Fluoroelastomers

Abstract

Fluoroelastomers comprising in the polymer chain units deriving from fluorovinyl ethers having the formula: CFX═CXOCF 2 OR  (I) wherein R is a C 2 -C 6 linear, branched or C 5 -C 6 cyclic (per) fluoroalkyl group, or a C 2 -C 6 linear, branched (per) fluorooxyalkyl group containing from one to three oxygen atoms; when R is fluoroalkyl or fluorooxyalkyl group as above defined, it can contain from 1 to 2 atoms, equal or different, selected from the following: H, Cl, Br, I; X═F, H.

I claim  
     
         1 . A fluoroelastomer comprising units derived from fluorovinyl ethers of formula:  
       CFX═CXOCF 2 OR  (I)  
       wherein: 
 1) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;  
 2) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with atoms selected from the group consisting of H, Cl, Br, and I; and  
 3) X is F or H.  
 
     
     
         2 . The fluoroelastomer of    claim 1    wherein R is CF 2 CF 2 Y and Y is F or OCF 3 .  
     
     
         3 . The fluoroelastomer of    claim 2    wherein each X is F.  
     
     
         4 . The fluoroelastomer of    claim 3    wherein Y is F.  
     
     
         5 . The fluoroelastomer of    claim 1    further comprising in the polymer chain units derived from either: 
 1) vinylidene fluoride and at least one additional copolymerizable comonomer selected from a C 2 -C 8  perfluoroolefin; a C 2 -C 8  chlorofluoroolefin; a C 2 -C 8  bromofluoroolefin; a C 2 -C 8  iodofluoroolefin; a fluoroalkyl vinyl ether of structure CF 2 ═CFOR t   f , wherein R t   f  is a C 1 -C 6  alkyl group in which from one up to all hydrogen atoms are replaced with fluorine atoms; a perfluorooxyalkyl vinyl ether of structure CF 2 ═CFOX t , wherein x t  is a C 1 -C 12  perfluorooxyalkyl group having one or more ether oxygens; or a C 2 -C 8  olefin; or  
 2) tetrafluoroethylene and at least one additional copolymerizable comonomer selected from; fluoroalkyl vinyl ethers of structure CF 2 ═CFOR t   f , wherein R t   f  is as above defined; perfluorooxyalkyl vinyl ethers of structure CF 2 ═CFOX t , wherein x t  is as above defined;  
 C 2 -C 8  fluoroolefin, chlorofluoroolefins, bromofluoroolefins, and iodofluoroolefins; and C 2 -C 8  olefins.  
 
     
     
         6 . The fluoroelastomer of    claim 5    wherein the C 2 -C 8  perfluoroolefin is either tetrafluoroethylene, hexafluoropropene, or hexafluoroisobutene.  
     
     
         7 . The fluoroelastomer of    claim 5    wherein the C 2 -C 8  chlorofluoroolefin is chlorotrifluoroethylene.  
     
     
         8 . The fluoroelastomer of    claim 5    wherein the C 2 -C 8  bromofluoroolefin is bromotrifluoroethylene.  
     
     
         9 . The fluoroelastomer of    claim 5    wherein the fluoroalkyl vinyl ether is heptafluoropropyl trifluorovinyl ether.  
     
     
         10 . The fluoroelastomer of    claim 5    wherein the perfluorooxyalkyl vinyl ether is tetradecylfluoro-2-propoxypropyl trifluorovinyl ether.  
     
     
         11 . The fluoroelastomer of    claim 5    wherein the C 2 -C 8  olefin is either ethylene or propylene.  
     
     
         12 . A fluoroelastomer made by the copolymerization of one or more comonomers, which comonomers together comprise a base fluoroelastomer composition, with a fluorovinyl ether of formula:  
       CFX═CXOCF 2 OR  (I)  
       wherein 
 1) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;  
 2) up to two fluorine atoms of the linear, branched or cyclic perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and  
 3) X is F or H; wherein  
 a sufficient amount of fluorovinyl ether is used in the copolymerization to result in an elastomeric copolymer.  
 
     
     
         13 . The fluoroelastomer of    claim 12    wherein R is CF 2 CF 2 Y and Y is F or OCF 3 .  
     
