AU2012268812A1 - Blowing agents for forming foam comprising unsaturated fluorocarbons - Google Patents

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.

Description

P/00/011 Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT ORIGINAL Name of Applicant: E. I. DU PONT DE NEMOURS AND COMPANY Actual Inventors: Joseph Anthony CREAZZO Mario Joseph NAPPA Allen Capron SIEVERT Ekaterina SWEARINGEN Address for Service: Houlihan 2, Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia Invention Title: BLOWING AGENTS FOR FORMING FOAM COMPRISING UNSATURATED FLUOROCARBONS The following statement is a full description of this invention, including the best method of performing it known to the Applicant:- TITLE BLOWING AGENTS FOR FORMING FOAM COMPRISING UNSATURATED FLUOROCARBONS 5 The present application is a divisional application from Australian patent application number 2006308690. The entire disclosures of Australian patent application number 2006308690 and its corresponding International application, PCT/US2006/042623, are incorporated herein by reference. 10 CROSS REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of priority of U.S. Provisional Application 60/732,771, filed November 1, 2005, and incorporated herein by reference, and is further related to co-filed and jointly owned application of the same title, (Attorney Docket No. FL1318 US NA) and further related 15 to co-filed and jointly owned application titled Methods for Making Foams Using Blowing Agents Comprising Unsaturated Fluorocarbons (Attorney Docket No. FL1319 US NA), both of which are also incorporated herein by reference. FIELD OF THE INVENTION 20 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. 25 BACKGROUND OF THE INVENTION 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 30 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. All of these various types of polyurethane foams require blowing (expansion) agents for their manufacture. Insulating foams depend on the 5 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-1 1, trichlorofluoromethane) and HCFCs (hydrochlorofluorocarbons, for example HCFC-141 b, 1,1 10 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 15 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). A second type of insulating foam is thermoplastic foam, primarily polystyrene foam. Polyolefin foams (polystyrene, polyethylene, and 20 polypropylene) are widely used in insulation and packaging applications. These thermoplastic foams were generally made with CFC-1 2 (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 25 polystyrene. A third important type of insulating foam is phenolic foam. These foams, which have very attractive flammability characteristics, were generally made with CFC-1 1 (trichlorofluoromethane) and CFC-1 13 (1,1,2 trichloro-1,2,2-trifluoroethane) blowing agents 30 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. Patent 6,703,431 (Dietzen, et. al.) describes open-cell foams based on thermoplastics polymers that are useful for fluidabsorbent hygiene articles such as wound contact materials. U.S. Patent 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 5 technologies, for example in the production of evacuated insulation panels as described in U.S. Patent 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 10 foam. These open-cell foams have traditionally been produced employing CFCs, HCFCs, or more recently, HFCs as blowing agents. Multimodal foams are also of commercial interest, and are described, for example, in U.S. Patent 6,787,580 (Chonde, et. al.) and U.S. Patent 5,332,761 (Paquet, et. al.). A multimodal foam is a foam 15 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. 20 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 25 stratospheric ozone, as well as their implication in contributing to global warming. 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 30 their use has come under scrutiny, and the widespread use of HCFCs is scheduled for eventual phase out under the Montreal Protocol. More recently HFCs have been proposed and employed as foam blowing agents. The HFCs do not contribute to the destruction of 3 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. 5 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 10 regulations. 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). 15 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. 20 SUMMARY OF THE INVENTION The present invention provides a composition comprising a polyol and a blowing agent having reduced solubility in said polyol, wherein said blowing agent is selected from the group consisting of: a hydrofluorocarbon having the formula E- or Z-R'CH=CHR 2 , 25 wherein R 1 and R 2 are, independently, C1 to C6 perfluoroalkyl groups; and a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF 3

CF=CFCF

3 , CF 3

CF

2

CF=CF

2 ,

CF

3

CF=CHCF

3 , CF 3

CH=CHCF

3 , CF 2

=CHCF

2

CF

3 , 30 CF 2

=CFCHFCF

3 , CF 2

=CFCF

2

CHF

2 , CHF 2

CH=CHCF

3 ,

(CF

3

)

2

C=CHCF

3 , CF 3

CF=CHCF

2

CF

3 , CF 3

CH=CFCF

2

CF

3 ,

CF

3

(CF

2

)

3

CF=CF

2 , CF 3

CF

2

CF=CFCF

2

CF

3 , (CF 3

)

2

C=C(CF

3

)

2 ,

(CF

3

)

2

CFCF=CHCF

3 , CF 2

=CFCF

2

CH

2 F, CF 2

=CFCHFCHF

2

,

0

CH

2

=C(CF

3

)

2 , CH 2

CF

2

CF=CF

2 , CH 2

FCF=CFCHF

2 ,

CH

2

FCF

2

CF=CF

2 , CF 2

=C(CF

3

)(CH

3 ), CF 2

=C(CHF

2

)(CH

3 ),

CF

3

CF=CFCH

3 , CH 3

CF=CHCF

3 , CF 2

=CFCF

2

CF

2

CF

3 ,

CHF=CFCF

2

CF

2

CF

3 , CF 2

=CHCF

2

CF

2

CF

3 , 5 CF 2

=CFCF

2

CF

2

CHF

2 , CHF 2

CF=CFCF

2

CF

3 ,

CF

3

CF=CFCF

2

CHF

2 , CF 3

CF=CFCHFCF

3 ,

CHF=CFCF(CF

3

)

2 , CF 2

=CFCH(CF

3 ) 2 , CF 3

CH=C(CF

3

)

2 ,

CF

2

=CHCF(CF

3

)

2 , CHF=CFCF 2

CF

2

CHF

2 , CF 2 =CHCH (CF 3

)

2 ,

CHF=CHCF(CF

3 ) 2 , CF 2

=C(CF

3

)CH

2

CF

3 , 10 CF 2

=CHCF

2

CH

2

CF

3 , CF 3

CF=C(CF

3

)(CH

3 ),

CHF=CHCH(CF

3

)

2 , CH 3

CF=C(CF

3

)

2 , CH 2

=CHCF

2

CHFCF

3 ,

CH

2

C(CF

3

)CH

2

CF

3 , (CF 3

)

2

C=CHC

2

F

5 , (CF 3

)

2

CFCF=CHCF

3 ,

(CF

3

)

2

C=C(CH

3

)(CF

3 ), CF 3

CF=C(CH

3

)CF

2

CF

3 ,

CF

3

CH=CHCH(CF

3

)

2 , (CF 3

)

2

C=CHCF

2

CH

3 , 15 CF 3

CF

2

CF=CFC

2

H

5 , CF 3

CF=CHCH(CF

3

)(CH

3 ),

(CF

3

)

2

C=CFC

2

H

5 , cyclo-CF 2

CF

2

CF

2 CH=CH-, cyclo

CF

2

CF

2 CH=CH-, CF 3

CF

2

CF

2

C(CH

3

)=CH

2 ,

CF

3

CF

2

CF

2

CH=CHCH

3 , cyclo-CF 2

CF

2 CF=CF-, cyclo

CF

2

CF=CFCF

2

CF

2 -, cyclo-CF 2

CF=CFCF

2

CF

2

CF

2 , 20 CF 3

CF

2

CF

2

CF

2

CH=CH

2 , CF 3

CH=CHCF

2

CF

3 ,

CF

2

CF

2

CH=CHCF

2

CF

3 , CF 3

CH=CHCF

2

CF

2

CF

3 ,

CF

3

CF=CFC

2

F

5 , CF 3

CF=CFCF

2

CF

2

C

2

F

5 ,

CF

3

CF

2

CF=CFCF

2

C

2

F

5 , CF 3

CH=CFCF

2

CF

2

C

2

F

5 ,

CF

3

CF=CHCF

2

CF

2

C

2

F

5 , CF 3

CF

2

CH=CFCF

2

C

2

F

5 , 25 CF 3

CF

2

CF=CHCF

2

C

2

F

5 , C 2

F

5

CF

2

CF=CHCH

3 ,

C

2

F

5

CF=CHCH

3 , (CF 3

)

2

C=CHCH

3 , CF 3

C(CH

3

)=CHCF

3 ,

CHF=CFC

2

F

5 , CHF 2

CF=CFCF

3 , (CF 3

)

2 C=CHF,

CH

2

FCF=CFCF

3 , CHF=CHCF 2

CF

3 , CHF 2

CH=CFCF

3 ,

CHF=CFCHFCF

3 , CF 3

CH=CFCHF

2 , CHF=CFCF 2

CHF

2 , 30 CHF 2

CF=CFCHF

2 , CH 2

CF=CFCF

3 , CH 2

FCH=CFCF

3 ,

CF

3

CH=CFCH

2 F, CHF=CFCH 2

CF

3 , CHF=CHCHFCF 3 ,

CHF=CHCF

2

CHF

2 , CHF 2

CF=CHCHF

2 , CHF=CFCHFCHF 2 ,

CF

3

CF=CHCH

3 , CF 2

=CHCF

2 Br, CHF=CBrCHF 2

,

I CHBr=CHCF 3 , CF 3 CBr=CFCF 3 , CHBr=CHCF 2

CF

3 ,

CH

3 CBr=CHCF 3 , CF 3 CBr=CHCH 3 , (CF 3

)

2 C=CHBr,

CF

3 CF=CBrCF 2

CF

3 , E-CHF 2 CBr=CFC 2

F

5 , Z

CHF

2 CBr=CFC 2

F

5 , CF 2 =CBrCHFC 2

F

5 , (CF 3

)

2 CFCBr=CH 2 , 5 CHBr=CF(CF 2

)

2

CHF

2 , CF 2

=C(CH

2 Br)CF 3 ,

CH

2 =C(CBrF 2

)CF

3 , (CF 3

)

2 CHCH=CHBr, (CF 3

)

