HYDROBROMOCARBON BLENDS TO PROTECT AGAINST FIRES AND EXPLOSIONS

WIPO Patent Application WO/1998/009686

A2

A set of blends for extinguishment of fires, suppression of explosions, and inertion against fires and explosions is disclosed. The blends are comprised of a bromine-containing component and a fluorine-containing component. The bromine-containing component is comprised of one or more hydrobromoalkanes, hydrobromoalkenes, and/or hydrobromoarenes. The fluorine-containing component is comprised of one or more fluorine-containing halocarbons, which may also contain chlorine. Specifically provided as fluorine-containing halocarbons are saturated and unsaturated hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, and/or hydrofluoropolyethers. This provides a blend that mimics the fire and explosion protection action of halons and hydrobromofluorocarbons without the environmental impact associated with these compounds, which contain bromine and fluorine in the same molecule.

Tapscott, Robert E. (3812 Palomas Drive, N.E. Albuquerque, NM, 87110, US)
Moore, Ted A. (6300 Acacia Street, N.M. Albuquerque, NM, 87120, US)
Lifke, Joseph L. (2900 Vista Del Rey, N.E. #15, Albuquerque NM, 87112, US)

PCT/US1997/016660

March 12, 1998

September 09, 1997

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THE UNIVERSITY OF NEW MEXICO (Albuquerque, NM, 87131, US)

A62C35/02; A62D1/00; A62D1/08; A62C35/00; A62D1/00; (IPC1-7): A62D/

ROBERT W. BECKER & ASSOCIATES (Suite B, 11896 N. Highway 14 Tijeras, NM, 87059, US)

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We claim '2.^-

1.

A method of extinguishing or suppressing a fire in a total flood application, said method comprising the steps of a) providing at least one hydrobromocarbon selected from the group consisting of hydrobromoalkanes, hydrobromoalkenes, and hydrobromoarenes, b) mixing said at least one hydrobromocarbon with at least one halocarbon selected from the group consisting of all fluorinecontaining nonbrominated halocarbons to give a blend, said halocarbons containing no bromine and no iodine c) disposing said blend in a pressurized discharge system, and d) discharging said blend into an area to extinguish or suppress fires in that area.

2.

The method of claim 1 wherein said at least one halocarbon is selected from the group consisting of saturated and unsaturated hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, hydrofluoropolyethers and halogenated aromatics, said hydrobromoalkanes either have the formula CnH2n+2χBr , where n is 2 or greater and x is at least 1 but not greater than 2n+l, or have the formula where n is 3 or greater, x is at least 1 but not greater than 2n+l2y, and y is the number of rings, and said hydrobromoalkenes have the formula C„H2n.2wt2.xBrx, where w is the number of carboncarbon double bonds, n is w+1 or greater, and x is 2n2w+l or less but at least 1 .

3.

