF.sub.3CH=C(CF.sub.3).sub.2 1,1,1,4,4,4-hexafluoro-3-
(trifluoromethyl)-2-butene HFC- CF.sub.2.dbd.CHCF(CF.sub.3).sub.2
1,1,3,4,4,4-hexafluoro-3- 1429czym (trifluoromethyl)-1-butene
HFC-1438s C.sub.5H.sub.2F.sub.8 HFC-1438fy
CH.sub.2.dbd.CFCF.sub.2CF2CF.sub.3 2,3,3,4,4,5,5,5-octafluoro-1-
pentene HFC- CHF.dbd.CFCF.sub.2CF.sub.2CHF.sub.2
1,2,3,3,4,4,5,5-octafluoro-1- 1438eycc pentene HFC-
CH.sub.2.dbd.C(CF.sub.3) CF.sub.2CF.sub.3 3,3,4,4,4-pentafluoro-2-
1438ftmc (trifluoromethyl)-1-butene HFC-
CF.sub.2.dbd.CHCH(CF.sub.3).sub.2 1,1,4,4,4-pentafluoro-3- 1438czzm
(trifluoromethyl)-1-butene HFC- CHF.dbd.CHCF(CF.sub.3).sub.2
1,3,4,4,4-pentafluoro-3- 1438ezym (trifluoromethyl)-1-butene HFC-
CF.sub.2.dbd.C(CF.sub.3) CH.sub.2CF.sub.3 1,1,4,4,4-pentafluoro-2-
1438ctmf (trifluoromethyl)-1-butene HFC-1447s C.sub.5H.sub.3F.sub.7
HFC-1447fzy (CF.sub.3).sub.2CFCH.dbd.CH.sub.2
3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447fz
CF.sub.3CF.sub.2CF.sub.2CH.dbd.CH.sub.2
3,3,4,4,5,5,5-heptafluoro-1- pentene HFC-1447fycc
CH.sub.2.dbd.CFCF.sub.2CF.sub.2CHF.sub.2
2,3,3,4,4,5,5-heptafluoro-1- pentene HFC-1447czcf
CF.sub.2.dbd.CHCF.sub.2CH.sub.2CF.sub.3
1,1,3,3,5,5,5-heptafluoro-1- pentene HFC-
CF.sub.3CF.dbd.C(CF.sub.3)(CH.sub.3) 1,1,1,2,4,4,4-heptafluoro-3-
1447mytm methy1-2-butene HFC-1447fyz
CH.sub.2.dbd.CFCH(CF.sub.3).sub.2 2,4,4,4-tetrafluoro-3-
(trifluoromethyl)-1-butene HFC-1447ezz CHF.dbd.CHCH(CF.sub.3).sub.2
1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447qzt
CH.sub.2FCH.dbd.C(CF.sub.3).sub.2 1,4,4,4-tetrafluoro-3-
(trifluoromethyl)-2-butene HFC-1447syt
CH.sub.3CF.dbd.C(CF.sub.3).sub.2 2,4,4,4-tetrafluoro-3-
(trifluoromethyl)-2-butene HFC-1456s C.sub.5H.sub.4F.sub.6
HFC-1456szt (CF.sub.3).sub.2C.dbd.CHCH.sub.3
3-(trifluoromethyl)-4,4,4- trifluoro-2-butene HFC-1456szy
CF.sub.3CF.sub.2CF.dbd.CHCH.sub.3 3,4,4,5,5,5-hexafluoro-2- pentene
HFC- CF.sub.3C(CH.sub.3).dbd.CHCF.sub.3 1,1,1,4,4,4-hexafluoro-2-
1456mstz methy1-2-butene HFC-1456fzce
CH.sub.2.dbd.CHCF.sub.2CHFCF.sub.3 3,3,4,5,5,5-hexafluoro-1-
pentene HFC-1456ftmf CH.sub.2.dbd.C(CF.sub.3)CH.sub.2CF.sub.3
4,4,4-trifluoro-2- (trifluoromethyl)-1-butene FC-151-12s
C.sub.6F.sub.12 FC-151-12c CF.sub.3(CF.sub.2).sub.3CF.dbd.CF.sub.2
1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene(or
perfluoro-1-hexene) FC-151-12mcy
CF.sub.3CF.sub.2CF.dbd.CFCF.sub.2CF.sub.3 1,1,1,2,2,3,4,5,5,6,6,6-
dodecafluoro-3-hexene(or perfluoro-3-hexene) FC-151-
(CF.sub.3).sub.2C.dbd.C(CF.sub.3).sub.2 1,1,1,4,4,4-hexafluoro-2,3-
12mmtt bis(trifluoromethyl)-2-butene FC-151-
(CF.sub.3).sub.2CFCF.dbd.CFCF.sub.3 1,1,1,2,3,4,5,5,5-nonafluoro-
12mmzz 4-(trifluoromethyl)-2-pentene HFC-152-11s C.sub.6HF.sub.11
HFC-152- (CF.sub.3).sub.2C.dbd.CHC.sub.2F.sub.5
1,1,1,4,4,5,5,5-octafluoro-2- 11mmtz (trifluoromethyl)-2-pentene
HFC-152- (CF.sub.3).sub.2CFCF.dbd.CHCF.sub.3
1,1,1,3,4,5,5,5-octafluoro-4- 11mmyyz (trifluoromethyl)-2-pentene
HFC-1549s C.sub.6H.sub.3F.sub.9 PFBE
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.dbd.CH.sub.2
3,3,4,4,5,5,6,6,6-nonafluoro- (or HFC- 1-hexene(or 1549fz)
perfluorobutylethylene) HFC- CH.sub.2.dbd.CHC(CF.sub.3).sub.3
4,4,4-trifluoro-3,3- 1549fztmm bis(trifluoromethyl)-1-butene HFC-