2

C=CHCH

2 Br,

CF

2

=CHCF

2

CH

2 CBrF 2 , CFBr=CHCF 3 , CFBr=CFCF 3 , and

CF

3

(CF

2

)

3 CBr=CH 2 wherein the global warming potential of the blowing agent is less 10 than 100, and the composition has a net global warming potential of less than 50 and an ozone depletion potential of not greater than 0.05. In one aspect, the present invention provides a closed cell foam prepared by foaming a foamable composition in the presence of a 15 composition described above. A further aspect is for a foamable composition comprising a polyol and a blowing agent described above. Another aspect is for a foam premix composition comprising a polyol and a blowing agent described above. 20 Additionally, one aspect is for a method of forming a foam comprising: (a) adding to a foamable composition a composition described above; and (b) reacting the foamable composition under conditions effective 25 to form a foam. 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 composition described above. Another aspect is for a polyisocyanate 30 foam produced by said method. Other aspects 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 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 5 Compositions Comprising Unsaturated Fluorinated Hydrocarbons" (Attorney Docket # FL 1181 US PRV, US Application No. 60/732,771), "Blowing Agents for Forming Foam Comprising Unsaturated Fluorocarbons" (Attorney Docket # FL 1184 US PRV, US Application No. 60/732,090), "Aerosol Propellants Comprising Unsaturated Fluorocarbons" 10 (Attorney Docket # FL 1185 US PRV, US Application No. 60/732,791), and "Compositions Comprising Fluoroolefins and Uses Thereof" (Attorney docket # FL 1159, US 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 15 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 20 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. One aspect provides blowing agents having the formula E- or Z

R

1

CH=CHR

2 (Formula I), wherein R 1 and R 2 are, independently, C 1 to C 6 25 perfluoroalkyl groups. Examples of R 1 and R 2 groups include, but are not limited to, CF 3 , C 2

F

5

CF

2

CF

2

CF

3 , CF(CF 3

)

2 , CF 2

CF

2

CF

2

CF

3 ,

CF(CF

3

)CF

2

CF

3 , CF 2

CF(CF

3

)

2 , C(CF 3

)

3 , CF 2

CF

2

CF

2

CF

2

CF

3 ,

CF

2

CF

2

CF(CF

3

)

2 , C(CF 3

)

2

C

2

F

5 , CF 2

CF

2

CF

2

CF

2

CF

2

CF

3 , CF(CF 3 )

CF

2

CF

2

C

2

F

5 , and C(CF 3

)

2

CF

2

C

2

F

5 . Exemplary, non-limiting Formula 1 30 compounds are presented in Table 1.

Table 1 Code Structure Chemical Name F11E CF 3

CH=CHCF

3 1,1 ,1 ,4,4,4-hexafluorobut-2-ene F12E CF 3

CH=CHC

2

F

5 1,1,1,4,4,5,5, 5-octafluoropent-2-ene F1 3E CF 3

CH=CHCF

2

C

2

F

5 1,1,1,4,4,5,5,6, 6,6-decafluorohex-2-ene F13iE CF 3

CH=CHCF(CF

3

)

2 1,1,1 4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22E C 2

F

5

CH=CHC

2

F

5 1,1,1,2,2,5,5,6, 6,6-decafluorohex-3-ene F1 4E CF 3

CH=CH(CF

2

)

3

CF

3 1,1,1,4,4,5,5,6,6,7, 7,7-dodecafluorohept-2-ene F14iE CF 3

CH=CHCF

2

CF-(CF

3

)

2 1, 1, 1,4,4,5,6, 6,6-nonaflIuoro-5-(triflIuorom ethyl) hex-2-ene Fl 4sF CF 3

CH=CHCF(CF

3

)-C

2

F

5 1, 1, 1,4,5,5,6, 6,6-nonaf Iuoro-4-(trif Iuorom ethyl) hex-2-ene F14tE CF 3

CH=CHC(CF

3

)

3 1,1,1,5,5, 5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23E C 2

F

5

CH=CHCF

2

C

2

F

5 1,1,1,2,2,5,5,6,6,7, 7,7-dodecafluorohept-3-ene F23iE C 2

F

5

CH=CHCF(CF

3

)

2 1, 1, 1,2,2,5,6, 6,6-nonaf Iuoro-5-(trif Iuorom ethyl) hex-3-ene F1l5E CF 3

CH=CH(CF

2

)

4

CF

3 1,1,1,4,4,5,5,6,6,7,7, 8,8,8-tetradecafluorooct-2-ene El5iE CF 3

CH=CH-CF

2

CF

2

CF(CF

3

)

2 1,1 ,1,4,4,5,5, 6,7,7,7-undecafluoro-6 (trifluoromethyl)hept-2-ene F1 StE CF 3

CH=CH-C(CF

3

)

2

C

2

F

5 1, 1, 1,5,5,6, 6,6-octaflIuoro-4,4-bis(triflIuorom ethyl) hex-2 ene F24E C 2

F

5

CH=CH(CF

2

)

3

CF

3 1,1,1,2,2,5,5,6,6,7,7, 8,8,8-tetradecafluorooct-3-ene F24iE C 2

F

5

CH=CHCF

2

CF-(CF

3

)

2 1,1 ,1 ,2,2,5,5, 6,7,7,7-undecafluoro-6 (trifluoromethyl)hept-3-ene F24sE C 2

F

5

CH=CHCF(CF

3

)-C

2

F

5 1,1 ,1 ,2,2,5,6, 6,7,7,7-undecafluoro-5 (trifluoromethyl)hept-3-ene F24tE C2FCH=CHC(CF3) 1,1,1,12,2,6, 6,6-octaflIuoro-S,S-bis(triflIuorom ethyl) hex-3 25\3J3ene F33E C 2

F

5

CF

2

CH=CH-CF

2

C

2

F

5 1,1,1,2,2,3,3,6,6,7,7, 8,8,8-tetradecafluorooct-4-ene F3i3iE 'CF3)CFCH=CH-CF'CF3) 1, 1, 1,2,5,6,6,6-octaflIuoro-2,5-bis(triflIuorom ethyl) hex-3 \3J2\3J2ene F33iE C 2

F

5

CF

2 CH=CH- CF(CF 3

)

2 1,1 ,1 ,2,5,5,6, 6,7,7,7-undecafluoro-2 (trifluoromethyl)hept-3-ene F1 6E CF 3

CH=CH(CF

2

)

5

CF

3 1,1,1 ,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16E CF 3

CH=CHCF(CF

3 )- 1,1,1,4,5,5,6,6, 7,7,8,8,8-tridecafluoro-4 Fl sF(CF 2

)

2

C

2

F

5 (trifluoromethyl)hept-2-ene F1 6tE CF 3

CH=CHC(CF

3

)

2 - CF 2

C

2

F

5 1, 1, 1 ,6,6,6-octaflIuoro-4,4-bis(triflIuorom ethyl) hept-2-en e F25E C 2

F

5

CH=CH(CF

2

)

4

CF

3 1,1,1,2,2,5,5,6,6,7,7,8, 8,9,9,9-hexadecafluoronon-3-ene F25iE C 2

F

5

CH=CH-CF

2

CF

2

CF(CF

3

)

2 1,1,1,2,2,5,5,6,6,7,8,8, 8-tridecafluoro-7 (trifluoromethyl)oct-3-ene F25tE C 2

F

5

CH=CH-C(CF

3

)

2

C

2

F

5 1,1,1,2,2,6, 6,7,7,7-decafluoro-5,5 bis(trif Iuorom ethyl) hept-3-e ne F34E C 2

F

5

CF

2

CH=CH-(CF

2

)

3

CF

3 1,1,1,2,2,3,3,6,6,7,7,8, 8,9,9,9-hexadecafluoronon-4-ene F4EC 2

F

5

CF

2 CH=CH- 1,1,1,2,2,3,3,6, 6,7,8,8,8-tridecafluoro-7 F34 FCF 2

CF(CF

3

)

2 (trifluoromethyl)oct-4-ene F4EC 2

F

5

CF

2 CH=CH- 1,1,1 ,2,2,3,3,6, 7,7,8,8,8-tridecafluoro-6 F34sECF (OF 3 ) C 2

F

5 (trifluorometh yI)oct-4-ene F34tE C 2

F

5

CF

2 CH=CH- C(CF 3

)

3 1,1,1,5,5,6, 6,7,7,7-decafluoro-2,2 bis(trif Iuorom ethyl) hept-3-e ne F3i4E (CF3)CFCH=OH-(CF2)CF3 1,1 ,l,2,S,S,6,6,7,7,8,8,8-tridecafluoro (3)2 2)332(trifluoromethyl)oct-3-ene IU FiE

(CF

3

)

2 CFCH=CH- 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6

CF

2

CF(CF

3

)

2 bis(trifluoromethyl) hept-3-ene F34sE

(CF

3

)

2 CFCH=CH- 1,1,1,2,5,6,6,7,7,7-decafluoro-2,5

CF(CF

3

)C

2

F

5 bis(trifluoromethyl) hept-3-ene F3i4tE (CF)CFCHCHC(CF) 1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3 \CF3J2C = 3 ene F26E C2FCH OH(CF2)CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec 3-ene F26sE C 2

F

5

CH=CHCF(CF

3 )- 1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5

(CF

2

)

2

C

2

F

5 (trifluoromethyl)non-3-ene F26tE C 2

F

5

CH=CHC(CF

3

)

2 - CF 2

C

2

F

5 1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5 bis(trifluoromethyl)oct-3-ene F35E C2F5CF2CH=CH-(CF2)4CF3 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec 4-ene F35iE C 2

F

5

CF

2 CH=CH- 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8

CF

2

CF

2

CF(CF

3

)

2 (trifluoromethyl)non-4-ene F35tE C 2

F

5

CF

2

CH=CH-C(CF

3

)

2

C

2

F

5 1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6 bis(trifluoromethyl)oct-4-ene F3i5E (CF 3