The method of claim 2 wherein said at least one hydrobromocarbon is selected from the group consisting of bromoethane (CH3CH2Br), 1 bromopropane (CH^CH2CH2Br), 2 bromopropane (CH3CHBrCH , 1bromobutane (CH3CH2CH2CH2Br), 2bromobutane (CH^CH2CHBrCH3), 1bromopentane (CH3CH2CH2CH2CH2B1), 2bromopentane (CH3CH2CH2CHBrCH3), 3bromopentane (CH3CH2CHBrCH2CH3), 1 bromohexane (CH3CH2CH2CH2CH2CH2Br), 2bromohexane ■in (CH3CH2CH2CH2CHBrCH3), 3bromohexane (CH3CH2CHBrCH2CH2CH3), l bromo2methylpropane (CH3CH(CH3)CH2Br), 2bromo2methyIpropane (CH3C(CH3)BrCH3), lbromo2methylbutane (CH3CH2CH(CH3)CH2Br), lbromo3 methylbutane (CH3CH(CH )CH2CH2Br), lbromo2methylpentane (CH3CH2CH2CH(CH3)CH2Br), lbromo3methylpentane (CH3CH2CH(CH3)CH2CH2Br), lbromo4methylpentane (CH3CH(CH3)CH2CH2CH2Br), 1 , 1dibromoethane (CH3CHBr2), 1 ,2 dibromoethane (CH2BrCH2Br), 1 , 1 dibromopropane (CH3CH2CHBr2), 1,2dibromopropane (CH3CHBrCH2Br), 1,3dibromopropane (CH2BrCH2CH2Br), bromocyclopropane (C3H5Br), bromocyclobutane (C H7Br), bromocyclopentane (CsHoBr), bromobenzene (CeH5Br), dibromobenzene (Cr,H4Br2), bromotoluene (C7H7Br), 3,3 dibromopropene (CH2=CHCHBr2), bromoethene (CH2=CHBr), 2 methyl 1, 1,3tribromopropene (CBr2=C(CH3)CH Br), 3bromopropene (CH2=CHCH2Br), 2bromopropene (CH2=CBrCH3), 1bromopropene (CHBr=CHCH3), 2,3dibromopropene (CH2=CBrCH2Br), 2methyll bro opropene (CHBr=C(CH3)CH3), 4bromol,3butanediene (CH2=CHCH=CHBr), 3bromol,3butanediene (CH2=CHCBr=CH2), 3bromo2methyll ,3butanediene (CH2=C(CH3)CBr=CH2), and 3,4 dibromo2methyll ,3butanediene (CH2=C(CH3)CBr=CHBr) and isomers thereof, and said at least one halocarbon is selected from the group consisting of 2,2dichlorol, l, l trifluoroethane (CHC12CF3), chlorodifluoromethane (CHC1F2), 2chloro 1, 1, 1 ,2tetrafluoroethane (CHC1FCF3), 1chloro 1, 1difluoroethane (CH3CC1F2), trifluoromethane (CHF3), difluoromethane (CH2F2), 1 , 1difluoroethane (CH3CHF2), pentafluoroethane (CHF2CF3), 1,1, 1,2tetrafluoroethane (CH2FCF3), 1, 1, 1,2,2pentafluoropropane (CF3CF2CH3), 1,1, 1,2,3,3 hexafluoropropane (CF3CHFCHF2), 1, 1, 1,3,3,3hexafluoropropane (CF3CH2CF3), 1,1, 1,2,2,3,3heρtafluoropropane (CF3CF2CF2H), 1, 1, 1,2,3, 3,3heptafluoropropane (CF3CHFCF3), 1 , 1 ,1,4,4,4 hexafluorobutane (CF3CH2CH2CF3), 1, 1,1,2,2,3,4,5,5,5 decafluoropentane (CF3CHFCHFCF2CF3), tetrafluoromethane (CF4), hexafluoroethane (CFtCFi), octafluoropropane (CF3CF2CF3), decafluorobutane (CF^CF2CF2CF3), dodecafluoropentane (CF3CF2CF2CF2CF3), tetradecafluorohexane (CF3CF2CF2CF2CF2CF3), perfluoromethylcyclohexane (CGFΠCF3), pcrfluorodimethylcyclohexane (C6Fιo(CF3)2), perfluoromethyldecali (C]oFι7CF ), perfluorodimethyl ether (CF3OCF3), perfluoromethylethylether (CF,CF2OCF3), perfluoromethylpropyl ether (CFιOCF2CF2CF3), perfluorodiethyl ether (CF3CF2OCF2CF3), methyl perfluorobutyl ether (CF3CF2CF2CF2OCH3), ethyl perfluorobutyl ether (CF3CF2CF2CF2OC2H5), bisdifluoromethyl ether (CHF2OCHF2), difluoromethyl 2,2,2trifluoroethyl ether (CF,CH2OCHF2), difluoromethyl 1,2,2,2tetrafluoroethyl ether (CHF2OCHFCF3), methyl 1, 1,2,2tetrafluoroethyl ether (CH3OCF2CHF2), methyl perfluoropropyl ether (CH3OCF2CF2CF3), methyl perfluoroisopropyl ether (CILOCF(CF3)2), 2,2,2trifluoroethyl perfluoroethyl ether (CF3CH2OCF CF3), methyl perfluoroethyl ether (CH3OCF2CF3), perfluoro1 butene (CF2=CFCF2CF3), perfluoro2 butene (CF3CF=CFCF3), and chloropentafluorobenzene (CβFsCI) .

4.