(CF.sub.3).sub.2C.dbd.C(CH.sub.3)(CF.sub.3)
1,1,1,4,4,4-hexafluoro-3- 1549mmtts methy1-2-(trifluoromethyl)-
2-butene HFC- CH.sub.2.dbd.CFCF.sub.2CH(CF.sub.3).sub.2
2,3,3,5,5,5-hexafluoro-4- 1549fycz (trifluoromethyl)-1-pentene HFC-
CF.sub.3CF.dbd.C(CH.sub.3)CF.sub.2CF.sub.3
1,1,1,2,4,4,5,5,5-nonafluoro- 1549myts 3-methy1-2-pentene HFC-
CF.sub.3CH.dbd.CHCH(CF.sub.3).sub.2 1,1,1,5,5,5-hexafluoro-4-
1549mzzz (trifluoromethyl)-2-pentene HFC-1558s
C.sub.6H.sub.4F.sub.8 HFC-1558szy
CF.sub.3CF.sub.2CF.sub.2CF.dbd.CHCH.sub.3
3,4,4,5,5,6,6,6-octafluoro-2- hexene HFC-
CH.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.2CHF.sub.2
3,3,4,4,5,5,6,6-octafluoro-2- 1558fzccc hexene HFC-
(CF.sub.3).sub.2C.dbd.CHCF.sub.2CH.sub.3 1,1,1,4,4-pentafluoro-2-
1558mmtzc (trifluoromethyl)-2-pentene HFC-
CH.sub.2.dbd.C(CF.sub.3)CH2C.sub.2F.sub.5 4,4,5,5,5-pentafluoro-2-
1558ftmf (trifluoromethyl)-1-pentene HFC-1567s
C.sub.6H.sub.5F.sub.7 HFC-1567fts
CF.sub.3CF.sub.2CF.sub.2C(CH.sub.3).dbd.CH.sub.2
3,3,4,4,5,5,5-heptafluoro-2- methyl-1-pentene HFC-1567szz
CF.sub.3CF.sub.2CF.sub.2CH.dbd.CHCH.sub.3
4,4,5,5,6,6,6-heptafluoro-2- hexene HFC-1567fzfc
CH.sub.2.dbd.CHCH.sub.2CF.sub.2C.sub.2F.sub.5
4,4,5,5,6,6,6-heptafluoro-1- hexene
HFC-1567sfyy CF.sub.3CF.sub.2CF.dbd.CFC.sub.2H.sub.5
1,1,1,2,2,3,4-heptafluoro-3- hexene HFC-1567fzfy
CH.sub.2.dbd.CHCH.sub.2CF(CF.sub.3).sub.2 4,5,5,5-tetrafluoro-4-
(trifluoromethyl)-1-pentene HFC-
CF.sub.3CF.dbd.CHCH(CF.sub.3)(CH.sub.3)
1,1,1,2,5,5,5-heptafluoro-4- 1567myzzm methyl-2-pentene HFC-
(CF.sub.3).sub.2C.dbd.CFC.sub.2H.sub.5 1,1,1,3-tetrafluoro-2-
1567mmtyf (trifluoromethyl)-2-pentene FC-161-14s C.sub.7F.sub.14
FC-161- CF.sub.3CF.dbd.CFCF.sub.2CF.sub.2C.sub.2F.sub.5
1,1,1,2,3,4,4,5,5,6,6,7,7,7- 14myy tetradecafluoro-2-heptene
FC-161- CF.sub.3CF.sub.2CF.dbd.CFCF.sub.2C.sub.2F.sub.5
1,1,1,2,2,3,4,5,5,6,6,7,7,7- 14mcyy tetradecafluoro-2-heptene
HFCs-162-13s C.sub.7HF.sub.13 HFC-162-
CF.sub.3CH.dbd.CFCF.sub.2CF.sub.2C.sub.2F.sub.5
1,1,1,3,4,4,5,5,6,6,7,7,7- 13mzy tridecafluoro-2-heptene HFC162-
CF.sub.3CF.dbd.CHCF.sub.2CF.sub.2C.sub.2F.sub.5
1,1,1,2,4,4,5,5,6,6,7,7,7- 13myz tridecafluoro-2-heptene HFC-162-
CF.sub.3CF.sub.2CH.dbd.CFCF.sub.2C.sub.2F.sub.5
1,1,1,2,2,4,5,5,6,6,7,7,7- 13mczy tridecafluoro-3-heptene HFC-162-
CF.sub.3CF.sub.2CF.dbd.CHCF.sub.2C.sub.2F.sub.5
1,1,1,2,2,3,5,5,6,6,7,7,7- 13mcyz tridecafluoro-3-heptene Cyclic
Cyclo[-CX.dbd.CY(CXY).sub.n--] fluoroolefins HFC-C1316cc
cyclo-CF.sub.2CF.sub.2CF.dbd.CF-- 1,2,3,3,4,4-
hexafluorocyclobutene HFC-C1334cc cyclo-CF.sub.2CF.sub.2CH.dbd.CH--
3,3,4,4- tetrafluorocyclobutene HFC-C1436
cyclo-CF.sub.2CF.sub.2CF.sub.2CH.dbd.CH-- 3,3,4,4,5,5,-
hexafluorocyclopentene HFC-C1418y
cyclo-CF.sub.2CF.dbd.CFCF.sub.2CF.sub.2-- 1,2,3,3,4,4,5,5-
octafluorocyclopentene FC-C151-10y cyclo- 1,2,3,3,4,4,5,5,6,6-
CF.sub.2CF.dbd.CFCF.sub.2CF.sub.2CF.sub.2--
decafluorocyclohexene
[0045] The compounds listed in Table 2 are available commercially
or may be prepared by processes known in the art.
[0046] In addition to the inventive compounds described above, the
bromine-containing fluorocarbons or hydrofluorocarbons presented in
Table 3 can be used as blowing agents.