)

2

CFCH=CH-(CF

2

)

4

CF

3 1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2 (trifluoromethyl)non-3-ene F35E (CF 3

)

2 CFCH=CH- 1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7

CF

2

CF

2

CF(CF

3

)

2 bis(trifluoromethyl)oct-3-ene F3i5tE (CF 3

)

2

CFCH=CH-C(CF

3

)

2

C

2

F

5 1,1,1s2,6,6,7, 7,7- nonaf uo ro-2,5,5 tris (trif Iuo romreth yl) hept-3-en e F44E CF3(CF2)CH=CH-

(CF

2

)

3

CF

3 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,1-octadecafluorodec 3(2)35-ene F44iE CF 3

(CF

2

)

3 CH=CH- 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2

CF

2

CF(CF

3

)

2 (trifluoromethyl)non-4-ene F44sE CF 3

(CF

2

)

3 CH=CH- 1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3

CF(CF

3

)C

2

F

5 (trifluoromethyl)non-4-ene F44tE CF 3

(CF

2

)

3 CH=CH- C(CF 3

)

3 1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2, bis(trifluoromethyl)oct-3-ene F4i4iE (CF 3

)

2

CFCF

2 CH=CH- 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7

CF

2

CF(CF

3

)

2 bis(trifluoromethyl)oct-4-ene F44sE (CF 3

)

2

CFCF

2 CH=CH- 1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6

CF(CF

3

)C

2

F

5 bis(trifluoromethyl)oct-4-ene F44tE (CF 3

)

2

CFCF

2 CH=CH- 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6

C(CF

3

)

3 tris(trifluoromethyl)hept-3-ene F4s4sE C 2

F

5

CF(CF

3 )CH=CH- 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6

CF(CF

3

)C

2

F

5 bis(trifluoromethyl)oct-4-ene F4s4tE C 2

F

5

CF(CF

3 )CH=CH- C(CF 3

)

3 1,1,1,5,6,6,7, 7,7-nonafluoro-2,2,5 tris(trif Iuoromnethyl) hept-3-ene F4t4tE (CF 3

)

3 CCH=CH- C(CF 3

)

3 1,1,1,6,6, 6-hexafuoro-2,2,5,5 tetrakis(trifluoromethyl)hex-3-ene Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R 1 I with a perfluoroalkyltrihydroolefin of the formula R 2

CH=CH

2 to form a trihydroiodoperfluoroalkane of the 5 formula R'CH 2

CHIR

2 . This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R'CH=CHR 2 . Alternatively, the olefin

R'CH=CHR

2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R 1

CHICH

2

R

2 formed in turn by I I reacting a perfluoroalkyl iodide of the formula R 2 1 with a perfluoroalkyltrihydroolefin of the formula R'CH=CH 2 . Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining 5 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@ nickel-copper alloys, Hastelloy@ nickel 10 based alloys and Inconel@ nickel-chromium alloys. 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. 15 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). 20 Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 1500C to 3000C, preferably from about 1700C to about 2500C, and most preferably from about 1800C to about 2300C. Suitable contact times for the reaction of the perfluoroalkyl iodide 25 with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours. 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 30 purified by distilled prior to the dehydroiodination step. 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 Ill/ 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 5 mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. 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. 10 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 15 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. Typically, the dehydroiodination reaction may be carried out by 20 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. Temperatures suitable for the dehydroiodination reaction are from 25 about 10 C to about 100 C, preferably from about 200C to about 700C. 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. 30 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 |i hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, or perch loroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, 5 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 10 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). Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid 15 or liquid basic substance. 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. 20 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. The compositions disclosed herein may comprise a single compound of Formula I, for example, one of the compounds in Table 1, or 25 may comprise a combination of compounds of Formula 1. In addition to the inventive compounds described above, compounds presented in Table 2 can be used as blowing agents. Table 2 Name Structure Chemical name HFC-1225s

C

3

HF

5 HFC-1225ye CF 3 CF=CHF 1,2,3,3,3-pentafluoro-1 -propene HFC-1225zc CF 3

CH=CF

2 1,1,3,3,3-pentafluoro-1 -propene HFC-1225yc CHF 2

CF=CF

2 1,1,2,3,3-pentafluoro-1 -propene HFC-1234s

C

3

H

2

F

4 HFC-1234ye CHF 2 CF=CHF 1,2,3,3-tetrafluoro-1 -propene 14 HFC-1234yf CF 3

CF=CH

2 2,3,3,3-tetrafluoro-1 -propene HFC-1234ze CF 3 CH=CHF 1,3,3,3-tetrafluoro-1 -propene HFC-1234yc CH 2

FCF=CF

2 1,1,2,3-tetrafluoro-1 -propene HFC-1234zc CHF 2

CH=CF

2 1,1,3,3-tetrafluoro-1 -propene HFC-1234ye CHF 2 CF=CHF 1,2,3,3-tetrafluoro-1-propene HFC-1243s

C

3

H

3

F

3 HFC-1243yf CHF 2

CF=CH

2 2,3,3-trifluoro-1 -propene HFC-1243zf CF 3

CH=CH

2 3,3,3-trifluoro-1 -propene HFC-1243yc CH 3

CF=CF

2 1,1,2-trifluoro-1 -propene HFC-1243zc CH 2

FCH=CF

2 1,1,3-trifluoro-1 -propene HFC-1243ye CHF 2 CF=CHF 1,2,3-trifluoro-1 -propene HFC-1243ze CHF 2 CH=CHF 1,3,3-trifluoro-1 -propene FC-1318s C 4

F

8 FC-1318my CF 3

CF=CFCF

3 1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF 3

CF

2

CF=CF

2 1,1,2,3,3,4,4,4-octafluoro-1 -butene HFC-1327s

C

4

HF

7 HFC-1327my CF 3

CF=CHCF

3 1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF=CFCF 2

CF

3 1,2,3,3,4,4,4-heptafluoro-1 -butene HFC-1327py CHF 2

CF=CFCF

3 1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF 3

)

2 C=CHF 1,3,3,3-tetrafluoro-2 (trifluoromethyl)-1 -propene HFC-1327cz CF 2

=CHCF

2

CF

3 1,1,3,3,4,4,4-heptafluoro-1 -butene HFC-1327cye CF 2

=CFCHFCF

3 1,1,2,3,4,4,4-heptafluoro-1 -butene HFC-1327cyc CF 2

=CFCF

2

CHF

2 1,1,2,3,3,4,4-heptafluoro-1 -butene HFC-1336s

C

4

H

2

F

6 HFC-1 336yf CF 3

CF

2

CF=CH

2 2,3,3,4,4,4-hexafluoro-1 -butene HFC-1336ze CHF=CHCF 2

CF

3 1,3,3,4,4,4-hexafluoro-1 -butene HFC-1336eye CHF=CFCHFCF 3 1,2,3,4,4,4-hexafluoro-1 -butene HFC-1336eyc CHF=CFCF 2

CHF

2 1,2,3,3,4,4-hexafluoro-1 -butene HFC-1336pyy CHF 2

CF=CFCHF

2 1,1,2,3,4,4-hexafluoro-2-butene HFC-1336gy CH 2

FCF=CFCF

3 1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF 2

CH=CFCF

3 1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF 3

CH=CFCHF

2 1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF 2

=CFCF

2

CH

2 F 1,1,2,3,3,4-hexafluoro-1 -butene HFC-1336pe CF 2

=CFCHFCHF

2 1,1,2,3,4,4-hexafluoro-1 -butene HFC-1336ft CH 2

=C(CF

3

)

2 3,3,3-trifluoro-2-(trifluoromethyl)-1 propene HFC-1345s

C

4

H

3

F

5 HFC-1345qz CH 2

FCH=CFCF

3 1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF 3

CH=CFCH

2 F 1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF 3

CF

2

CH=CH

2 3,3,4,4,4-pentafluoro-1 -butene HFC-1345mzz CHF 2

CH=CHCF

3 1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH 3

CF=CFCF

3 1,1,1,2,3-pentafluoro-2-butene HFC-1 345fyc CH 2

=CFCF

2

CHF

2 2,3,3,4,4-pentaf I uoro-1 -butene HFC-1345pyz CHF 2

CF=CHCHF

2 1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH 3

CF

2

CF=CF

2 1,1,2,3,3-pentafluoro-1 -butene HFC-1345pyy CH 2

FCF=CFCHF

2 1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH 2

FCF

2

CF=CF

2 1,2,3,3,4-pentafluoro-1 -butene HFC-1345ctm CF 2

=C(CF

3

)(CH

3 ) 1,1,3,3,3-pentafluoro-2-methyl- 1 propene HFC-1345ftp CH 2

=C(CHF

2

)(CF

3 ) 2-(difluoromethyl)-3,3,3-trifluoro-1 propene HFC-1354s

C

4

H

4

F

4 HFC-1354fzc CH 2

=CHCF

2

CHF

2 3,3,4,4-tetrafluoro-1 -butene HFC-1354ctp CF 2

=C(CHF

2

)(CH

3 ) 1,1,3,3-tetrafluoro-2-methyl-1 propene 10 HFC-1354etm CHF=C(CF 3

)(CH

3 ) 1,3,3,3-tetrafluoro-2-methyl-1 propene HFC-1 354tfp CH 2

=C(CHF

2

)

2 2-(difluoromethyl)-3,3-difluoro-1 propene HFC-1354my CF 3

CF=CFCH

3 1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH 3

CF=CHCF

3 1,1,1,3-tetrafluoro-2-butene FC-141-10s C5F10 FC-141-1Omyy CF 3

CF=CFCF

2

CF

3 1,1,1,2,3,4,4,5,5,5-decafluoro-2 pentene FC-141-1 Ocy CF 2

=CFCF

2

CF

2

CF

3 1,1,2,3,3,4,4,5,5,5-decafluoro-1 pentene HFC-1429s C 5

HF

9 HFC-1429mzt (CF 3

)