A method of extinguishing or suppressing a fire in a streaming application, said method comprising the steps of a) providing at least one hydrobromocarbon selected from the group consisting of hydrobromoalkanes, hydrobromoalkenes, and hydrobromoarenes, b) mixing said at least one hydrobromocarbon with at least one halocarbon selected from the group consisting of all fluorinecontaining halocarbons to give a blend, said halocarbons containing no bromine and no iodine c) disposing said blend in a pressurized discharge system, and d) discharging said blend from said system toward an existing fire to suppress or extinguish said fire.

5.

The method of claim 4 wherein said at least one halocarbon is selected from the group consisting of saturated and unsaturated hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, hydrofluoropolyethers and halogenated aromatics, said hydrobromoalkanes either have the formula CnH2n+2 Brs, where n is 2 or greater and x is at least 1 but not greater than 2n+l, or have the formula C„H2l,+2.2y BrN, where n is 3 or greater, x is at least 1 but not greater than 2n+l2y, and y is the number of rings, and said hydrobromoalkenes have the formula CnH2n.2v.+ xBrx, where w is the number of carboncarbon double bonds, n is w+1 or greater, and x is 2n2w+l or less but at least 1 .

6.

The method of claim 5 wherein said at least one hydrobromocarbon is selected from the group consisting of bromoethane (CFLCH2Br), 1 bromopropane (CH^CH2CH Br), 2 bromopropane (CHiCHBrCH , 1 bromobutane (CH,CH2CH2CH2Br), 2bromobutane (CH3CH2CHBrCH3), 1 bromopentane (CH3CH2CH2CH2CH2Br), 2bromopentane (CH3CH2CH2CHBrCH3), 3bromopentane (CH3CH2CHBrCH2CH3), 1bromohexane (CH3CH2CH2CH2CH2CH2Br), 2bromohexane (CH3CH2CH2CH2CHBrCH3), 3bromohexane (CH3CH2CHBrCH2CH2CH3), lbromo2methylpropane (CH3CH(CH3)CH2Br), 2bromo2methylpropane (CH3C(CH3)BrCH3), lbromo2methylbutane (CILCH2CH(CH3)CH2Br), l bromo3 ethylbutane (CH3CH(CH3)CH2CH2Br), lbromo2methylpentane (CH3CH2CH2CH(CH3)CH2Br), 1 bromo3methylpentane (CH3CH2CH(CH3)CH2CH2Br), 1 bromo4methylpentane (CH3CH(CH3)CH2CH2CH2Br), 1, 1dibromoethane (CH,CHBr2), 1,2 dibro oethane (CH2BrCH2Br), 1 , 1dibromopropane (CH3CH2CHBr2), 1,2dibromopropane (CH3CHBrCH2Br), 1,3dibromopropane (CH2BrCH2CH2Br), bromocyclopropane (C~,H5Br), bromocyclobutane (C4H7Br), bromocyclopentane (C5H9Br), bromobenzene (CcHsBr), dibromobenzene (CcH Br2), bromotoluene (C7H7Br), 3,3 dibromopropene (CH2=CHCHBr2), bromoethene (CH2=CHBr), 2 methyl 1,1,3tribromopropene (CBr2=C(CH3)CH2Br), 3bromopropene (CH2=CHCH2Br), 2bromopropene (CH2=CBrCH3), 1bromopropene (CHBr=CHCH3), 2,3dibromopropene (CH2=CBrCH2Br), 2methyll bromopropene 4bromol,3butanediene (CH2=CHCH=CHBr), 3bromol,3butanediene (CH2=CHCBr=CH2), 3bromo2methyll,3butanediene and 3,4 dibromo2methyll,3butanediene (CH2=C(CH3)CBr=CHBr) and isomers thereof and said at least one halocarbon is selected from the group consisting of 2,2dichlorol,l,ltrifluoroethane (CHC12CF3), chlorodifluoromethane (CHC1F2), 2chloro 1,1,1 ,2tetrafluoroethane (CHC1FCF3), 1chloro 1,1difluoroethane (CH3CC1F2), trifluoromethane (CHF3), difluoromethane (CH2F2), 1,1difluoroethane (CH3CHF2), pentafluoroethane (CHF2CF,), 1,1,1,2tetrafluoroethane (CH2FCF3), 1,1,1,2,2pentafluoropropane (CF3CF2CH3), 1,1,1,2,3,3 hexafluoropropane (CF3CHFCHF2), 1,1,1,3,3,3hexafluoropropane (CF3CH2CF3), 1,1,1, 2,2,3, 3heptafluoropropane (CF3CF2CF2H), 1,1,1,2,3,3,3heptafluoroρropane (CF3CHFCF3), 1,1,1,4,4,4 hexafluorobutane (CF3CH2CH2CF3), 1,1,1,2,2,3,4,5,5,5 decafluoropentane (CF3CHFCHFCF2CF3), tetrafluoromethane (CF4), hexafluoroethane (CF F3), octafluoropropane (CFιCF2CF3), decafluorobutane (CF3CF2CF2CF3), dodecafluoropentane (CF3CF2CF2CF2CF3), tetradecafluorohexane (CF3CF2CF2CF2CF2CF3), perfluoromethylcyclohexane (CcFnCF), perfluorodimethylcyclohexane (C6Fio(CF3)2), perfluoromethyldecalin perfluorodimethyl ether (CF3OCF3), perfluoromethylethylether (CF3CF2OCF3), perfluoromethylpropyl ether (CF3OCF2CF2CF), perfluorodiethyl ether (CF3CF2OCF2CF3), methyl perfluorobutyl ether (CF3CF2CF2CF2OCH3), ethyl perfluorobutyl ether (CF3CF2CF2CF2OC2H5), bisdifluoromethyl ether (CHF2OCHF2), difluoromethyl 2,2,2trifluoroethyl ether (CF3CH2OCHF2), difluoromethyl 1,2,2,2tetrafluoroethyl ether (CHF2OCHFCF3), methyl 1,1,2,2tetrafluoroethyl ether (CH3OCF2CHF2), methyl perfluoropropyl ether (CH3OCF2CF2CF3), methyl perfluoroisopropyl ether (CH3OCF(CF3)2), 2,2,2trifluoroethyl perfluoroethyl ether (CF^CH2OCF2CF3), methyl perfluoroethyl ether o \ (CH3OCF2CF3), perfluoro1butene (CF2=CFCF2CF3), perfluoro2 butene (CF3CF=CFCF3), and chloropentafluorobenzene (CδFsCl).