TABLE-US-00003 TABLE 3 Structure Chemical Names
CF.sub.2.dbd.CHCF.sub.2Br 3-bromo-1,1,3,3-tetrafluoropropene
CF.sub.2.dbd.CFCBrH.sub.2 3-bromo-1,1,2-trifluoropropene
CHF.dbd.CBrCF.sub.3 2-bromo-1,3,3,3-tetrafluoropropene
CHF.dbd.CHCBrF.sub.2 3-bromo-1,3,3-trifluoropropene
CHF.dbd.CBrCHF.sub.2 2-bromo-1,3,3-trifluoropropene
CHBr.dbd.CFCF.sub.3 1-bromo-2,3,3,3-tetrafluoropropene
CHBr.dbd.CHCF.sub.3 1-bromo-3,3,3-trifluoropropene
CH.sub.2.dbd.CBrCF.sub.3 2-bromo-3,3,3-trifluoropropene
CH.sub.2.dbd.CFCBrF.sub.2 3-bromo-2,3,3-trifluoropropene
CFBr.dbd.CHCF.sub.3 1-bromo-1,3,3,3-tetrafluoropropene
CFBr.dbd.CFCF.sub.3 1-bromopentafluoropropene
CH.sub.2.dbd.CBrCF.sub.2CF.sub.3
2-bromo-3,3,4,4,4-pentafluoro-1-butene CHBr.dbd.CHCF.sub.2CF.sub.3
1-bromo-3,3,4,4,4-pentafluoro-1-butene
CH.sub.2.dbd.CHCF.sub.2CF.sub.2Br
4-bromo-3,3,4,4-tetrafluoro-1-butene CH.sub.2.dbd.CHCBrFCF.sub.3
3-bromo-3,4,4,4-tetrafluoro-1-butene CF.sub.3CBr.dbd.CFCF.sub.3
2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene
CH.sub.3CBr.dbd.CHCF.sub.3 2-bromo-4,4,4-trifluoro-2-butene
CF.sub.3CBr.dbd.CHCH.sub.3 2-bromo-1,1,1-trifluoro-2-butene
(CF.sub.3).sub.2C.dbd.CHBr
1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)- propene
CF.sub.3CF.dbd.CBrCF.sub.2CF.sub.3
3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene
E-CHF.sub.2CBr.dbd.CFC.sub.2F.sub.5
E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene
Z-CHF.sub.2CBr.dbd.CFC.sub.2F.sub.5
Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene
CF.sub.2.dbd.CBrCHFC.sub.2F.sub.5
2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene
CHBr.dbd.CF(CF.sub.2).sub.2CHF.sub.2
1-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene
CH.sub.2.dbd.CBrCF.sub.2C.sub.2F.sub.5
2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene
CF.sub.2.dbd.CHCF.sub.2CH.sub.2CBrF.sub.2
5-bromo-1,1,3,3,5,5-hexafluoro-1-pentene
(CF.sub.3).sub.2CFCBr.dbd.CH.sub.2
2-bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene
CF.sub.2.dbd.C(CH.sub.2Br)CF.sub.3
2-(bromomethyl)-1,1,3,3,3-pentafluoropropene
CH.sub.2.dbd.C(CBrF.sub.2)CF.sub.3
2-(bromodifluoromethyl)-3,3,3-trifluoropropene
(CF.sub.3).sub.2CHCH.dbd.CHBr
1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1- butene
(CF.sub.3).sub.2C.dbd.CHCH.sub.2Br
4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2- butene
CH.sub.2.dbd.CHCF(CF.sub.3)CBrF.sub.2
3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1- butene
CF.sub.3CF.sub.2CF.sub.2CBr.dbd.CH.sub.2
2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene
CF.sub.3(CF.sub.2).sub.3CBr.dbd.CH.sub.2
2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene
[0047] The compounds listed in Table 3 are available commercially
or may be prepared by processes known in the art.
[0048] 1-Bromo-3,3,4,4,4-pentafluoro-1-butene may be prepared by a
three step sequence beginning with reaction of phosphorous
tribromide with 3,3,4,4,4-pentafluoro-1-butanol to give
4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of
4-bromo-1,1,1,2,2-pentafluorobutane at 350-400.degree. C. gives
4,4-dibromo-1,1,1,2,2-pentafluorobutane which may in turn be heated
with powdered potassium hydroxide to give the desired
bromobutene.
[0049] 2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may
be prepared by addition of bromine to
3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene followed by
treatment of the resulting dibromide with ethanolic potassium
hydroxide.
[0050] Many of the compounds of Formula I, Table 1, Table 2 and
Table 3 exist as different configurational isomers or
stereoisomers. When the specific isomer is not designated, the
present disclosure is intended to include all single
configurational isomers, single stereoisomers, or any combination
thereof. For instance, CF.sub.3CH.dbd.CHCF.sub.3 is meant to
represent the E-isomer, Z-isomer, or any combination or mixture of
both isomers in any ratio. Another example is
C.sub.2F.sub.5CF.sub.2CH.dbd.CH--CF.sub.2C.sub.2F.sub.5, by which
is represented the E-isomer, Z-isomer, or any combination or
mixture of both isomers in any ratio.
[0051] HFC-1225ye may exist as one of two configurational isomers,
E or Z. HFC-1225ye as used herein refers to the isomers,
E-HFC-1225ye (CAS reg no. 5595-10-8) or Z--HFC-1225ye (CAS reg. no.
5528-43-8), as well as any combinations or mixtures of such
isomers.
[0052] Blowing agents can comprise a single compound as listed, for
example, in Table 2, or may comprise a combination of compounds
from Table 2 or, alternatively, a combination of compounds from
Table 1, Table 2, Table 3, and/or Formula I.
[0053] The amount of the fluorocarbons (FCs) or HFCs contained in
the present compositions (from, e.g., Formula I, Table 1, or Table
2, or Table 3) can vary widely, depending the particular
application, and compositions containing more than trace amounts
and less than 100% of the compound are within broad the scope of
the present disclosure.
[0054] The compositions disclosed herein may be prepared by any
convenient method to combine the desired amounts of the individual
components. A preferred method is to weigh the desired component
amounts and thereafter combine the components in an appropriate
vessel. Agitation may be used, if desired.
[0055] Other embodiments provide foamable compositions, and
preferably thermoset or thermoplastic foam compositions, prepared
using the compositions of the present disclosure. In such foam
embodiments, one or more of the present compositions are included
as or part of a blowing agent in a foamable composition, which
composition preferably includes one or more additional components
capable of reacting and/or foaming under the proper conditions to
form a foam or cellular structure. Another aspect relates to foam,
and preferably closed cell foam, prepared from a polymer foam
formulation containing a blowing agent comprising the compositions
of the present disclosure.
[0056] The present disclosure further relates to a method for
replacing or substituting for the blowing agent in a foamable
composition having a GWP of about 150 or more, or a high GWP
blowing agent, with a composition having a lower GWP. One method
comprises providing a composition comprising at least one
fluoroolefin of the present invention as the replacement. In
another embodiment of the present invention the foamable
composition of the present invention, having a lower GWP than the
composition being replaced or substituted is used to produce
thermoplastic or thermoset foams. Global warming potentials (GWPs)
are an index for estimating relative global warming contribution
due to atmospheric emission of a kilogram of a particular
greenhouse gas compared to emission of a kilogram of carbon
dioxide. GWP can be calculated for different time horizons showing
the effect of atmospheric lifetime for a given gas. The GWP for the
100 year time horizon is commonly the value referenced.
[0057] A high GWP blowing agent would be any compound capable of
functioning as a blowing agent having a GWP at the 100 year time
horizon of about 1000 or greater, alternatively 500 or greater, 150
or greater, 100 or greater, or 50 or greater. Foam expansion agents
that are in need of replacement, based upon GWP calculations
published by the Intergovernmental Panel on Climate Change (IPCC),
include but are not limited to HFC-134a and HFC-227ea.
[0058] The present disclosure will provide compositions that have
zero or low ozone depletion potential and low global warming
potential (GWP). The fluoroolefins of the present invention or
mixtures of fluoroolefins of this invention with other blowing
agents or foamable compositions will have global warming potentials
that are less than many hydrofluorocarbon blowing agents or
foamable compositions currently in use. Typically, the
fluoroolefins of the present invention are expected to have GWP of
less than about 25. One aspect of the present invention is to
provide a blowing agent with a global warming potential of less
than 1000, less than 500, less than 150, less than 100, or less
than 50. Another aspect of the present invention is to reduce the
net GWP of foamable compositions by adding fluoroolefins to said
mixtures.