2

C=CHCF

3 1,1,1,4,4,4-hexafluoro-2 (trifluoromethyl)-2-butene HFC-1429myz CF 3

CF=CHCF

2

CF

3 1,1,1,2,4,4,5,5,5-nonafluoro-2 pentene HFC-1429mzy CF 3

CH=CFCF

2

CF

3 1,1,1,3,4,4,5,5,5-nonafluoro-2 pentene HFC-1429eyc CHF=CFCF 2

CF

2

CF

3 1,2,3,3,4,4,5,5,5-nonafluoro-1 pentene HFC-1429czc CF 2

=CHCF

2

CF

2

CF

3 1,1,3,3,4,4,5,5,5-nonafluoro-1 pentene HFC-1429cycc CF 2

=CFCF

2

CF

2

CHF

2 1,1,2,3,3,4,4,5,5-nonafluoro-1 pentene HFC-1429pyy CHF 2

CF=CFCF

2

CF

3 1,1,2,3,4,4,5,5,5-nonafluoro-2 pentene HFC-1429myyc CF 3

CF=CFCF

2

CHF

2 1,1,1,2,3,4,4,5,5-nonafluoro-2 pentene HFC-1429myye CF 3

CF=CFCHFCF

3 1,1,1,2,3,4,5,5,5-nonafluoro-2 pentene HFC-1429eyym CHF=CFCF(CF 3

)

2 1,2,3,4,4,4-hexafluoro-3 (trifluoromethyl)-1 -butene HFC-1429cyzm CF 2

=CFCH(CF

3

)

2 1,1,2,4,4,4-hexafluoro-3 (trifluoromethyl)-1 -butene HFC-1429mzt CF 3 CH= C(CF 3

)

2 1,1,1,4,4,4-hexafluoro-3 (trifluoromethyl)-2-butene HFC-1429czym CF 2

=CHCF(CF

3

)

2 1,1,3,4,4,4-hexafluoro-3 (trifluoromethyl)-1 -butene HFC-1438s C 5

H

2

F

8 HFC-1 438fy CH 2

=CFCF

2

CF

2

CF

3 2,3,3,4,4,5,5,5-octafluoro-1 pentene HFC-1438eycc CHF=CFCF 2

CF

2

CHF

2 1,2,3,3,4,4,5,5-octafluoro-1 pentene H FC- 1 438ftmc CH 2

=C(CF

3

)CF

2

CF

3 3,3,4,4,4-pentafluoro-2 (trifluoromethyl)-1 -butene HFC-1438czzm CF 2

=CHCH(CF

3

)

2 1,1,4,4,4-pentafluoro-3 (trifluoromethyl)-1 -butene HFC-1438ezym CHF=CHCF(CF 3

)

2 1,3,4,4,4-pentafluoro-3 (trifluoromethyl)-1 -butene H FC- 1 438ctmf CF 2

=C(CF

3

)CH

2

CF

3 1,1,4,4,4-pentafluoro-2 (trifluoromethyl)-1 -butene HFC-1447s C 5

H

3

F

7 HFC-1 447fzy (CF 3

)

2

CFCH=CH

2 3,4,4,4-tetrafluoro-3 (trifluoromethyl)-1 -butene HFC-1447fz CF 3

CF

2

CF

2

CH=CH

2 3,3,4,4,5,5,5-heptafluoro-1 -pentene HFC-1 447fycc CH 2

=CFCF

2

CF

2

CHF

2 2,3,3,4,4,5,5-heptafluoro-1 -pentene HFC-1 447czcf CF 2

=CHCF

2

CH

2

CF

3 1,1,3,3,5,5,5-heptafluoro-1 -pentene 110 HFC-1 447mytm CF 3

CF=C(CF

3

)(CH

3 ) 1, 1, 1,2,4,4,4-heptaflIuoro-3-methyl 2-butene H FC- 1 447fyz CH 2

=CFCH(CF

3

)

2 2,4,4,4-tetraflIuoro-3 (triflIuorom ethyl)- 1 -butene H FC- 1447ezz OH F=CHCH(CF 3

)

2 1 ,4,4,4-tetrafluoro-3 (triflIuorom ethyl)- 1 -butene H FC- 1447qzt CH 2

FCH=C(CF

3

)

2 1 ,4,4,4-tetrafluoro-3 (trifluoromethyl)-2-butene H FC- 1 447syt CH 3

CF=C(CF

3

)

2 2,4,4,4-tetrafluoro-3 (trifluoromethyl)-2-butene HFC-1456s C 5

H

4

F

6 H FC- 1456szt (CF 3

)

2

C=CHCH

3 3-(trifluoromethyl)-4,4,4-trifluoro-2 butene HFC-1 456szy CF 3

CF

2

CF=CHCH

3 3,4,4,5,5,5-hexafluoro-2-pentene HFC-1 4b6mstz CF 3

C(CH

3

)=CHCF

3 1,1,1 ,4,4,4-hexafluoro-2-methyl-2 butene HFC-1 4b6fzce CH 2

=CHCF

2

CHFCF

3 3,3,4,5,5,5-hexafluoro-1 -pentene HFC-1 4b6ftmf CH 2

=C(CF

3

)CH

2

CF

3 4,4,4-trifluoro-2-(trifluoromethyl)-1 butene FC-151-12s C 6

F

12 FC- 151 -12c CF 3

(CF

2

)

3

CF=CF

2 1, 1, 2,3,3,4,4,5,5,6,6,6 dodecafluoro-1 -hexene (or perfluoro-1 -hexene) FC-1 51 -l2mcy CF 3

CF

2

CF=CFCF

2

CF

3 1, 1, 1,2,2,3,4,5,5,6,6,6 dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-1 51-1 2mmtt (CF 3

)

2

C=C(CF

3

)

2 1,1,1 ,4,4,4-hexafluoro-2,3 bis(trifluoromethyl)-2-butene FC-1 51-1 2mmzz (CF 3

)

2

CFCF=CFCF

3 1,1,1 ,2,3,4,5,5,5-nonafluoro-4 (trifluoromethyl)-2-pentene HFC-152-lls C 6

HF

11 HFC-1 52-1 1 mmtz (CF 3

)

2

C=CHC

2

F

5 1,1,1 ,4,4,5,5,5-octafluoro-2 (trifluoromethyl)-2-pentene HFC-1 52-1 1 mmyyz (CF 3

)

2

CFCF=CHCF

3 1,1,1 ,3,4,5,5,5-octafluoro-4 (trifluoromethyl)-2-pentene HFC-1549s C 6

H

3 Fq PEBE CF 3

CF

2

CF

2

CF

2

CH=CH

2 3,3,4,4,5,5,6,6,6-nonafluoro-1 (or HFC-1 549fz) hexene (or perflIuorobutyl ethyl en e) H FC- 1 49fztmm CH 2

=CHC(CF

3

)

3 4,4,4-trifluoro-3,3 bis(triflIuorom ethyl)- 1 -butene HFC-1 S49mmtts (CF 3

)

2

C=C(CH

3

)(CF

3 ) 1,1,1 ,4,4,4-hexafluoro-3-methyl-2 (trifluoromethyl)-2-butene HFC-1 S49fycz CH 2

=CFCF

2

CH(CF

3

)

2 2,3,3,5,5,5-hexafluoro-4 (triflIuorom ethyl)- 1 -pentene HFC-1 S49myts CF 3

CF=C(CH

3

)CF

2

CF

3 1,1,1 ,2,4,4,5,5,5-nonafluoro-3 m ethyl -2-pentene HFC-1 S49mzzz CF 3

CH=CHCH(CF

3

)

2 1,1,1 ,5,5,5-hexafluoro-4 (trifluoromethyl)-2-pentene HFC-1558s C 6

H

4

F

8 HFC-1 558szy CF 3

CF

2

CF

2

CF=CHCH

3 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1 S58fzccc CH 2

=CHCF

2

CF

2

CF

2

CHF

2 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1 S58mmtzc (CF 3

)

2

C=CHCF

2

CH

3 1,1,1 ,4,4-pentafluoro-2 (trifluoromethyl)-2-pentene H FC- 1 S58ftmf CH 2

=C(CF

3

)CH

2

C

2

F

5 4,4,5 ,5,5-pentaflIuoro-2 (triflIuorom ethyl)- 1 -pentene HFC-1567s C 6

H

5

F

7 H FC- 1 567fts CF 3

CF

2

CF

2

C(CH

3

)=CH

2 3,3,4,4,5,5,5- heptaflIuo ro-2- methyl 1 -pentene I / HFC-1567szz CF 3

CF

2

CF

2

CH=CHCH

3 4,4,5,5,6,6,6-heptafluoro-2-hexene HFC-1 567fzfc CH 2

=CHCH

2

CF

2

C

2

F

5 4,4,5,5,6,6,6-heptafluoro-1 -hexene HFC-1 567sfyy CF 3

CF

2

CF=CFC

2

H

5 1,1,1,2,2,3,4-heptafluoro-3-hexene HFC-1 567fzfy CH 2

=CHCH

2

CF(CF

3

)

2 4,5,5,5-tetrafluoro-4 (trifluoromethyl)-1 -pentene HFC-1 567myzzm CF 3

CF=CHCH(CF

3

)(CH

3 ) 1,1,1,2,5,5,5-heptafluoro-4-methyl 2-pentene HFC-1 567mmtyf (CF 3

)

2

C=CFC

2

H

5 1,1,1 ,3-tetrafluoro-2 (trifluoromethyl)-2-pentene FC-161-14s CF FC-1 61-14myy CF 3