7.

A method of suppressing an explosion, said method comprising the steps of a) providing at least one hydrobromocarbon selected from the group consisting of hydrobromoalkanes, hydrobromoalkenes, and hydrobromoarenes, b) mixing said at least one hydrobromocarbon with at least one halocarbon selected from the group consisting of all fluorinecontaining halocarbons to give a blend, said halocarbons containing no bromine and no iodine, c) detecting an explosion and discharging said blend into the area of the explosion to suppress the explosion.

8.

The method of claim 7 wherein said at least one halocarbon is selected from the group consisting of saturated and unsaturated hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, hydrofluoropolyethers and halogenated aromatics, said hydrobromoalkanes either have the formula CnH2n+2.xBrx, where n is 2 or greater and x is at least 1 but not greater than 2n+l, or have the formula C,,H2n+2.2y.NBrχ, where n is 3 or greater, x is at least 1 but not greater than 2n+l2y, and y is the number of rings, and said hydrobromoalkenes have the formula CnH2n.2w+2.xBrx, where w is the number of carboncarbon double bonds, n is w+1 or greater, and x is 2n2w+l or less but at least 1.

9.

The method of claim 8 wherein said at least one hydrobromocarbon is selected from the group consisting of bromoethane (CH3CH2Br), 1 bromopropane (CH3CH2CH2Br), 2 bromopropane (CFI5CHBrCH3), 1bromobutane (CH3CH2CH2CH2Br), 2bromobutane (CH3CH2CHBrCH3), 1bromopentane (CH3CH2CH2CH2CH2Br), 2bromopentane (CH3CH2CH2CHBrCH3), 3bromopentane (CH3CH2CHBrCH2CH3), 1bromohexane (CH3CH2CH2CH2CH2CH2Br), 2bromohexane (CH3CH2CH2CH2CHBrCH3), 3bromohexane (CH3CH2CHBrCH2CH2CH3), lbromo2methylpropane (CH3CH(CH3)CH2Br), 2bromo2methyIpropane (CH3C(CH3)BrCH3), lbromo2methylbutane (CH3CH2CH(CH3)CII2Br), lbromo3 methylbutane (CH,CH(CH3)CH2CII2Br), lbromo2methylpentane (CH3CH2CH2CH(CH3)CFI2Br), 1 bromo3methylpentane (CH3CH2CH(CH3)CH2CH2Br), lbromo4methylpentane (CH3CH(CH3)CH2CH2CH2Br), 1,1dibromoethane (CH3CHBr2), 1,2 dibromoethane (CH2BrCH2Br), 1,1dibromoρropane (CH,CH2CHBr2), 1,2dibromopropane (CH3CHBrCH2Br), 1,3dibromopropane (CH2BrCH2CH2Br), bromocyclopropane (CiHsBr), bromocyclobutane (CII7Br), bromocyclopentane (CsI^Br), bromobenzene (C6H5Br), dibromobenzene (C6HBr), bromotoluene (C7II7Br), 3,3 dibromopropene (CH=CHCHBr2), bromoethene (CIl2=CHBr), 2 methyl 1,1,3tribromopropene (CBr2=C(CH3)CH2Br), 3bromopropene (CH2=CHCH2Br), 2bromopropene (CH2=CBrCH3), 1bromopropene (CHBr=CHCH3), 2,3dibromopropene (CH2=CBrCH2Br), 2methyll bromopropene (CHBr=C(CH,)CH3), 4bromol,3butanediene (CH2=CHCH=CHBr), 3bromol,3butanediene (CH2=CHCBr=CH2), 3bromo2methyll,3butanediene and 3,4 dibromo2methyll,3butanediene (CH2=C(CH3)CBr=CHBr) and isomers thereof and said at least one halocarbon is selected from the group consisting of 2,2dich!orol,l,ltrifluoroethane (CHC12CF3), chlorodifluoromethane (CHCIF2), 2chloro 1,1,1 ,2tetrafluoroethane (CHC1FCF3), 1chloro 1,1difluoroethane (CH3CC1F2), trifluoromethane (CHF3), difluoromethane (CH2F), 1,1difluoroethane (CH3CHF2), pentafluoroethane (CHF2CF3), 1,1,1,2tetrafluoroethane (CH2FCF3), 1,1,1,2,2pentafluoropropane (CF,CF2CH3), 1,1,1,2,3,3 hexafluoropropane (CF3CHFCHF2), 1,1,1,3,3,3hexafluoropropane (CF3CH2CF3), 1,1, 1,2,2,3, 3heptafluoropropane (CF,CF2CF2H), 1,1,1,2,3,3,3heptafluoropropane (CF3CHFCF3), 1,1,1,4,4,4 hexafluorobutane (CF3CH2CH2CF3), 1,1,1,2,2,3,4,5,5,5 decafluoropentane (CF3CHFCHFCF2CF3), tetrafluoromethane (CF4), hexafluoroethane (CF3CF3), octafluoropropane (CF3CF2CF3), decafluorobutane (CF3CF2CF2CF3), dodecafluoropentane (CF3CF2CF2CF2CF3), tetradecafluorohexane (CF3CF2CF2CF2CF2CF3), perfluoromethylcyclohexane (C6FπCF3), perfluorodimethylcyclohexane (C6Fιo(CF3)2), perfluoromethyldecalin (CιoFπCF3), perfluorodimethyl ether (CF3OCF3), perfluoromethylethylether (CF3CF2OCF3), perfluoromethylpropyl ether (CF3OCF CF2CF3), perfluorodiethyl ether (CF3CF2OCF2CF3), methyl perfluorobutyl ether (CF3CF2CF2CF2OCH3), ethyl perfluorobutyl ether (CF3CF2CF2CF2OC2H5), bisdifluoromethyl ether (CHF2OCHF2), difluoromethyl 2,2,2trifluoroethyl ether (CF3CH2OCHF2), difluoromethyl 1 ,2,2,2tetrafluoroethyl ether (CHF2OCHFCF3), methyl 1, 1,2,2tetrafluoroethyl ether (CH3OCF2CHF2), methyl perfluoropropyl ether (CH3OCF2CF2CF3), methyl perfluoroisopropyl ether (CH3OCF(CF3)2), 2,2,2trifluoroethyl perfluoroethyl ether (CF3CH OCF2CF3), methyl perfluoroethyl ether (CH3OCF2CF3), perfluoro 1 butene (CF2=CFCF2CF3), perfluoro2 butene (CF3CF=CFCF3), and chloropentafluorobenzene (C6F5C1).