[0059] The present invention further relates to a method for
lowering the GWP of the methods for manufacturing open, closed and
multi-modal foams, said method comprising combining at least one
fluoroolefin of the present invention with a resin (for
thermoplastic foams) or into a B-side mixture (thermoplastic) to
produce a foamable composition with a GWP of lower than 25. The GWP
of may be determined that the GWP of a mixture or combination of
compounds may be calculated as a weighted average of the GWP for
each of the pure compounds.
[0060] The present compositions also preferably have an Ozone
Depletion Potential (ODP) of not greater than 0.05, more preferably
not greater than 0.02 and even more preferably about zero. As used
herein, "ODP" is as defined in "The Scientific Assessment of Ozone
Depletion, 2002, A report of the World Meteorological Association's
Global Ozone Research and Monitoring Project," which is
incorporated herein by reference.
[0061] Certain embodiments provide foam premixes, foamable
compositions, and preferably polyurethane or polyisocyanate foam
compositions, and methods of preparing foams. In such foam
embodiments, one or more of the compositions of the present
disclosure are included as a blowing agent in a foamable
composition, which foamable composition preferably includes one or
more additional components capable of reacting and/or foaming under
the proper conditions to form a foam or cellular structure. Any of
the methods well known in the art, such as those described in
"Polyurethanes Chemistry and Technology," Volumes I and II,
Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y.,
which is incorporated herein by reference, may be used or adapted
for use in accordance with the foam embodiments.
[0062] In certain embodiments, it is often desirable to employ
certain other ingredients in preparing foams. Among these
additional ingredients are catalysts, surfactants, flame
retardants, preservatives, colorants, antioxidants, reinforcing
agents, filler, antistatic agents, nucleating agents and the
like.
[0063] Polyurethane foams are generally prepared by combining and
reacting an isocyanate with a polyol in the presence of a blowing
or expanding agent and auxiliary chemicals added to control and
modify both the polyurethane reaction itself and the properties of
the final polymer. For processing convenience, these materials can
be premixed into two non-reacting parts typically referred to as
the "A-side" and the "B-side".
[0064] The term "B-side" is intended to mean polyol or polyol
containing mixture. A polyol containing mixture usually includes
the polyol, the blowing or expanding agent and auxiliary chemicals,
like catalysts, surfactants, stabilizers, chain extenders,
cross-linkers, water, fire retardants, smoke suppressants,
pigments, coloring materials, fillers, etc.
[0065] The term "A-side" is intended to mean isocyanate or
isocyanate containing mixture. An isocyanate containing mixture may
include the isocyanate, the blowing or expanding agent and
auxiliary chemicals, like catalysts, surfactants, stabilizers,
chain extenders, cross-linkers, water, fire retardants, smoke
suppressants, pigments, coloring materials, fillers, etc.
[0066] To prepare the foam, appropriate amounts of A-side and
B-side are then combined to react.
[0067] When preparing a foam by a process disclosed herein, it is
generally preferred to employ a minor amount of a surfactant to
stabilize the foaming reaction mixture until it cures. Such
surfactants may comprise a liquid or solid organosilicone compound.
Other, less preferred surfactants include polyethylene glycol
ethers of long chain alcohols, tertiary amine or alkanolamine salts
of long chain alkyl acid sulfate esters, alkyl sulfonic esters and
alkyl arylsulfonic acids. The surfactants are employed in amounts
sufficient to stabilize the foaming reaction mixture against
collapse and to prevent the formation of large, uneven cells. About
0.2 to about 5 parts or even more of the surfactant per 100 parts
by weight of polyol are usually sufficient.
[0068] One or more catalysts for the reaction of the polyol with
the polyisocyanate may also be used. Any suitable urethane catalyst
may be used, including tertiary amine compounds and organometallic
compounds. Such catalysts are used in an amount which measurably
increases the rate of reaction of the polyisocyanate. Typical
amounts are about 0.1 to about 5 parts of catalyst per 100 parts by
weight of polyol.
[0069] Useful flame retardants include, for example,
tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,
tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl)
phosphate, diammonium phosphate, various halogenated aromatic
compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride,
and the like.
[0070] The methods of forming a foam generally comprise providing a
blowing agent composition of the present disclosure, adding
(directly or indirectly) the blowing agent composition to a
foamable composition, and reacting the foamable composition under
the conditions effective to form a foam or cellular structure. Any
of the methods well known in the art, such as those described in
"Polyurethanes Chemistry and Technology," Volumes I and II,
Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y.,
which is incorporated herein by reference, may be used or adapted
for use in accordance with the foam embodiments.
[0071] Polyisocyanate-based foams are prepared, e.g., by reacting
at least one organic polyisocyanate with at least one active
hydrogen-containing compound in the presence of the blowing agent
composition described herein-above.
[0072] An isocyanate reactive composition can be prepared by
blending at least one active hydrogen-containing compound with the
blowing agent composition. Advantageously, the blend contains at
least 1 and up to 50, preferably up to 25 weight percent of the
blowing agent composition, based on the total weight of active
hydrogen-containing compound and blowing agent composition.
[0073] Active hydrogen-containing compounds include those materials
having two or more groups which contain an active hydrogen atom
which reacts with an isocyanate. Preferred among such compounds are
materials having at least two hydroxyl, primary or secondary amine,
carboxylic acid, or thiol groups per molecule. Polyols, i.e.,
compounds having at least two hydroxyl groups per molecule, are
especially preferred due to their desirable reactivity with
polyisocyanates.
[0074] Additional examples of suitable active hydrogen containing
compounds can be found in U.S. Pat. No. 6,590,005, incorporated
herein by reference. For example, suitable polyester polyols
include those prepared by reacting a carboxylic acid and/or a
derivative thereof or a polycarboxylic anhydride with a polyhydric
alcohol. The polycarboxylic acids may be any of the known
aliphatic, cycloaliphatic, aromatic, and/or heterocyclic
polycarboxylic acids and may be substituted, (e.g., with halogen
atoms) and/or unsaturated. Examples of suitable polycarboxylic
acids and anhydrides include oxalic acid, malonic acid, glutaric
acid, pimelic acid, succinic acid, adipic acid, suberic acid,
azelaic acid, sebacic acid, phthalic acid, isophthalic acid,
terephthalic acid, trimellitic acid, trimellitic acid anhydride,
pyromellitic dianhydride, phthalic acid anhydride,
tetrahydrophthalic acid anhydride, hexahydrophthalic acid
anhydride, endomethylene tetrahydrophthalic acid anhydride,
glutaric acid anhydride acid, maleic acid, maleic acid anhydride,
fumaric acid, and dimeric and trimeric fatty acids, such as those
of oleic acid which may be in admixture with monomeric fatty acids.