     
         14 . The fluoroelastomer of    claim 13    wherein each X is F.  
     
     
         15 . The fluoroelastomer of    claim 14    wherein Y is F.  
     
     
         16 . The fluoroelastomer of    claim 12    wherein the amount of fluorovinyl ether used in the copolymerization is at least about 10 mole %, the remainder comprising one or more comonomers.  
     
     
         17 . The fluoroelastomer of    claim 16    wherein the amount of fluorovinyl ether used is at least about 15 mole %.  
     
     
         18 . The fluoroelastomer of    claim 17    wherein the amount of fluorovinyl ether used is between about 15 mole % and about 20 mole %.  
     
     
         19 . The fluoroelastomer of    claim 12    wherein the one or more comonomers are fluorinated compounds having at least one polymerizable carbon-carbon double bond, said comonomers being capable of forming copolymers with the fluorovinyl ether.  
     
     
         20 . The fluoroelastomer of    claim 19    wherein the fluorinated compound further comprises at least one atom selected from the group consisting of chlorine, bromine, iodine, and oxygen.  
     
     
         21 . The fluoroelastomer of    claim 19   , wherein the olefin is copolymerized with at least one comonomer that is a C 2 -C 8  olefin.  
     
     
         22 . The fluoroelastomer of    claim 21    wherein the olefinically unsaturated hydrocarbon is selected from the group consisting of ethylene, propylene, and isobutylene.  
     
     
         23 . The fluoroelastomer of    claim 19    wherein the one or more comonomers are selected from the following: 
 1) C 2 -C 8  perfluoroolefins;  
 2) C 2 -C 8  fluoroolefins;  
 3) C 2 -C 8  chlorofluoroolefins,  
 4) C 2 -C 8  bromofluoroolefins,  
 5) C 2 -C 8  iodofluoroolefins;  
 6) perfluoroalkyl vinyl ethers having the structure CF 2 =CFOR f (PAVE), wherein R f is a Cl-C 6  perfluoroalkyl group in which 0 or 1 of the fluorine atoms is replaced with a bromine atom;  
 7) fluorooxyalkyl vinyl ethers having the structure CF 2 ═CFOX a , wherein X a  is a C 1 -C 12  alkyl group, a C 1 -C 12  oxyalkyl group, or a C 1 -C 12  perfluorooxyalkyl group having at least one ether oxygen;  
 8) sulphonic monomers having the structure CF 2 ═CFOX b SO 2 F, wherein X b  is selected from CF 2 CF 2 , CF 2 CF 2 CF 2 , and CF 2 CF(CFX C ), and wherein X c  is selected from F, Cl, and Br;  
 9) a bis-olefin having the general formula R I   1 R I   2 C═CR I   3 ,—Z—CR I   4 ═CR I   5 R I   6   (IA)  
   
 wherein;  
 R I   1 , R I   2 , R I   3 , R I   4 , R I   5 , and R I   6 , are the same or different and are either H or C 1 -C 5  alkyl; and Z is a C 1 -C 18  linear or branched alkylene or cycloalkylene diradical in which none to all of the hydrogen atoms are replaced with fluorine, or Z is a polyoxyalkylene diradical in which none to all of the hydrogen atoms are replaced with fluorine.  
 
     
     
         24 . The fluoroelastomer of    claim 23    wherein the perfluoroolefin is selected from the group consisting of tetrafluoroethylene (TFE), hexafluoropropene (HFP), and hexafluoroisobutene.  
     
     
         25 . The fluoroelastomer of    claim 23    wherein the fluoroolefin is selected from the group consisting of vinylfluoride (VF), vinylidene fluoride (VDF), trifluoroethylene, and fluoroalkenes represented by the formula CH 2 ═CHR 2   f , wherein R 2   f  is a linear or branched C 1 -C 6  perfluoroalkyl group.  
     
     
         26 . The fluoroelastomer of    claim 23    wherein the comonomer is either chlorotrifluoroethylene or bromotrifluoroethylene.  
     
     
         27 . The fluoroelastomer of    claim 23    wherein X a  is the tetradecafluoro-2-propoxypropyl group.  
     
     
         28 . The fluoroelastomer of    claim 23    wherein Z is at least partially fluorinated.  
     