CF=CFCF

2

CF

2

C

2

F

5 1,1,1,2,3,4,4,5,5,6,6,7,7,7 tetradecafluoro-2-heptene FC-1 61-14mcyy CF 3

CF

2

CF=CFCF

2

C

2

F

5 1,1,1,2,2,3,4,5,5,6,6,7,7,7 tetradecafluoro-2-heptene HFCs-162-13s C 7

HF

13 HFC-1 62-13mzy CF 3

CH=CFCF

2

CF

2

C

2

F

5 1,1,1,3,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene HFC1 62-13myz CF 3

CF=CHCF

2

CF

2

C

2

F

5 1,1,1,2,4,4,5,5,6,6,7,7,7 tridecafluoro-2-heptene HFC-1 62-13mczy CF 3

CF

2

CH=CFCF

2

C

2

F

5 1,1,1,2,2,4,5,5,6,6,7,7,7 tridecafluoro-3-heptene HFC-1 62-13mcyz CF 3

CF

2

CF=CHCF

2

C

2

F

5 1,1,1,2,2,3,5,5,6,6,7,7,7 tridecafluoro-3-heptene Cyclic Cyclo[-CX=CY(CXY).-] fluoroolefins HFC-C1316cc cyclo-CF 2

CF

2 CF=CF- 1,2,3,3,4,4-hexafluorocyclobutene HFC-C1334cc cyclo-CF 2

CF

2 CH=CH- 3,3,4,4-tetrafluorocyclobutene HFC-C1436 cyclo-CF 2

CF

2

CF

2 CH=CH- 3,3,4,4,5,5, hexafluorocyclopentene HFC-C1418y cyclo-CF 2

CF=CFCF

2

CF

2 - 1,2,3,3,4,4,5,5 octafluorocyclopentene FC-C1 51-1 Oy cyclo- 1,2,3,3,4,4,5,5,6,6

CF

2

CF=CFCF

2

CF

2

CF

2 - decafluorocyclohexene The compounds listed in Table 2 are available commercially or may be prepared by processes known in the art. In addition to the inventive compounds described above, the 5 bromine-containing fluorocarbons or hydrofluorocarbons presented in Table 3 can be used as blowing agents. TABLE 3 Structure Chemical Names

CF

2

=CHCF

2 Br 3-bromo-1,1,3,3-tetrafluoropropene

CF

2 =CFCBrH 2 3-bromo-1,1,2-trifluoropropene CHF=CBrCF 3 2-bromo-1,3,3,3-tetrafluoropropene CHF=CHCBrF 2 3-bromo-1,3,3-trifluoropropene CHF=CBrCHF 2 2-bromo-1,3,3-trifluoropropene CHBr=CFCF 3 1 -bromo-2,3,3,3-tetrafluoropropene 10 CHBr=CHCF 3 1-bromo-3,3,3-trifluoropropene

CH

2 =CBrCF 3 2-bromo-3,3,3-trifluoropropene

CH

2 =CFCBrF 2 3-bromo-2,3,3-trifluoropropene CFBr=CHCF 3 1 -bromo-1,3,3,3-tetrafluoropropene CFBr=CFCF 3 1 -bromopentafluoropropene

CH

2 =CBrCF 2

CF

3 2-bromo-3,3,4,4,4-pentafluoro-1 -butene CHBr=CHCF 2

CF

3 1 -bromo-3,3,4,4,4-pentafluoro-1 -butene

CH

2

=CHCF

2

CF

2 Br 4-bromo-3,3,4,4-tetrafluoro-1 -butene

CH

2 =CHCBrFCF 3 3-bromo-3,4,4,4-tetrafluoro-1 -butene

CF

3 CBr=CFCF 3 2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene

CH

3 CBr=CHCF 3 2-bromo-4,4,4-trifluoro-2-butene

CF

3 CBr=CHCH 3 2-bromo-1,1,1 -trifluoro-2-butene

(CF

3

)

2 C=CHBr 1 -bromo-3,3,3-trifluoro-2-(trifluoromethyl)-propene

CF

3 CF=CBrCF 2

CF

3 3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene

E-CHF

2 CBr=CFC 2

F

5 E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene

Z-CHF

2 CBr=CFC 2

F

5 Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene

CF

2 =CBrCHFC 2

F

5 2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene CHBr=CF(CF2) 2

CHF

2 1 -bromo-2,3,3,4,4,5,5-heptafluoro-1 -pentene

CH

2 =CBrCF 2

C

2

F

5 2-bromo-3,3,4,4,5,5,5-heptafluoro-1 -pentene

CF

2

=CHCF

2

CH

2 CBrF 2 5-bromo-1,1,3,3,5,5-hexafluoro-1 -pentene

(CF

3

)

2 CFCBr=CH 2 2-bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene

CF

2

=C(CH

2 Br)CF 3 2-(bromomethyl)-1,1,3,3,3-pentafluoropropene

CH

2 =C(CBrF2)CF 3 2-(bromodifluoromethyl)-3,3,3-trifluoropropene

(CF

3

)

2 CHCH=CHBr 1 -bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1 -butene

(CF

3

)

2

C=CHCH

2 Br 4-bromo-1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene

CH

2

=CHCF(CF

3 )CBrF 2 3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1 -butene

CF

3

CF

2

CF

2 CBr=CH 2 2-bromo-3,3,4,4,5,5,5-heptafluoro-1 -pentene

CF

3 (CF2) 3 CBr=CH 2 2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene The compounds listed in Table 3 are available commercially or may be prepared by processes known in the art. 1 -Bromo-3,3,4,4,4-pentafluoro-1 -butene may be prepared by a 5 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 350-400C gives 4,4-dibromo-1,1,1,2,2- I Oj pentafluorobutane which may in turn be heated with powdered potassium hydroxide to give the desired bromobutene. 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 5 butene followed by treatment of the resulting dibromide with ethanolic potassium hydroxide. 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 10 include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, CF 3

CH=CHCF

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 2

F

5

CF

2

CH=CH-CF

2

C

2

F

5 , by which is represented the E-isomer, Z-isomer, or any combination or mixture of both 15 isomers in any ratio. HFC-1225ye may exist as one of two configurational isomers, E or Z HFC-1 225ye as used herein refers to the isomers, E-HFC-1 225ye (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. 20 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 1. The amount of the fluorocarbons (FCs) or HFCs contained in the 25 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. The compositions disclosed herein may be prepared by any 30 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.

ZU 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 5 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 10 compositions of the present disclosure. 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 15 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 20 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 25 commonly the value referenced. 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 30 replacement, based upon GWP calculations published by the Intergovernmental Panel on Climate Change (IPCC), include but are not limited to HFC-1 34a and HFC-227ea.

Z I 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 5 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, 10 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. The present invention further relates to a method for lowering the GWP of the methods for manufacturing open, closed and multi-modal 15 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 20 the GWP for each of the pure compounds. 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 25 of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. Certain embodiments provide foam premixes, foamable compositions, and preferably polyurethane or polyisocyanate foam compositions, and methods of preparing foams. In such foam 30 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 5 reference, may be used or adapted for use in accordance with the foam embodiments. 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, 10 antioxidants, reinforcing agents, filler, antistatic agents, nucleating agents and the like. 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 15 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". The term "B-side" is intended to mean polyol or polyol containing mixture. A polyol containing mixture usually includes the polyol, the 20 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. The term "A-side" is intended to mean isocyanate or isocyanate containing mixture. An isocyanate containing mixture may include the 25 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. To prepare the foam, appropriate amounts of A-side and B-side are 30 then combined to react. 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 5 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. One or more catalysts for the reaction of the polyol with the 10 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. 15 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. 20 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 25 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. Polyisocyanate-based foams are prepared, e.g., by reacting at least 30 one organic polyisocyanate with at least one active hydrogen-containing compound in the presence of the blowing agent composition described herein-above.

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, 5 based on the total weight of active hydrogen-containing compound and blowing agent composition. 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 10 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. Additional examples of suitable active hydrogen containing 15 compounds can be found in U.S. Patent 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 20 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, 25 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 30 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 5 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. Suitable additional isocyanate-reactive materials include polyether 10 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. 15 Other polyols include alkylene oxide derivatives of Mannich condensates, and aminoalkylpiperazine-initiated polyethers as described in U.S. Patent 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. 20 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 25 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. 30 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.

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 5 500, preferably from about 18 to about 100 kg/M 3 (1 kg/m 3 =0.062 lb./ft.

3 ). 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 10 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. One aspect is for a rigid, closed-celled polyisocyanate-based foam. 15 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. The rigid closed-cell celled polyisocyanate-based foams are useful 20 in spray insulation, as foam-in-place appliance foams, rigid insulating board stock, or in laminates. 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. 25 Any of a wide range of conventional methods for blowing such thermoplastic foams can be adapted for use herein. Another embodiment provides a foamable composition comprising thermoplastic foams, such as polystyrene, polyethylene (PE), preferably low density PE, or polypropylene (PP). 30 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 5 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 10 ruptured cells at ambient temperature; e.g., 25 OC and atmospheric pressure; and (6) recovering the extruded foam body. 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 15 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. In one aspect, the foaming amount of the blowing agent is in the 20 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 25 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 OC 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 30 temperature of about 115 to 150 OC, normally 130 OC, and extruded into the expansion zone at or below ambient temperature and at or below atmospheric pressure.

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. Patent No. 5,204,169; (2) extruded 5 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 10 (pcf) (25 to 160 kilograms per cubic meter (kg/M 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 15 (96 to 240 kg/M 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. All of the compositions and methods disclosed and claimed herein 20 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 25 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 30 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 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 5 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 10 Synthesis of 1, 1, 1,445,5,6,6,7,7,7-dodecafluorohept-2-ene (F1 4E) Synthesis of C 4

F

9

CH

2 CHICF3 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 Hastelloy TM shaker tube and heated to 200 C for 8 hours under autogenous pressure, which 15 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 20 products of the three reactions were combined and distilled to give 322.4 gm of C 4

F

9

CH

2

CHICF

3 (52.2 0/35 mm) in 70% yield. Conversion of C 4

F

9

CH

2

CHICF

3 to F14E

C

4

F

9

CH

2

CHICF

3 (322.4 gm, 0.73 moles) was added dropwise via addition 25 funnel to a 2L 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 4 and distilled through a 6" column filled with glass helices. The 30 product, F14E (173.4 gm, 76%) boils at 78.2 C. It was characterized by 19 F NMR (6 -66.7 (CF 3 , m, 3F), -81.7(CF 3 , m 3F), -124.8 (CF 2 , m, 2F), 126.4 (CF 2 , m, 2F), and -114.9 ppm (CF 2 , m, 2F)) 1 H NMR(6 6.45D) in chloroform-d solution.

