Fluorosulfates of Hexafluoroisobutylene and Its Higher Homologs and Their Derivatives

Abstract

Hexafluoroisobutylene and its higher homologs are easily reacted with SO 3 to give fluorosulfates of the formula CH 2 ═C(R)CF 2 OSO 2 F, wherein R is a linear, branched or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen. These compounds react under mild conditions with many nucleophiles to give CH 2 ═C(R)CF 2 X, where X is derived from the nucleophile. This reaction provides a route to many substituted hexafluoroisobutylenes, which copolymerize easily with other fluoro- and hydrocarbon monomers such as vinylidene fluoride and ethylene.

1 . Copolymers of CH 2 ═C(R)CF 2 X, wherein R is a linear, branched, or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen, and X is selected from the group consisting of hydride, halides except fluoride, cyanide, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryl oxides, fluoroaryloxides, and perfluoroaryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, cyanate, isocyanate, thiocyanate, hydroxyalkoxides, haloalkoxides, epoxy alkoxides, cyanoalkoxides, ester alkoxides and thiolmercaptides, and at least one other monomer. 
     
     
         2 . The copolymers of  claim 1  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, vinyl acetate, perfluoroalkyl ethylenes of the formula CH 2 ═CH—C n F 2n+1  where n=1-10, tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoro- and perfluoromonomers of the dioxole type, and perfluoro(alkyl vinyl ethers). 
     
     
         3 . Copolymers of CH 2 ═C(R)CF 2 X, wherein R is a linear, branched, or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen, and X is selected from the group consisting of hydride, halides except fluoride, cyanide, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryl oxides, fluoroaryloxides, and perfluoroaryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, cyanate, isocyanate, thiocyanate, hydroxyalkoxides, haloalkoxides, epoxy alkoxides, cyanoalkoxides, ester alkoxides and thiolmercaptides, and at least one other monomer, wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, trifluoroethylene, and vinyl acetate. 
     
     
         4 . Copolymers of CH 2 ═C(R)CF 2 X, wherein R is a linear, branched, or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen, and X is selected from the group consisting of hydride, halides except fluoride, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, hydroxyalkoxides, ester alkoxides, and at least one other monomer. 
     
     
         5 . The copolymers of  claim 4  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, vinyl acetate, perfluoroalkyl ethylenes of the formula CH 2 ═CH—C n F 2n+1  where n=1-10, tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoro- and perfluoromonomers of the dioxole type, and perfluoro(alkyl vinyl ethers). 
     
     
         6 . Copolymers of CH 2 ═C(R)CF 2 X, wherein R is a linear, branched, or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen, and X is selected from the group consisting of hydride, halides except fluoride, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, hydroxyalkoxides, ester alkoxides, and at least one other monomer, wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, trifluoroethylene, and vinyl acetate. 
     
     
         7 . Copolymers of CF 2 ═C(R)CH 2 X, wherein R is a linear, branched, or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen, and X is selected from the group consisting of hydride, halides except fluoride, cyanide, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryl oxides, fluoroaryloxides, and perfluoroaryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, cyanate, isocyanate, thiocyanate, hydroxyalkoxides, haloalkoxides, epoxy alkoxides, cyanoalkoxides, ester alkoxides and thiolmercaptides, and at least one other monomer. 
     
     
         8 . The copolymers of  claim 7  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, vinyl acetate, perfluoroalkyl ethylenes of the formula CH 2 ═CH—C n F 2n+1  where n=1-10, tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoro- and perfluoromonomers of the dioxole type, and perfluoro(alkyl vinyl ethers). 
     
     
         9 . The copolymers of  claim 7  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, trifluoroethylene, and vinyl acetate. 
     
     
         10 . Copolymers of CF 2 ═C(CF 2 X)CH 2 X′, wherein X and X′ are independently selected from the group consisting of hydride, halides except fluoride, cyanide, alkoxides, fluoroalkoxides, and perfluoroalkoxides, aryl oxides, fluoroaryloxides, and perfluoroaryloxides, mercaptides, fluoromercaptides, perfluoromercaptides, secondary amines which may be fluorinated, azide, cyanate, isocyanate, thiocyanate, hydroxyalkoxides, haloalkoxides, epoxy alkoxides, cyanoalkoxides, ester alkoxides, and thiolmercaptides, and at least one other monomer. 
     
     
         11 . The copolymers of  claim 10  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, vinyl acetate, perfluoroalkyl ethylenes of the formula CH 2 ═CH—C n F 2n+1  where n=1-10, tetrafluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoro- and perfluoromonomers of the dioxole type, and perfluoro(alkyl vinyl ethers). 
     
     
         12 . The copolymers of  claim 10  wherein said at least one other monomer is selected from the group consisting of vinyl fluoride, vinylidene fluoride, ethylene, propylene, trifluoroethylene, and vinyl acetate.