10.

A method of inerting an area to prevent a fire or explosion, said method comprising the steps of: a) providing at least one hydrobromocarbon selected from the group consisting of hydrobromoalkanes, hydrobromoalkenes, and hydrobromoarenes, b) mixing said at least one hydrobromocarbon with at least one halocarbon selected from the group consisting of all fluorinecontaining halocarbons to give a blend, said halocarbon containing no bromine and no iodine, c) disposing said blend in a pressurized discharge system, and d) discharging said agent into said area to prevent a fire or an explosion from occurring.

11.

The method of claim 10 wherein said at least one halocarbon is selected from the group consisting of saturated and unsaturated hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, hydrofluoropolyethers and halogenated aromatics, said hydrobromoalkanes either have the formula C„H2ll t2.vBι\, where n is 2 or greater and x is at least 1 but not greater than 2n+l, or have the formula where n is 3 or greater, x is at least 1 but not greater than 2n+l 2y, and y is the number of rings, and said hydrobromoalkenes have the formula C,,H2n.2w, .xBrx, where w is the number of carboncarbon double bonds, n is w+1 or greater, and x is 2n2w+l or less but at least 1 .

12.

The method of claim 1 1 wherein said al least one hydrobromocarbon is selected from the group consisting of bromoethane (CH*CH2Br), 1 bromopropane (CH,CH2CH2Br), 2 bro opropane (CHiCHBrCH?), 1bromobutane (CH3CH2CH2CH2Br), 2bromobutane (CH^CH2CHBrCH3), 1 bromopentane (CH3CH2CH2CH2CH2B1), 2bromopentane (CILCH2CH2CHBrCH3), 3bromopentane (CILCH2CHBrCH2CH ), 1 bromohexane (CH3CH2CH2CH2CH2CH2B , 2bromohexane (CH3CH2CH2CH2CHBrCH3), 3bromohexane lbromo2methylpropane (CH3CH(CFI3)CH2Br), 2bromo2methylpropane (CH,C(CH3)BrCH3), lbromo2methylbutane (CH3CH2CH(CH3)CH2Br), lbromo3 methylbutane (CH3CH(CH3)CH2CH2Br), l bromo2methylpentane (CH3CH2CH2CH(CH3)CI I2Br), 1 bromo3methylpentane (CH3CH2CH(CH3)CH2CH2Br), l bromo4methylpentane (CH3CH(CH3)CH2CH2CH2Br), 1 , 1dibromoethane (CH3CHBr2), 1,2 dibromoethane (CH2BrCH2Br), 1 , 1dibromopropane (CH3CH2CHBr2), 1,2dibromopropane (CH3CHBrCH2Br), 1 ,3dibromopropane (CH2BrCH2CH2Br), bromocyclopropane (C3H5Br), bromocyclobutane (C4H7Br), bromocyclopentane (C5H9Br), bromobenzene (CβHsBr), dibromobenzene (C6H4Br2), bromotoluene (C7H7Br), 3,3 dibromopropene (CH2=CHCHBr2), bromoethene (CH2=CHBr), 2 methyl 1,1 ,3tribromopropene (CBr2=C(CIL)CH2Br), 3bromopropene (CH2=CHCH2Br), 2bromopropene (CH2=CBrCH3), 1bromopropene (CHBr=CHCH3), 2,3dibromopropene (CH2=CBrCH2Br), 2methyll bromopropene (CHBr=C(CH3)CH3), 4bromol,3butanediene (CH2=CHCH=CHBr), 3bromol,3butanediene (CH2=CIICBr=CH2), 3bromo2methyll,3butanediene (CH2=C(ClL)CBr=CH2), and 3,4 dibromo2methyl 1 ,3butanediene (CH2=C(CIL)CBrCHBr) and isomers thereof and said at least one halocarbon is selected from the group consisting of 2,2dichlorol,l,ltrifluoroethane (CHC12CF3), chlorodifluoromethane (CHC1F2), 2chloro 1,1,1 ,2tetrafluoroethane (CHCIFCF3), 1chloro 1,1difluoroethane (CH3CC1F2), trifluoromethane (CHF3), difluoromethane (CH2F2), 1,1difluoroethane (CH3CHF2), pentafluoroethane (CHF2CF3), 1,1,1,2tetrafluoroethane (CH2FCF), 1,1,1,2,2pentafluoropropane (CF*CF2CHι), 1,1,1,2,3,3 hexafluoropropane (CF,CHFCHF2), 1,1,1,3,3,3hexafluoropropane (CF3CH2CF3), 1,1,1, 2,2,3, 3heptafluoropropane (CF3CF2CF2H), 1,1,1,2,3,3,3heptafluoropropane (CF,CHFCF3), 1,1,1,4,4,4 hexafluorobutane (CF,CH2CH2CF3), 1,1,1,2,2,3,4,5,5,5 decafluoropentane (CF,CHFCHFCF2CF~,), tetrafluoromethane (CF4), hexafluoroethane (CF3CF3), octafluoropropane (CF3CF2CF3), decafluorobutane (CF^CF2CF2CF3), dodecafluoropentane (CF3CF2CF2CF2CF3), tetradecafluorohexane (CF3CF2CF2CF2CF2CF3), perfluoromethylcyclohexane (C6FnCF3), perfluorodimethylcyclohexane (C6F)0(CF3)2), perfluoromethyldecalin (C10FπCF3), perfluorodimethyl ether (CF3OCF3), perfluoromethylethylether (CF3CF2OCF3), perfluoromethylpropyl ether (CF3OCF2CF2CF3), perfluorodiethyl ether (CF3CF2OCF2CF3), methyl perfluorobutyl ether (CF,CF2CF2CF2OCH3), ethyl perfluorobutyl ether (CF,CF2CF2CF2OC2H5), bisdifluoromethyl ether (CHF2OCHF2), difluoromethyl 2,2,2trifluoroethyl ether (CF3CH2OCHF), difluoromethyl 1,2,2,2tetrafluoroethyl ether (CHF2OCHFCF3), methyl 1,1,2,2tetrafluoroethyl ether (CH3OCF2CHF2), methyl perfluoropropyl ether (CH,OCF2CF2CF3), methyl perfluoroisopropyl ether (CH3OCF(CF3)2), 2,2,2trifluoroethyl perfluoroethyl ether (CF3CH2OCF2CF3), methyl perfluoroethyl ether (CH3OCF2CF3), perfluoro1butene (CF2=CFCF2CF3), perfluoro2 butene (CF3CF=CFCF3), and chloropentafluorobenzene (CGFSCI).