Simple esters of polycarboxylic acids may also be used such as
terephthalic acid dimethylester, terephthalic acid bisglycol and
extracts thereof. The polyhydric alcohols suitable for the
preparation of polyester polyols may be aliphatic, cycloaliphatic,
aromatic, and/or heterocyclic. The polyhydric alcohols optionally
may include substituents which are inert in the reaction, for
example, chlorine and bromine substituents, and/or may be
unsaturated. Suitable amino alcohols, such as monoethanolamine,
diethanolamine or the like may also be used. Examples of suitable
polyhydric alcohols include ethylene glycol, propylene glycol,
polyoxyalkylene glycols (such as diethylene glycol, polyethylene
glycol, dipropylene glycol and polypropylene glycol), glycerol and
trimethylolpropane.
[0075] Suitable additional isocyanate-reactive materials include
polyether polyols, polyester polyols, polyhydroxy-terminated acetal
resins, hydroxyl-terminated amines and polyamines, and the like.
These additional isocyanate-reactive materials include hydrogen
terminated polythioethers, polyamides, polyester amides,
polycarbonates, polyacetals, polyolefins, polysiloxanes, and
polymer polyols.
[0076] Other polyols include alkylene oxide derivatives of Mannich
condensates, and aminoalkylpiperazine-initiated polyethers as
described in U.S. Pat. Nos. 4,704,410 and 4,704,411. The low
hydroxyl number, high equivalent weight alkylene oxide adducts of
carbohydrate initiators such as sucrose and sorbitol may also be
used.
[0077] In the process of making a polyisocyanate-based foam, the
polyol(s), polyisocyanate and other components are contacted,
thoroughly mixed and permitted to expand and cure into a cellular
polymer. The particular mixing apparatus is not critical, and
various types of mixing head and spray apparatus are conveniently
used. It is often convenient, but not necessary, to preblend
certain of the raw materials prior to reacting the polyisocyanate
and active hydrogen-containing components. For example, it is often
useful to blend the polyol(s), blowing agent, surfactant(s),
catalyst(s) and other components except for polyisocyanates, and
then contact this mixture with the polyisocyanate. Alternatively,
all the components may be introduced individually to the mixing
zone where the polyisocyanate and polyol(s) are contacted. It is
also possible to pre-react all or a portion of the polyol(s) with
the polyisocyanate to form a prepolymer.
[0078] The quantity of blowing agent composition employed when
preparing a foam is sufficient to give a desired density to the
foam. Advantageously, sufficient blowing agent is employed to
provide a polyurethane foam having an overall density of from about
10 to about 500, preferably from about 18 to about 100 kg/m.sup.3
(1 kg/m.sup.3=0.062 lb./ft..sup.3).
[0079] It is often convenient to preblend the blowing agent
composition with the active hydrogen-containing compound before
contacting the resulting blend with the polyisocyanate. It is also
possible to simultaneously blend together the polyisocyanate,
active hydrogen-containing compound and blowing agent composition
in one operation resulting in the production of
polyisocyanate-based foam. Preferably the blowing agent composition
is blended with the active hydrogen-containing compound before
contacting with the polyisocyanate.
[0080] One aspect is for a rigid, closed-celled
polyisocyanate-based foam. It is prepared by contacting an organic
polyisocyanate with an active hydrogen-containing compound in the
presence of the blowing agent composition characterized in that the
so-prepared foam contains within its cells gaseous blowing
agents.
[0081] The rigid closed-cell celled polyisocyanate-based foams are
useful in spray insulation, as foam-in-place appliance foams, rigid
insulating board stock, or in laminates.
[0082] In addition, according to certain embodiments, the blowing
agents are used to blow thermoplastic foams, such as polystyrene,
polyethylene foams, including low-density polyethylene foams, or
polypropylene foams. Any of a wide range of conventional methods
for blowing such thermoplastic foams can be adapted for use
herein.
[0083] Another embodiment provides a foamable composition
comprising thermoplastic foams, such as polystyrene, polyethylene
(PE), preferably low density PE, or polypropylene (PP).
[0084] The thermoplastic foam bodies are conveniently produced by
using conventional equipment comprising an extruder and associated
means for (1) melting the resin; (2) homogeneously blending the
blowing agent composition with the melt to form a plasticized mass
at nonfoaming temperatures and pressures; (3) passing the
plasticized mass at a controlled rate, temperature and pressure
through a die having a desired shape, e.g., slit die for producing
rectangular slabs of foam board having desired thickness and
surface area, into an expansion zone; (4) allowing the extrudate to
foam in the expansion zone maintainable at suitable temperatures
and low pressures; (5) maintaining the expanding extrudate under
such temperatures and pressures for a time sufficient for the
viscosity of the extrudate to increase such that the cell size and
density of the foam remain substantially unchanged and
substantially free of ruptured cells at ambient temperature; e.g.,
25.degree. C. and atmospheric pressure; and (6) recovering the
extruded foam body.
[0085] When preparing foams, it is often desirable to add a
nucleating agent or other additives into the resin. Nucleating
agents serve primarily to increase cell count and decrease cell
size in the foam, and may be used in an amount of about 0.1 to
about 10 parts by weight per 100 parts by weight of the resin.
Typical nucleating agents comprise at lease one member selected
from the group consisting of talc, sodium bicarbonate-citric acid
mixtures, calcium silicate, carbon dioxide, among others.
[0086] In one aspect, the foaming amount of the blowing agent is in
the range of from about 1 to about 30 weight percent based on the
total weight of the resin plus blowing agent mixture, typically
about 2 to 20 weight percent, and normally about 2 to about 10
weight percent. The lower the concentration of blowing agent, the
greater the density of the resulting foam. The proper amount of
blowing agent or resultant characteristics of the foam for any
desired end-use is readily determined by a skilled person in this
art. The resin is melted at a temperature of about 200 to about
235.degree. C. depending upon the grade employed, and at nonfoaming
pressures of about 600 psig or higher. The plasticized
resin-blowing agent mixture is cooled under nonfoaming pressure to
a temperature of about 115 to 150.degree. C., normally 130.degree.
C., and extruded into the expansion zone at or below ambient
temperature and at or below atmospheric pressure.
[0087] Representative foamed products that can be made in
accordance with the present disclosure include, for example: (1)
polystyrene foam sheet for the production of disposable
thermoformed packaging materials; e.g., as disclosed in York, U.S.