Ju 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 4

F

9

CHICH

2

C

2

F

5 5 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 Hastelloy TM shaker tube and heated to 200 OC 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 10 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

4

F

9

CH

2

CHICF

3 (79-81 OC/ 67-68 mm Hg) in 37% yield. Conversion of C 4

F

9

CHICH

2

C

2

F

5 to F24E 15 A 1 L round bottom flask equipped with a mechanical stirrer, addition funnel, condenser, and thermocouple was charged with

C

4

F

9

CHICH

2

C

2

F

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 20 dropwise to the flask with rapid stirring over the course of about one hour as the temperature slowly increased from 210C to 420C. 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 25 distilled at atmospheric pressure. The product, F24E (128.7 gm, 63%) boils at 95.50C. It was characterized by 1 9 F NMR (6 -81.6 (CF 3 , m, 3F), 85.4(CF 3 , m 3F), -114.7 (CF 2 , m, 2F), -118.1 (CF 2 , m, 2F), -124.8 ppm

(CF

2 , m, 2F), -126.3 ppm (CF 2 , m, 2F)) and1H NMR (66.48) in chloroform-d solution. 30 0I EXAMPLE 3 Synthesis of CF 3

CH=CHCF(CF)

2 Synthesis of CF 3

CHICH

2

CF(CF

3

)

2

(CF

3

)

2 CFI (265 gm, 0.9 moles) and 3,3,3-trifluoropropene (44.0 gm, 5 0.45 moles) were added to a 400 ml Hastelloy shaker tube and heated to 2000C 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 3

)

2

CFCH

2

CHICF

3 (76-77 C/200 mm) in 62% yield. 10 Conversion of (CF 3 ) 2

CFCH

2

CHICF

3 to F1 3iE

(CF

3

)

2

CFCH

2

CHICF

3 (109 gM, 0.28 moles) was slowly added dropwise via addition funnel to a 500 ml round bottom flask heated to 420C 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 15 gm, 1.96 moles) and water (109 ml). During the addition, the temperature increased from 42 to 550C. After refluxing for 30 minutes, the temperature in the flask increased to 620C. Product was collected, washed with water, dried with MgSO 4 and distilled. The product, F13iE (41 gm, 55%), boils at 48-50 C and was characterized by 19F NMR (8 -187.6 (CF, m 1F), -77.1 20 (CF3, m 6F), - 66.3 (CF3, m 3F) in chloroform-d solution. POLYISOCYANATE-BASED FOAM EXAMPLES To demonstrate effectiveness of unsaturated fluorocarbon blowing agents, polyurethane and polyisocyanurate foam samples were prepared 25 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. 30 For molded foams, the reaction mixture is poured into a 2 M" x 13" x 15" (6.35 cm x 30.02 cm x 38.1 cm) heated aluminum mold.

Example 4: Polvisocyanurate Foam Component Parts by Weight aromatic polyester polyol (Stepanpol" PS- 120 2502A) polysiloxane surfactant (Dabco DC-1 93) 1.8 potassium octanoate catalyst (Hexcem 977) 3.2 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 (HFC- 80 1438mzz) (Blowing Agent) polymethylene polyphenylisocyanate 190 isocyanate (Papi" 580) All components except the isocyanate were premixed as a B-side. 5 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 1 00 0 F and allowed to expand. When cured, a 1" X 1" X 12" sample was cut from the core of the molded foam. The core sample was about 2.2 pounds/ft 3 (PCF) (35.2 kg/M 3 ) 10 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 (pt). Using a LaserComp FOX 304 Thermal Conductivity Meter, initial insulation value (R-value) was measured at 7.4/inch (thermal conductivity 15 of 19.5 milliW/(mK) at a mean temperature of 24.00C or 0.135 BTU-in/hr ft 2 -oF at a mean temperature of 75.2 0 F). Example 5: Polyurethane Pour-in-Place Foam Component Parts by Weight sucrose/glycerine initiated polyether polyol 140 (Voranol ® 360) silicone surfactant (Witco L-6900) 3.0 1515 N,N-Dimethylcyclohexylamine catalyst 1.7 (Polycat 8) pentamethyldiethylenetriamine catalyst 0.4 (Polycat 5) 2-Methyl(n-methyl amino b-sodium acetate 0.5 nonyl phenol) catalyst (Curithane" 52) Water 2.1 Blowing Agent 1,1,1,4,4,5,5,5,Octafluooro-2- 70 pentene (HFC-1438mzz) polymethylene polyphenylisocyanate 169 isocyanate (Papi" 27) 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 5 aluminum mold warmed to about 1 00 0 F and allowed to expand. When cured, a 1" X 1" X 12" sample was cut from the core of the molded foam. The core sample was about 2.0 pounds/ft 3 (PCF) (32.0 kg/M 3 ) density, had a good cell structure though it did contain some voids, and remained dimensionally stable. Magnified photographs of the foam 10 showed a uniform, highly closed cell structure, excluding the voids, and cell sizes about 200-300 microns (pt). 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 24.00C or thermal conductivity of 0.2044 BTU-in/hr-ft 2 -OF at a mean temperature of 75.2 0 F), 15 Example 6: Polvisocyanurate Foam Component Parts by Weight aromatic polyester polyol (Stepanpol@ PS-2502A) 14.4 polysiloxane surfactant (Dabco DC-1 93) 0.42 Potassium octanoate catalyst (Hexcem 977) 0.8 Tris-2,4,6-(dimethylaminomethyl)phenol/Bis(di methylaminomethyl)phenol catalyst 0.15 (Dabco TMR 30) 1,1,1,4,4,4 Hexafluooro-2-butene (HFC-1336mzz, Z-isomer) (Blowing Agent) 12.0 polymethylene polyphenylisocyanate isocyanate (Papi@ 22.8 580) 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 5 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-1 336mzz boiling point, and the amounts of catalyst were adjusted to decrease density. 10 EXAMPLE 7: Blowing Agent Solubility Effect on Foam Cell structure 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, 15 and being somewhat insoluble, act to help seed small cell growth during the foaming reaction. 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 20 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. 25 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 30 these unsaturated fluorocarbons can improve cell structure and foam 133 properties such as to overcome potential processing difficulties that otherwise would detrimentally impact foam performance. THERMOPLASTIC FOAM EXAMPLES 5 EXAMPLE 8 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 10 structure, long-term insulation value, and good dimensional stability. 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 15 general purpose, 2.5 melt index, and a typical nucleator would be magnesium silicate talc. 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 (0C) 129 Die gap (mm) 1.9 Die width (mm) 100 Foam thickness (mm) 52 Foam width (mm) 317 Foam density (kg/m3) 30.5 20 150 EXAMPLE 9 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 5 cartons, hamburger cartons, meat trays, plates, etc. 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. 10 A typical formulation is: 88 to 97 wt. percent polystyrene resin 2 to 8 wt. percent unsaturated fluorocarbon blowing agent 1 to 4 wt. percent nucleating agent The polystyrene sheet is typically extruded to a thickness of 50 to 15 300 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 OF to 400 OF (93.3 OC to 204.4 OC). The blowing agent concentration in the feed material will change depending on the desired thickness (thicker product requires more blowing agent). Once the 20 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. After storage, the rolls of foam are thermoformed, producing the desired 25 type of end-product (e.g., clam-shell containers, plates, etc.). EXAMPLE 10 Experiments were conducted to assess the stability of HFC-1 225ye for thermoplastic foams. 1,2,3,3,3-pentafluoro-1 -propene (HFC-1 225ye), 1,1 30 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 2600C in a pressure vessel with blowing agent and held 15/ 24 hours. After 24 hours, the vessel was cooled and all gaseous products were collected from the vessel for analysis. GC/MS A alysis of Gases after Exposure to 260 0 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 Magnesium Silicate 3 3 3 3 3 3 Talc Safoam@ FPN3 (sodium salts of 3 3 3 carbonic & polycarboxylic acids) HFC-1225ye 10 10 10 10 10 10 10 10 HFC-152a 10 10 HFC-134a 10 1010 Mild Steel X Coupon Air X x x x x x x x x x X Blowing Agent Purity >99.9% 93. 96. 100 >99.9% after Exposure 4% 7% % 5 The test data show that HFC-1 225ye was surprisingly as stable as HFC 134a and more stable than HFC-1 52a under extrusion conditions. The steel coupons from runs 32a, 32b and 24d were analyzed by Electron Spectroscopy for Chemical Analysis (ESCA). Fluoride ions (F-) were observed on the surface of all coupons. Estimated concentrations of 10 fluoride ion are shown in the table below. ESCA Analysis Results (unit: atom%) Sample Number Blowing Agents Talc Fluoride ion (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 Experiments were conducted to assess the compatibility of the unsaturated fluorocarbons for thermoplastic foams. Polystyrene and talc nucleator were heated to 2600C in a pressure vessel with blowing agent 5 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 10 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. # Sample Blowing Agent Weight Loss@ 3000C - 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 15 Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of 20 one or more other feature, integer, step, component or group thereof. Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia.