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AL Albania AM Armenia AT Austria AU Australia AZ Azerbaijan BA Bosnia and Herzegovina BB Barbados BE Belgium BF Burkina Faso BG Bulgaria BJ Benin BR Brazil BY Belarus CA Canada CF Central African Republic CG Congo CH Switzerland Cl Côte d'lvoire CM Cameroon CN China <BR> <BR> CU Cuba<BR> CZ Czech Republic DE Germany DK Denmark EE Estonia ES Spain Fl Finland <BR> <BR> FR France<BR> GA Gabon GB United Kingdom GE Georgia GH Ghana <BR> <BR> GN Guinea<BR> GR Greece HU Hungary IE Ireland IL Israel IS Iceland IT Italy JP Japan<BR> KE Kenya KG Kyrgyzstan KP Democratic People's Republic of Korea KR Republic of Korea KZ Kazakstan LC Saint Lucia LI Liechtenstein LK Sri Lanka LR Liberia LS Lesotho LT Lithuania LU Luxembourg LV Latvia MC Monaco MD Republic of Moldova MG Madagascar MK The former Yugoslav Republic of Macedonia ML Mali MN Mongolia MR Mauritania MW Malawi MX Mexico NE Niger NL Netherlands NO Norway NZ New Zealand<BR> PL Poland PT Portugal RO Romania RU Russian Federation SD Sudan SE Sweden SG Singapore SI Slovenia SK Slovakia SN Senegal SZ Swaziland TD Chad TG Togo<BR> TJ Tajikistan TM Turkmenistan TR Turkey TT Trinidad and Tobago UA Ukraine UG Uganda US United States of America UZ Uzbekistan VN Viet Nam <BR> <BR> YU Yugoslavia<BR> ZW Zimbabwe

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