Pat. No. 5,204,169; (2) extruded polystyrene foam boards for use as
residential and industrial sheathing and roofing materials, which
may be from about 0.5 to 6 inches (1.25 to 15 cm) thick, up to 4
feet (122 cm) wide, with cross-sectional areas of from 0.17 to 3
square feet (0.016 to 0.28 square meter), and up to 27 feet (813
meters) long, with densities of from about 1.5 to 10 pounds per
cubic foot (pcf) (25 to 160 kilograms per cubic meter (kg/m.sup.3);
(3) expandable foams in the form of large billets which may be up
to about 2 feet (61 cm) thick, often at least 1.5 feet 46 cm)
thick, up to 4 feet (1.22 meters) wide, up to 16 feet (4.8 meters)
long, having a cross-sectional area of about 2 to 8 square feet
(0.19 to 0.74 square meter) and a density of from 6 to 15 pcf (96
to 240 kg/m.sup.3). Such foamed products are more fully described
by Stockdopole and Welsh in the Encyclopedia of Polymer Science and
Engineering, vol. 16, pages 193-205, John Wiley & Sons, 1989;
hereby incorporated by reference.
[0088] All of the compositions and methods disclosed and claimed
herein can be made and executed without undue experimentation in
light of the present disclosure. While the compositions and methods
of this disclosure have been described in terms of preferred
embodiments, it will be apparent to those of skill in the art that
variations may be applied to the compositions and methods and in
the steps or in the sequence of steps of the method described
herein without departing from the concept, spirit, and scope of the
present disclosure. More specifically, it will be apparent that
certain agents which are chemically related may be substituted for
the agents described herein while the same or similar results would
be achieved. All such similar substitutes and modifications
apparent to those skilled in the art are deemed to be within the
spirit, scope, and concept of the present disclosure as defined by
the appended claims.
EXAMPLES
[0089] The present disclosure is further defined in the following
Examples. It should be understood that these Examples, while
indicating preferred embodiments, are given by way of illustration
only. From the above discussion and these Examples, one skilled in
the art can ascertain the preferred features, and without departing
from the spirit and scope thereof, can make various changes and
modifications to adapt it to various uses and conditions.
Example 1
Synthesis of 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene
(F14E)
Synthesis of C.sub.4F.sub.9CH.sub.2CHICF.sub.3
[0090] Perfluoro-n-butyliodide (180.1 gm, 0.52 moles) and
3,3,3-trifluoropropene (25.0 gm, 0.26 moles) were added to a 400 ml
HasteHoy.TM. shaker tube and heated to 200.degree. C. for 8 hours
under autogenous pressure, which increased to a maximum of 428 PSI.
The product was collected at room temperature. The above reaction
was carried out again at these conditions and the products
combined. It was then repeated doubling the amount of
perfluoro-n-butyliodide and 3,3,3-trifluoropropene in the same 400
ml reactor. In this case the pressure increased to 573 PSI. The
products of the three reactions were combined and distilled to give
322.4 gm of C.sub.4F.sub.9CH.sub.2CHICF.sub.3 (52.2.degree./35 mm)
in 70% yield.
Conversion of C.sub.4F.sub.9CH.sub.2CHICF.sub.3 to F14E
[0091] C.sub.4F.sub.9CH.sub.2CHICF.sub.3 (322.4 gm, 0.73 moles) was
added dropwise via addition funnel to a 2 L round bottom flask
equipped with stir a bar and connected to a packed distillation
column and still head. The flask contained isopropyl alcohol (95
ml), KOH (303.7 gm, 0.54 moles) and water (303 ml). Product was
collected, washed with sodium metabisulfite, water, dried with
MgSO.sub.4 and distilled through a 6'' column filled with glass
helices. The product, F14E (173.4 gm, 76%) boils at 78.2.degree. C.
It was characterized by .sup.19F NMR (.delta.-66.7 (CF.sub.3, m,
3F), -81.7 (CF.sub.3, m 3F), -124.8 (CF.sub.2, m, 2F), -126.4
(CF.sub.2, m, 2F), and -114.9 ppm (CF.sub.2, m, 2F)) .sup.1H NMR
(.delta. 6.4{tilde over (5)}) in chloroform-d solution.
Example 2
Synthesis of 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene
(F24E)
Synthesis of C.sub.4F.sub.9CHICH.sub.2C.sub.2F.sub.5
[0092] Perfluoroethyliodide (220 gm, 0.895 mole) and
3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (123 gm, 0.50 mole) were
added to a 400 ml HasteHoy.TM. shaker tube and heated to
200.degree. C. for 10 hours under autogenous pressure. The product
from this and two others carried out under similar conditions were
combined and washed with two 200 mL portions of 10 wt % aqueous
sodium bisulfite. The organic phase was dried over calcium chloride
and then distilled to give 277.4 gm of
C.sub.4F.sub.9CH.sub.2CHICF.sub.3 (79-81.degree. C./67-68 mm Hg) in
37% yield.
Conversion of C.sub.4F.sub.9CHICH.sub.2C.sub.2F.sub.5 to F24E
[0093] A 1 L round bottom flask equipped with a mechanical stirrer,
addition funnel, condenser, and thermocouple was charged with
C.sub.4F.sub.9CHICH.sub.2C.sub.2F.sub.5 (277.4 gm, 0.56 moles) and
isopropanol (217.8 g). The addition funnel was charged with a
solution of potassium hydroxide (74.5 g, 1.13 moles) dissolved in
83.8 g of water. The KOH solution was added dropwise to the flask
with rapid stirring over the course of about one hour as the
temperature slowly increased from 21.degree. C. to 42.degree. C.
The reaction mass was diluted with water and the product recovered
by phase separation. The product was washed with 50 mL portions of
10 wt % aqueous sodium bisulfite and water, dried over calcium
chloride, and then distilled at atmospheric pressure. The product,
F24E (128.7 gm, 63%) boils at 95.5.degree. C. It was characterized
by .sup.19F NMR (.delta. -81.6 (CF.sub.3, m, 3F), -85.4 (CF.sub.3,
m 3F), -114.7 (CF.sub.2, m, 2F), -118.1 (CF.sub.2, m, 2F), -124.8
ppm (CF.sub.2, m, 2F), -126.3 ppm (CF.sub.2, m, 2F)) and .sup.1H
NMR (.delta.6.48) in chloroform-d solution.
Example 3
Synthesis oc CF.sub.3CH.dbd.CHCF(CF.sub.3).sub.2
Synthesis of CF.sub.3CHICH.sub.2CF(CF.sub.3).sub.2
[0094] (CF.sub.3).sub.2CFI (265 gm, 0.9 moles) and
3,3,3-trifluoropropene (44.0 gm, 0.45 moles) were added to a 400 ml
Hastelloy shaker tube and heated to 200.degree. C. for 8 hours
under autogenous pressure, which increased to a maximum of 585 psi.
The product was collected at room temperature to give 110 gm of
(CF.sub.3).sub.2CFCH.sub.2CHICF.sub.3 (76-77.degree. C./200 mm) in
62% yield.