Claims (7)

1. A composition comprising a polyol and a blowing agent having reduced solubility in said polyol, wherein said blowing agent is selected from the group consisting of: a hydrofluorocarbon having the formula E- or Z-R'CH=CHR 2 , wherein R 1 and R 2 are, independently, C, to C6 perfluoroalkyl groups provided that in the Zisomer, R 1 and R 2 cannot both be CF 3 ; and a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF 3 CF=CFCF 3 , CF 3 CF 2 CF=CF 2 , CF 3 CF=CHCF 3 , CF 2 =CHCF 2 CF 3 , CF 2 =CFCHFCF 3 , CF 2 =CFCF 2 CHF 2 , CHF 2 CH=CHCF 3 , (CF 3 ) 2 C=CHCF 3 , CF 3 CF=CHCF 2 CF 3 , CF 3 CH=CFCF 2 CF 3 , CF 3 (CF 2 ) 3 CF=CF 2 , CF 3 CF 2 CF=CFCF 2 CF 3 , (CF 3 ) 2 C=C(CF 3 ) 2 , (CF 3 ) 2 CFCF=CHCF 3 , CF 2 =CFCF 2 CH 2 F, CF 2 =CFCHFCHF 2 , CH 2 =C(CF 3 ) 2 , CH 2 CF 2 CF=CF 2 , CH 2 FCF=CFCHF 2 , CH 2 FCF 2 CF=CF 2 , CF 2 =C(CF 3 )(CH 3 ), CF 2 =C(CHF 2 )(CH 3 ), CF 3 CF=CFCH 3 , CH 3 CF=CHCF 3 , CF 2 =CFCF 2 CF 2 CF 3 , CHF=CFCF 2 CF 2 CF 3 , CF 2 =CHCF 2 CF 2 CF 3 , CF 2 =CFCF 2 CF 2 CHF 2 , CHF 2 CF=CFCF 2 CF 3 , CF 3 CF=CFCF 2 CHF 2 , CF 3 CF=CFCHFCF 3 , CHF=CFCF(CF 3 ) 2 , CF 2 =CFCH(CF 3 ) 2 , CF 3 CH=C(CF 3 ) 2 , CF 2 =CHCF(CF 3 ) 2 , CHF=CFCF 2 CF 2 CHF 2 , CF 2 =CHCH(CF 3 ) 2 , CHF=CHCF(CF 3 ) 2 , CF 2 =C(CF 3 )CH 2 CF 3 , CF 2 =CHCF 2 CH 2 CF 3 , CF 3 CF=C(CF 3 )(CH 3 ), CHF=CHCH(CF 3 ) 2 , CH 3 CF=C(CF 3 ) 2 , CH 2 =CHCF 2 CHFCF 3 , CH 2 C(CF 3 )CH 2 CF 3 , (CF 3 ) 2 C=CHC 2 F 5 , (CF 3 ) 2 CFCF=CHCF 3 , (CF 3 ) 2 C=C(CH 3 )(CF 3 ), CF 3 CF=C(CH 3 )CF 2 CF 3 , CF 3 CH=CHCH(CF 3 ) 2 , (CF 3 ) 2 C=CHCF 2 CH 3 , CF 3 CF 2 CF=CFC 2 H 5 , CF 3 CF=CHCH(CF 3 )(CH 3 ), (CF 3 ) 2 C=CFC 2 H 5 , cyclo-CF 2 CF 2 CF 2 CH=CH-, cyclo CF 2 CF 2 CH=CH-, CF 3 CF 2 CF 2 C(CH 3 )=CH 2 , CF 3 CF 2 CF 2 CH=CHCH 3 , cyclo-CF 2 CF 2 CF=CF-, cyclo- z4U CF 2 CF=CFCF 2 CF 2 -, cyclo-CF 2 CF=CFCF 2 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 CH=CH 2 , CF 3 CH=CHCF 2 CF 3 , CF 2 CF 2 CH=CHCF 2 CF 3 , CF 3 CH=CHCF 2 CF 2 CF 3 , CF 3 CF=CFC 2 F 5 , CF 3 CF=CFCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CF=CFCF 2 C 2 F 5 , CF 3 CH=CFCF 2 CF 2 C 2 F 5 , CF 3 CF=CHCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CH=CFCF 2 C 2 F 5 , CF 3 CF 2 CF=CHCF 2 C 2 F 5 , C 2 F 5 CF 2 CF=CHCH 3 , C 2 F 5 CF=CHCH 3 , (CF 3 ) 2 C=CHCH 3 , CF 3 C(CH 3 )=CHCF 3 , CHF=CFC 2 F 5 , CHF 2 CF=CFCF 3 , (CF 3 ) 2 C=CHF, CH 2 FCF=CFCF 3 , CHF=CHCF 2 CF 3 , CHF 2 CH=CFCF 3 , CHF=CFCHFCF 3 , CF 3 CH=CFCHF 2 , CHF=CFCF 2 CHF 2 , CHF 2 CF=CFCHF 2 , CH 2 CF=CFCF 3 , CH 2 FCH=CFCF 3 , CF 3 CH=CFCH 2 F, CHF=CFCH 2 CF 3 , CHF=CHCHFCF 3 , CHF=CHCF 2 CHF 2 , CHF 2 CF=CHCHF 2 , CHF=CFCHFCHF 2 , CF 3 CF=CHCH 3 , CF 2 =CHCF 2 Br, CHF=CBrCHF 2 , CHBr=CHCF 3 , CF 3 CBr=CFCF 3 , CHBr=CHCF 2 CF 3 , CH 3 CBr=CHCF 3 , CF 3 CBr=CHCH 3 , (CF 3 ) 2 C=CHBr, CF 3 CF=CBrCF 2 CF 3 , E-CHF 2 CBr=CFC 2 F 5 , Z CHF 2 CBr=CFC 2 F 5 , CF 2 =CBrCHFC 2 F 5 , (CF 3 ) 2 CFCBr=CH 2 , CHBr=CF(CF 2 ) 2 CHF 2 , CF 2 =C(CH 2 Br)CF 3 , CH 2 =C(CBrF 2 )CF 3 , (CF 3 ) 2 CHCH=CHBr, (CF 3 ) 2 C=CHCH 2 Br, CF 2 =CHCF 2 CH 2 CBrF 2 , CFBr=CHCF 3 , CFBr=CFCF 3 , and CF 3 (CF 2 ) 3 CBr=CH 2 wherein the global warming potential of the blowing agent is less than 100, and the composition has a net global warming potential of less than 50 and an ozone depletion potential of not greater than 0.05.

2. The composition of claim 1, wherein R 1 and R 2 are, independently, CF 3 , C 2 F 5 , CF 2 CF 2 CF 3 , CF(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , CF(CF 3 )CF 2 CF 3 , CF 2 CF(CF 3 ) 2 , C(CF 3 ) 3 , CF 2 CF 2 CF 2 CF 2 CF 3 , CF 2 CF 2 CF(CF 3 ) 2 , C(CF 3 ) 2 C 2 F 5 , CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 , CF(CF 3 ) CF 2 CF 2 C 2 F 5 , or 4 1 C(CF 3 ) 2 CF 2 C 2 F 5 , provided that in the Z-isomer, R 1 and R 2 cannot both be CF 3 .

3. The composition of claim 1, wherein said blowing agent is selected from the group consisting of E-CF 3 CH=CHCF 3 , CF 3 CH=CHC 2 F 5 , CF 3 CH=CHCF 2 C 2 F 5 , CF 3 CH=CHCF(CF 3 ) 2 , C 2 F 5 CH=CHC 2 F 5 , CF 3 CH=CH(CF 2 ) 3 CF 3 , CF 3 CH=CHCF 2 CF(CF 3 ) 2 , CF 3 CH=CHCF(CF 3 )C 2 F 5 , CF 3 CH=CHC(CF 3 ) 3 , C 2 F 5 CH=CHCF 2 C 2 F 5 , C 2 F 5 CH=CHCF(CF 3 ) 2 , CF 3 CH=CH(CF 2 ) 4 CF 3 , CF 3 CH=CHCF 2 CF 2 CF(CF 3 ) 2 , CF 3 CH=CHC(CF 3 ) 2 C 2 F 5 , C 2 F 5 CH=CH(CF 2 ) 3 CF 3 , C 2 F 5 CH=CHCF 2 CF(CF 3 ) 2 , C 2 F 5 CH=CHCF(CF 3 )C 2 F 5 , C 2 F 5 CH=CHC(CF 3 ) 3 , C 2 F 5 CF 2 CH=CHCF 2 C 2 F 5 , (CF 3 ) 2 CFCH=CHCF(CF 3 ) 2 , C 2 F 5 CH=CHCF(CF 3 ) 2 , CF 3 CH=CH(CF 2 ) 5 CF 3 , CF 3 CH=CHCF(CF 3 )(CF 2 ) 2 C 2 F 5 , CF 3 CH=CHC(CF 3 ) 2 CF 2 C 2 F 5 , C 2 F 5 CH=CH(CF 2 ) 4 CF 3 , C 2 F 5 CH=CHCF 2 CF 2 CF(CF 3 ) 2 , C 2 F 5 CH=CHC(CF 3 ) 2 C 2 F 5 , C 2 F 5 CF 2 CH=CH(CF 2 ) 3 CF 3 , C 2 F 5 CF 2 CH=CHCF 2 CF(CF 3 ) 2 , C 2 F 5 CF 2 CH=CHCF(CF 3 )C 2 F 5 , C 2 F 5 CF 2 CH=CHC(CF 3 ) 3 , (CF 3 ) 2 CFCH=CH(CF 2 ) 3 CF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCH=CHCF(CF 3 )C 2 F 5 , (CF 3 ) 2 CFCH=CHC(CF 3 ) 3 , C 2 F 5 CH=CH(CF 2 ) 5 CF 3 , C 2 F 5 CH=CHCF(CF 3 )(CF 2 ) 2 C 2 F 5 , C 2 F 5 CH=CHC(CF 3 ) 2 CF 2 C 2 F 5 , C 2 F 5 CF 2 CH=CH(CF 2 ) 4 CF 3 , C 2 F 5 CF 2 CH=CHCF 2 CF 2 CF(CF 3 ) 2 , C 2 F 5 CF 2 CH=CHC(CF 3 ) 2 C 2 F 5 , (CF 3 ) 2 CFCH=CH(CF 2 ) 44 CF 3 , (CF 3 ) 2 CFCH=CHCF 2 CF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCH=CHC(CF 3 ) 2 C 2 F 5 , CF 3 (CF 2 ) 3 CH=CH(CF 2 ) 3 CF 3 , CF 3 (CF 2 ) 3 CH=CHCF 2 CF(CF 3 ) 2 , CF 3 (CF 2 ) 3 CH=CHCF(CF 3 )C 2 F 5 , CF 3 (CF 2 ) 3 CH=CHC(CF 3 ) 3 , (CF 3 ) 2 CFCF 2 CH=CHCF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCF 2 CH=CHCF(CF 3 )C 2 F 5 , (CF 3 ) 2 CFCF 2 CH=CHC(CF 3 ) 3 , C 2 F 5 CF(CF 3 )CH=CHCF(CF 3 )C 2 F 5 , C 2 F 5 CF(CF 3 )CH=CHC(CF 3 ) 3 , or (CF 3 ) 3 CCH=CHC(CF 3 ) 3 .