     
         29 . The fluoroelastomer of    claim 23    wherein Z is a perfluoropolyoxyalkylene diradical.  
     
     
         30 . The fluoroelastomer of    claim 23    wherein Z is a C 4 -C 12  perfluoroalkylene diradical and R I   1 , R I   2 , R I   3 , R I   4 , R I   5 , R I   6  are H.  
     
     
         31 . The fluoroelastomer of    claim 23    wherein Z is a fluoropolyoxyalkylene diradical having the formula:  
       —(Q) p —CF 2 O—(CF 2 CF 2 O) ma (CF 2 O) na —CF 2 —(Q) p —  (IIA)  
       wherein: 
 a) Q is a C 1 -C 10  alkylene or oxyalkylene radical;  
 b) p is 0 or 1;  
 c) ma and na are integers such that the ma/na ratio is between about 0.2 and about 5; and  
 d) the molecular weight of the fluoropolyoxyalkylene diradical is between about 500 and about 10,000.  
 
     
     
         32 . The fluoroelastomer of    claim 31    wherein the molecular weight of the fluoropolyoxyalkylene diradical is between about 1,000 and about 4,000.  
     
     
         33 . The fluoroelastomer of    claim 31    wherein Q is selected from —CH 2 OCH 2 — and —CH 2 O(CH 2 CH 2 O) s CH 2 — wherein s is 1 to 3.  
     
     
         34 . The fluoroelastomer of    claim 23    wherein the amount of bis-olefin of formula (IA) used in copolymerization is such that between about 0.001 and about 1 mole percent of repeat units in the polymer are dervied from the bis-olefin.  
     
     
         35 . The fluoroelastomer of    claim 12    wherein the base fluoroelastomer composition is comprised of one or more comonomers selected from: 
 1) vinylidene fluoride and at least one additional comonomer selected from a C 2 -C 8  perfluoroolefin; a C 2 -C 8  chlorofluoroolefin; a C 2 -C 8  bromofluoroolefin; a C 2 -C 8  iodofluoroolefin; a fluoroalkyl vinyl ether of structure CF 2 ═CFOR t   f , wherein R t   f  is a C 1 -C 6  alkyl group in which from one up to all hydrogen atoms replaced with fluorine and up to one such hydrogen atom not replaced with fluorine is replaced with bromine; perfluorooxyalkyl vinyl ethers of structure CF 2 ═CFOX t , wherein x t  is a C 1 -C 12  perfluorooxyalkyl group having one or more ether oxygens; and a C 2 -C 8  olefin; or  
 2) tetrafluoroethylene and at least one additional comonomer selected from a perfluoroalkylvinylether of structure CF 2 ═CFOR t   f , wherein R t   f  is as above defined; perfluorooxyalkylvinyl ethers of structure CF 2 ═CFOX t , wherein x t  is as above defined; a C 2 -C 8  fluoroolefin, a C 2 -C 8  chlorofluoroolefin, a C 2 -C 8  bromofluoroolefins, or a C 2 -C 8  iodofluoroolefin; and a C 2 -C 8  olefin.  
 
     
     
         36 . The fluoroelastomer of    claim 35    wherein the C 2 -C 8  perfluoroolefin is selected from tetrafluoroethylene and hexafluoropropylene.  
     
     
         37 . The fluoroelastomer of    claim 35    wherein the C 2 -C 8  chlorofluoroolefin is chlorotrifluoroethylene.  
     
     
         38 . The fluoroelastomer of    claim 35    wherein the C 2 -C 8  bromofluoroolefin is bromotrifluoroethylene.  
     
     
         39 . The fluoroelastomer of    claim 35    wherein the fluoroalkyl vinyl ether is pentafluoropropyl trifluorovinyl ether.  
     
     
         40 . The fluoroelastomer of    claim 35    wherein the perfluorooxyalkyl vinyl ether is perfluoro-2-propoxypropyl vinyl ether.  
     
     
         41 . The fluoroelastomer of    claim 35    wherein the C 2 -C 8  olefin is either ethylene or propylene.  
     