Conversion of (CF.sub.3).sub.2CFCH.sub.2CHICF.sub.3 to F13iE
[0095] (CF.sub.3).sub.2CFCH.sub.2CHICF.sub.3 (109 gm, 0.28 moles)
was slowly added dropwise via addition funnel to a 500 ml round
bottom flask heated to 42.degree. C. equipped with stir a bar and
connected to a short path distillation column and dry ice trap. The
flask contained isopropyl alcohol (50 ml), KOH (109 gm, 1.96 moles)
and water (109 ml). During the addition, the temperature increased
from 42 to 55.degree. C. After refluxing for 30 minutes, the
temperature in the flask increased to 62.degree. C. Product was
collected, washed with water, dried with MgSO.sub.4 and distilled.
The product, F13iE (41 gm, 55%), boils at 48-50.degree. C. and was
characterized by .sup.19F NMR (.delta. -187.6 (CF, m 1F), -77.1
(CF3, m 6F), -66.3 (CF3, m 3F) in chloroform-d solution.
Polyisocyanate-Based Foam Examples
[0096] To demonstrate effectiveness of unsaturated fluorocarbon
blowing agents, polyurethane and polyisocyanurate foam samples were
prepared by hand-mixing, using the two basic polyurethane foam
formulations described in Example 4 and Example 5 below. The
blowing agents may be generally premixed with the polyol or B-side
for convenience. Foams may be prepared either as free-rise or
molded samples. For free-rise foams, the reaction mixture is poured
into an open, round cardboard container. For molded foams, the
reaction mixture is poured into a 21/2''.times.13''.times.15''
(6.35 cm.times.30.02 cm.times.38.1 cm) heated aluminum mold.
Example 4
Polyisocyanurate Foam
TABLE-US-00004 [0097] Component Parts by Weight aromatic polyester
polyol (Stepanpol .RTM. 120 PS-2502A) polysiloxane surfactant
(Dabco DC- 1.8 193) potassium octanoate catalyst 3.2 (Hexcem 977)
Tris-2,4,6- 0.4 (dimethylaminomethyl)phenol/Bis(di-
methylaminomethyl)phenol catalyst (Dabco TMR 30)
1,1,1,4,4,5,5,5,Octafluooro-2-pentene 80 (HFC-1438mzz) (Blowing
Agent) polymethylene polyphenylisocyanate 190 isocyanate (Papi
.RTM. 580)
[0098] All components except the isocyanate were premixed as a
B-side. The isocyanate (A-side) was then added and mixed with a
mechanical stirrer for 10 seconds. The foam reaction mixture was
poured into a closed aluminum mold warmed to about 100.degree. F.
and allowed to expand. When cured, a 1''.times.1''.times.12''
sample was cut from the core of the molded foam.
[0099] The core sample was about 2.2 pounds/ft.sup.3 (PCF) (35.2
kg/m.sup.3) density, had an exceptionally fine cell structure, and
remained dimensionally stable. Magnified photographs of the foam
showed a uniform, highly closed cell structure and cell sizes about
200-300 microns (.mu.). Using a LaserComp FOX 304 Thermal
Conductivity Meter, initial insulation value (R-value) was measured
at 7.4/inch (thermal conductivity of 19.5 milliW/(mK) at a mean
temperature of 24.0.degree. C. or 0.135 BTU-in/hr-ft.sup.2-.degree.
F. at a mean temperature of 75.2.degree. F.).
Example 5
Polyurethane Pour-in-Place Foam
TABLE-US-00005 [0100] Component Parts by Weight sucrose/glycerine
initiated polyether 140 polyol (Voranol .RTM. 360) silicone
surfactant (Witco L-6900) 3.0 N,N-Dimethylcyclohexylamine 1.7
catalyst (Polycat 8) pentamethyldiethylenetriamine 0.4 catalyst
(Polycat 5) 2-Methyl(n-methyl amino b-sodium 0.5 acetate nonyl
phenol) catalyst (Curithane .RTM. 52) Water 2.1 Blowing Agent 70
1,1,1,4,4,5,5,5,Octafluooro-2-pentene (HFC-1438mzz) polymethylene
polyphenylisocyanate 169 isocyanate (Papi .RTM. 27)
[0101] All components except the isocyanate were premixed as a
B-side. The isocyanate (A-side) was then added and mixed with a
mechanical stirrer for 10 seconds. The foam reaction mixture was
poured into a closed aluminum mold warmed to about 100.degree. F.
and allowed to expand. When cured, a 1''.times.1''.times.12''
sample was cut from the core of the molded foam.
[0102] The core sample was about 2.0 pounds/ft.sup.3 (PCF) (32.0
kg/m.sup.3) density, had a good cell structure though it did
contain some voids, and remained dimensionally stable. Magnified
photographs of the foam showed a uniform, highly closed cell
structure, excluding the voids, and cell sizes about 200-300
microns (.mu.). Using a LaserComp FOX 304 Thermal Conductivity
Meter, initial insulation value was measured at 4.9/inch (29.5
milliW/(mK) at a mean temperature of 24.0.degree. C. or thermal
conductivity of 0.2044 BTU-in/hr-ft.sup.2-.degree. F. at a mean
temperature of 75.2.degree. F.),
Example 6
Polyisocyanurate Foam
TABLE-US-00006 [0103] Component Parts by Weight aromatic polyester
polyol 14.4 (Stepanpol .RTM. PS-2502A) polysiloxane surfactant 0.42
(Dabco DC-193) Potassium octanoate catalyst 0.8 (Hexcem 977)
Tris-2,4,6-(dimethylaminomethyl)phenol/Bis(di- 0.15
methylaminomethyl)phenol catalyst (Dabco TMR 30) 1,1,1,4,4,4
Hexafluooro-2-butene 12.0 (HFC-1336mzz, Z-isomer) (Blowing Agent)
polymethylene polyphenylisocyanate isocyanate 22.8 (Papi .RTM.
580)
[0104] All components except the isocyanate were premixed as a
B-side. The isocyanate (A-side) was then added and hand-mixed for
about 30 seconds. The foam reaction mixture was allowed to rise in
the beaker. The blowing agent mixed well with the B-side and foamed
the polymer. Foam density was initially high because the catalyst
amounts and ratio were not optimal for the HFC-1336mzz boiling
point, and the amounts of catalyst were adjusted to decrease
density.
Example 7
Blowing Agent Solubility Effect on Foam Cell structure
[0105] These unsaturated fluorocarbons offer an advantage of
improved foam cell structure because their solubility is different
than other typically used blowing agents. Their reduced solubility
in the B-side requires proper mixing, but once mixed, they
demonstrate a good affinity for the B-side, and being somewhat
insoluble, act to help seed small cell growth during the foaming
reaction.
[0106] This was observed in preparing the foam examples 4 and 5,
above. In the case of example 4, the blowing agent (HFC-1438mzz)
was mixed in the B-side until a mousse-like consistency was
obtained. At that point, the blowing agent was well dispersed in
the B-side, with no loss upon sitting at room temperature. When
this B-side mixture was foamed, it resulted in the exceptionally
fine cell structure described above, and contributed to the high
R-value.