4. The composition of claim 1, wherein said blowing agent is selected from the group consisting of E-CF 3 CF=CHF, Z-CF 3 CF=CHF, Z-CF 3 CH=CHCF 3 , E-CF 3 CH=CFCF 3 , Z-CF 3 CH=CFCF 3 , E-CF 3 CF=CFCF 3 , Z-CF 3 CF=CFCF 3 , E-CF 3 CH=CHCF 2 CF 3 , Z-CF 3 CH=CHCF 2 CF 3 , E CF 3 CF=CHCF 2 CF 3 , Z-CF 3 CF=CHCF 2 CF 3 , E-CF 3 CH=CFCF 2 CF 3 , Z CF 3 CH=CFCF 2 CF 3 and E-CF 3 CF=CFCF 2 CF 3 and wherein the composition has an ozone depletion potential of about zero.

5. The composition of claim 1, wherein said blowing agent is selected from the group consisting of a hydrofluorocarbon having the formula E- or Z-R'CH=CHR 2 , wherein R 1 and R 2 are, independently, CF 3 , C 2 F 5 , CF 2 CF 2 CF 3 , CF(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , CF(CF 3 )CF 2 CF 3 , CF 2 CF(CF 3 ) 2 , C(CF 3 ) 3 , CF 2 CF 2 CF 2 CF 2 CF 3 , CF 2 CF 2 CF(CF 3 ) 2 , C(CF 3 ) 2 C 2 F 5 , CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 , CF(CF 3 ) CF 2 CF 2 C 2 F 5 , or C(CF 3 ) 2 CF 2 C 2 F 5 , provided that in the Z-isomer, R 1 and R 2 cannot both be CF 3 .

6. The composition of claim 1, wherein said blowing agent is selected from the group consisting of CF 3 CF=CHF, CF 3 CH=CF 2 , CHF 2 CF=CF 2 , CHF 2 CH=CHF, CF 3 CF=CH 2 , CH 2 FCF=CF 2 , CHF 2 CH=CF 2 , CHF 2 CF=CHF, CHF 2 CF=CH 2 , CF 3 CH=CH 2 , CH 3 CF=CF 2 , CH 2 FCHCF 2 , CH 2 FCF=CHF, CHF 2 CH=CHF, CF 3 CF=CFCF 3 , CF 3 CF 2 CF=CF 2 , CF 3 CF=CHCF 3 , CF 2 =CHCF 2 CF 3 , CF 2 =CFCHFCF 3 , CF 2 =CFCF 2 CHF 2 , CHF 2 CH=CHCF 3 , (CF 3 ) 2 C=CHCF 3 , CF 3 CF=CHCF 2 CF 3 , CF 3 CH=CFCF 2 CF 3 , (CF 3 ) 2 CFCH=CH 2 , CF 3 CF 2 CF 2 CH=CH 2 , CF 3 (CF 2 ) 3 CF=CF 2 , CF 3 CF 2 CF=CFCF 2 CF 3 , (CF 3 ) 2 C=C(CF 3 ) 2 , (CF 3 ) 2 CFCF=CHCF 3 , CF 2 =CFCF 2 CH 2 F, CF 2 =CFCHFCHF 2 , CH 2 CF 2 CF=CF 2 , CH 2 FCF=CFCHF 2 , CH 2 FCF 2 CF=CF 2 , CF 2 =C(CF 3 )(CH 3 ), CH 2 =CHCF 2 CHF 2 , CF 2 =C(CHF 2 )(CH 3 ), CHF=C(CF 3 )(CH 3 ), CF 3 CF=CFCH 3 , CH 3 CF=CHCF 3 , CF 2 =CFCF 2 CF 2 CF 3 , CHF=CFCF 2 CF 2 CF 3 , CF 2 =CHCF 2 CF 2 CF 3 , CF 2 =CFCF 2 CF 2 CHF 2 , CHF 2 CF=CFCF 2 CF 3 , CF 3 CF=CFCF 2 CHF 2 , CF 3 CF=CFCHFCF 3 , CHF=CFCF(CF 3 ) 2 , CF 2 =CFCH(CF 3 ) 2 , CF 3 CH=C(CF 3 ) 2 , CF 2 =CHCF(CF 3 ) 2 , CHF=CFCF 2 CF 2 CHF 2 , CF 2 =CHCH(CF 3 ) 2 , CHF=CHCF(CF 3 ) 2 , CF 2 =C(CF 3 )CH 2 CF 3 , CF 2 =CHCF 2 CH 2 CF 3 , CF 3 CF=C(CF 3 )(CH 3 ), CHF=CHCH(CF 3 ) 2 , CH 2 FCH=C(CF 3 ) 2 , CH 3 CF=C(CF 3 ) 2 , CH 2 C(CF 3 )CH 2 CF 3 , (CF 3 ) 2 C=CHC 2 F 5 , (CF 3 ) 2 CFCF=CHCF 3 , z4,3 CH 2 =CHC(CF 3 ) 3 , (CF 3 ) 2 C=C(CH 3 )(CF 3 ), CF 3 CF=C(CH 3 )CF 2 CF 3 , CF 3 CH=CHCH(CF 3 ) 2 , (CF 3 ) 2 C=CHCF 2 CH 3 , CF 3 CF 2 CF=CFC 2 H 5 , CF 3 CF=CHCH(CF 3 )(CH 3 ), (CF 3 ) 2 C=CFC 2 H 5 , cyclo-CF 2 CF 2 CF 2 CH=CH-, cyclo-CF 2 CF 2 CH=CH-, CF 3 CF 2 CF 2 CH=CHCH 3 , cyclo-CF 2 CF 2 CF=CF-, cyclo-CF 2 CF=CFCF 2 CF 2 -, cyclo-CF 2 CF=CFCF 2 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 CH=CH 2 , CF 3 CH=CHCF 2 CF 3 , CF 2 CF 2 CH=CHCF 2 CF 3 , CF 3 CH=CHCF 2 CF 2 CF 3 , CF 3 CF=CFC 2 F 5 , CF 3 CF=CFCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CF=CFCF 2 C 2 F 5 , CF 3 CH=CFCF 2 CF 2 C 2 F 5 , CF 3 CF=CHCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CH=CFCF 2 C 2 F 5 , CF 3 CF 2 CF=CHCF 2 C 2 F 5 , C 2 F 5 CF 2 CF=CHCH 3 , C 2 F 5 CF=CHCH 3 , (CF 3 ) 2 C=CHCH 3 , CF 3 C(CH 3 )=CHCF 3 , CHF=CFC 2 F 5 , CHF 2 CF=CFCF 3 , (CF 3 ) 2 C=CHF, CH 2 FCF=CFCF 3 , CHF=CHCF 2 CF 3 , CHF 2 CH=CFCF 3 , CHF=CFCHFCF 3 , CF 3 CH=CFCHF 2 , CHF=CFCF 2 CHF 2 , CHF 2 CF=CFCHF 2 , CH 2 CF=CFCF 3 , CH 2 FCH=CFCF 3 , CH 2 =CFCHFCF 3 , CF 3 CH=CFCH 2 F, CHF=CFCH 2 CF 3 , CHF=CHCHFCF 3 , CHF=CHCF 2 CHF 2 , CHF 2 CF=CHCHF 2 , CHF=CFCHFCHF 2 , CF 3 CF=CHCH 3 , CF 2 =CHCF 2 Br, CHF=CBrCHF 2 , CHBr=CHCF 3 , CF 3 CBr=CFCF 3 , CHBr=CHCF 2 CF 3 , CH 3 CBr=CHCF 3 , CF 3 CBr=CHCH 3 , (CF 3 ) 2 C=CHBr, CF 3 CF=CBrCF 2 CF 3 , E CHF 2 CBr=CFC 2 F 5 , Z-CHF 2 CBr=CFC 2 F 5 , CF 2 =CBrCHFC 2 F 5 , (CF 3 ) 2 CFCBr=CH 2 , CHBr=CF(CF 2 ) 2 CHF 2 , CF 2 =C(CH 2 Br)CF 3 , (CF 3 ) 2 CHCH=CHBr, (CF 3 ) 2 C=CHCH 2 Br, CF 2 =CHCF 2 CH 2 CBrF 2 , CFBr=CHCF 3 , CFBr=CFCF 3 , CF 3 CF 2 CF 2 CBr=CH 2 , and CF 3 (CF 2 ) 3 CBr=CH 2 .

7. The composition of any one of claims 1 to 6, substantially as hereinbefore described with reference to any one of the Examples.