     
         42 . A fluoroelastomer, curable by a peroxidic route, comprising units derived from the following monomers: 
 1) from about 45 mole % to about 65 mole % vinylidene fluoride;    2) from 0 to about 45 mole % of either hexafluoropropene or a perfluoroalkyl vinyl ether of structure CF 2 ═CFOR 2   f , wherein R 2 f is a C 1 -C 6  perfluoroalkyl group in which 0 or 1 fluorine atoms are replaced with bromine atoms;    3) from 0 to about 30 mole % tetrafluoroethylene;    4) from 0 to about 40 mole % of a C 2 -C 8  olefin; and    5) from 5 to about 40 mole % of a fluorovinyl ether of formula    CFX═CXOCF 2 OR  (I)    wherein:    a) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;    b) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and    c) X is F or H; with the proviso that, together, less than about 45 mole % of all units in the fluoroelastomer are dervived from hexafluoropropene, perfluoroalky vinyl ether, and perfluorovinyl ether combined.    
     
     
         43 . The fluoroelastomer of    claim 42    having one or more atoms selected from bromine and iodine.  
     
     
         44 . The fluoroelastomer of    claim 42    in the form of an O-ring.  
     
     
         45 . A fluoroelastomer, curable by a peroxidic route, comprising units derived from the following monomers: 
 1) from about 50 mole % to about 85 mole % tetrafluoroethylene;    2) from 0 to about 50 mole % of a perfluoroalkyl vinyl ether of structure CF 2 ═CFOR 2   f , wherein R 2   f  is a C 1 -C 6  perfluoroalkyl group in which 0 or 1 fluorine atoms are replaced with bromine atoms;    4) from 0 to about 40 mole % of a C 2 -C 8  olefin; and    5) from about 1 to about 40 mole % of a fluorovinyl ether of formula    CFX═CXOCF 2 OR    wherein:    a) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;    b) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and    c) X is F or H; with the proviso that, together, less than about 50 mole % of the units are derived from perfluoroalky vinyl ether and fluorovinyl ether.    
     
     
         46 . The fluoroelastomer of    claim 45    having one or more atoms that selected from bromine and iodine.  
     
     
         47 . The fluoroelastomer of    claim 45    in the form of an 0-ring.  
     
     
         48 . A fluoroelastomer, curable by an ionic route, comprising units derived from the following monomers in the given amounts: 
 1) between about 48 mole % and about 85 mole % vinylidene fluoride;    2) from 20 mole % up to about 35 mole % hexafluoropropene;    3) from 0 up to about 6 mole % of a perfluoroalkyl vinyl ether of structure CF 2 =CFOR 2   f , wherein R 2 f is a C 1 -C 6  perfluoroalkyl group in which 0 or 1 fluorine atoms are replaced with bromine atoms;    3) from 0 up to about 20 mole % tetrafluoroethylene;    4) from about 3 mole % to about 9 mole % of a fluorovinyl ether of formula    CFX═CXOCF 2 OR    wherein:    a) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;    b) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and    c) X is F or H; with the proviso that, together, less than about 10 mole % of the units are derived from perfluoroalkyl vinyl ether and perfluoorovinyl ether combined.    
     
     
         49 . The fluoroelastomer of    claim 48    in the form of an O-ring.  
     
     
         50 . A fluoroelastomer, curable by an ionic route, comprising units derived from the following monomers: 
 1) from about 30 mole % to about 47 mole % vinylidene fluoride;    2) from about 20 mole % to about 40 mole % hexafluoropropene;    3) from 0 up to about 17 mole % of a perfluoroalkyl vinyl ether of structure CF 2 ═CFOR 2   f , wherein R 2 f is a C 1 -C 6  perfluoroalkyl group in which 0 or 1 fluorine atoms are replaced with bromine atoms;    4) from about 10 mole % to about 30 mole % tetrafluoroethylene; and    5) from about 3 mole % to about 20 mole % of a fluorovinyl ether of formula    CFX═CXOCF 2 OR    wherein:    1) R is a C 2 -C 6  linear or branched perfluoroalkyl group, a C 5 -C 6  cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms;    2) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and    3) X is F or H; with the proviso that, together, less than about 20 mole % of the units are derived from perfluoroalkyl vinyl ether and perfluorovinyl ether combined.    
     
     
         51 . The fluoroelastomer of    claim 50    in the form of a hose.