[0107] In example 5, the blowing agent was not mixed as thoroughly
in the B-side. In this case, voids were observed in the foam, but
the cell structure excluding the voids remained small and
consistent. The resultant insulation value was acceptable despite
the voids, demonstrating that these unsaturated fluorocarbons can
improve cell structure and foam properties such as to overcome
potential processing difficulties that otherwise would
detrimentally impact foam performance.
Thermoplastic Foam Examples
Example 8
[0108] The following example serves to illustrate the ability to
use unsaturated fluorocarbon blowing agents to produce
thermoplastic foam insulation, specifically a polystyrene
insulation foam, with fine, uniform cell structure, long-term
insulation value, and good dimensional stability.
[0109] To produce polystyrene foam insulation board, a commercial
tandem extruder equipped with die, designed for insulation board
foam, is used. Such a configuration employs a primary extruder and
a secondary extruder, with a slit die. A typical polystyrene resin
would be Shell NX600 general purpose, 2.5 melt index, and a typical
nucleator would be magnesium silicate talc.
TABLE-US-00007 TABLE 4 Typical Extruder Operating Parameters
Primary extruder (rpm) 70 Extrusion rate (kg/hr) 430 Blowing agent
rate (kg/hr) 46.5 Blowing agent concentration (wt %) 10.8 Nucleator
concentration (wt %) 0.6 Secondary extruder speed (rpm) 4.9 Die
pressure (psig) 1484 Melt temperature (.degree. C.) 129 Die gap
(mm) 1.9 Die width (mm) 100 Foam thickness (mm) 52 Foam width (mm)
317 Foam density (kg/m.sup.3) 30.5
Example 9
[0110] In this example, polystyrene foam sheet is prepared using
unsaturated fluorocarbons as the blowing agent. The polystyrene
foam sheet is ultimately thermoformed into food service packaging,
like egg cartons, hamburger cartons, meat trays, plates, etc.
[0111] Foam sheet is produced using a conventional tandem extrusion
system. Foam is extruded through an annular die, stretched over a
mandrel about 4 times the die's diameter, and slit to produce a
single sheet.
[0112] A typical formulation is:
[0113] 88 to 97 wt. percent polystyrene resin
[0114] 2 to 8 wt. percent unsaturated fluorocarbon blowing
agent
[0115] 1 to 4 wt. percent nucleating agent
[0116] The polystyrene sheet is typically extruded to a thickness
of 50 to 300 mils and at a rate of approximately 1,000 pounds of
plastic per hour. Typical extruder conditions range from 1,000 to
4,000 psi (70.3 kg/cm to 281.3 kg/cm) and 200.degree. F. to
400.degree. F. (93.3.degree. C. to 204.4.degree. C.). The blowing
agent concentration in the feed material will change depending on
the desired thickness (thicker product requires more blowing
agent). Once the polystyrene has been extruded, it is typically
aged between 3 days to 2 weeks. During this time, it is stored in
rolls in a warehouse. Some blowing agent permeates out of the foam
at this time, but at a relatively slow rate.
[0117] After storage, the rolls of foam are thermoformed, producing
the desired type of end-product (e.g., clam-shell containers,
plates, etc.).
Example 10
[0118] Experiments were conducted to assess the stability of
HFC-1225ye for thermoplastic foams. 1,2,3,3,3-pentafluoro-1-propene
(HFC-1225ye), 1,1-difluoroethane (HFC-152a) and
1,1,1,2-tetrafluoroethane (HFC-134a) were all analyzed by GC/MS
prior to the testing and were found to be 100% pure. Polystyrene,
talc nucleator, a 1010 Mild Steel Coupon, and air was heated to
260.degree. C. in a pressure vessel with blowing agent and held 24
hours. After 24 hours, the vessel was cooled and all gaseous
products were collected from the vessel for analysis.
TABLE-US-00008 GC/MS Analysis of Gases after Exposure to
260.degree. C. for 24 Hours Sample Number 24a 24b 24c 32b 39c 32a
39b 39d 22 24d 39a Composition in Wt %: Polystyrene 90 90 87 87 87
87 87 87 87 87 87 Mistron Vapor 3 3 3 3 3 3 Magnesium Silicate Talc
Safoam .RTM. FPN3 (sodium 3 3 3 salts of carbonic &
polycarboxylic acids) HFC-1225ye 10 10 10 10 10 10 10 10 HFC-152a
10 10 HFC-134a 10 1010 Mild Steel Coupon x x x x x x x x x x X Air
X x x x x x x x x x X Blowing Agent Purity >99.9% 93.4% 96.7%
100% >99.9% after Exposure
The test data show that HFC-1225ye was surprisingly as stable as
HFC-134a and more stable than HFC-152a under extrusion
conditions.
[0119] The steel coupons from runs 32a, 32b and 24d were analyzed
by Electron Spectroscopy for Chemical Analysis (ESCA). Fluoride
ions (F.sup.-) were observed on the surface of all coupons.
Estimated concentrations of fluoride ion are shown in the table
below.
ESCA Analysis Results (unit: atom %)
TABLE-US-00009 Fluoride ion Sample Number Blowing Agents Talc (atom
%) 32a HFC-152a Mistron 15 32b HFC-1225ye Mistron 0.3 24d
HFC-1225ye Safoam 0.2 39d HFC-1225ye Mistron 0.3
Example 11
[0120] Experiments were conducted to assess the compatibility of
the unsaturated fluorocarbons for thermoplastic foams. Polystyrene
and talc nucleator were heated to 260.degree. C. in a pressure
vessel with blowing agent and held 24 hours. After 24 hours, the
vessel was cooled and a polystyrene sample recovered for thermal
gravimetric analysis (TGA). Weight loss versus temperature was
compared for the polystyrene samples heated with blowing agents to
a control sample of starting polystyrene material. The TGA analysis
shows that blowing agent was admixed in the melt and the weight
loss provides an approximation of the amount of blowing agent that
mixed in the melt. The data indicates improved solubility for the
unsaturated fluorocarbon blowing agent versus current HFC
products.
TABLE-US-00010 # Sample Blowing Agent Weight Loss@ 300.degree. C.
-- Polystyrene Control None 0.7% 24a Polystyrene
1,2,3,3,3-pentafluoro-1- 4.26% propene 24b Polystyrene
1,2,3,3,3-pentafluoro-1- 2.5% propene 39c Polystyrene + Talc
1,2,3,3,3-pentafluoro-1- 5.38% propene 39b Polystyrene + Talc
HFC-152a 2.44% 39d Polystyrene + Talc HFC-134a 3.99% 39a
Polystyrene + Safoam 1,2,3,3,3-pentafluoro-1- 4.79% propene
* * * * *