New fluoromonomers and methods of production, and new fluoropolymers produced therefrom

Abstract

The present invention provides new fluoromonomers having the generic structure: CF 2 ═CF(OCH 2 CH 2 ) n OR where n is an integer and R is a functional group and methods for producing same. A new method of synthesizing the fluoromonomers is provided. The present invention also relates to new fluoropolymers prepared from any one or combination of the new fluoromonomers and having the generic structure: —[—CF 2 CF{(OCH 2 CH 2 ) n OR}—] m — where n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group. The method also relates to new copolymers or terpolymers prepared from the new fluoromonomers alone, the new fluoromonomers and existing fluoromonomers or the new fluoromonomers and existing hydrocarbon or functionalized hydrocarbon monomers.

Therefore what is claimed is:  
     
         1 . A fluoromonomer of the following general formula (I), comprising; 
       CF 2 ═CF(OCH 2 CH 2 ) n OR  (I) 
       wherein n is an integer greater than or equal to 1 and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group.  
     
     
         2 . The fluoromonomer according to  claim 1  wherein CF 2 ═CF(OCH 2 CH 2 ) n OR is 1-(2-phenoxyethoxy)-1,2,2-trifluoroethene.  
     
     
         3 . The fluoromonomer according to  claim 1  wherein CF 2 ═CF(OCH 2 CH 2 ) n OR is 1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene.  
     
     
         4 . The fluoromonomer according to  claim 1  wherein CF 2 ═CF(OCH 2 CH 2 ) n OR is 1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene.  
     
     
         5 . A process for synthesis of a fluoromonomer having the following general formula (I), 
       CF 2 ═CF(OCH 2 CH 2 ) n OR  (I) 
       wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, comprising the steps of: 
 providing an effective alkali metal alkoxide;  
 mixing tetrafluoroethylene with said alkali metal alkoxide in the presence of an effective phase transfer catalyst at an effective temperature to form a mixture, the phase transfer catalyst being selected from the group consisting of crown ethers and tetraalkylammonium salts; and  
 isolating said fluoromonomer from said mixture.  
 
     
     
         6 . The process according to  claim 5  wherein said phase transfer catalyst is a crown ether.  
     
     
         7 . The process according to  claim 6  wherein said crown ether is selected from the group consisting of 18-crown-6 and 15-crown-5 ethers.  
     
     
         8 . The process according to  claim 6  wherein said alkoxyethanol is selected from the group consisting of 2-phenoxyethanol, 2-(2-ethoxyethoxy) ethanol and 2-(2-tertiary butoxyethoxy)ethanol.  
     
     
         9 . The process according to  claim 8  wherein the step mixing tetrafluoroethylene with the alkali metal alkoxide comprises pumping tetrafluoroethylene gas into a reactor containing said alkoxide heated to a preselected temperature.  
     
     
         10 . A fluoropolymer of the following general formula (II), comprising: 
       —[CF 2 CF{(OCH 2 CH 2 ) n OR}] m —  (II) 
       wherein n is an integer, m is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group.  
     
     
         11 . A copolymer, comprising: 
 a first fluoromonomer of the general formula CF 2 ═CF(OCH 2 CH 2 ) n OR, and a second fluoromonomer of the general formula CF 2 CXY, wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein X and Y are selected from the group consisting of hydrogen, halogen, hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         12 . The copolymer according to  claim 11  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         13 . The copolymer according to  claim 12  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         14 . The copolymer according to  claim 12  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         15 . A copolymer, comprising: 
 a first fluoromonomer of the general formula CF 2 ═CF(OCH 2 CH 2 ) n OR, and a second fluoromonomer of the general formula CFXCYZ, wherein n is an integer, wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein X, Y and Z are selected from the group consisting of hydrogen, halogens, unsubstituted hydrocarbyl and inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         16 . The copolymer according to  claim 15  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         17 . The copolymer according to  claim 16  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         18 . The copolymer according to  claim 16  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         19 . A copolymer, comprising: 
 a first fluoromonomer having a general formula CF 2 ═CF(OCH 2 CH 2 ) n OR and a second monomer having a generic formula CXYCAB, wherein n is an integer and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         20 . The copolymer according to  claim 19  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         21 . The copolymer according to  claim 20  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         22 . The copolymer according to  claim 20  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         23 . A fluoromonomer of the following general formula CGJ═CL(OCH 2 OCH 2 ) n OR wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine.  
     
     
         24 . A fluoropolymer of the following general formula, comprising: 
       —[CGJCL{(OCH 2 CH 2 ) n OR}] m — 
       wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine.  
     
     
         25 . A copolymer, comprising: 
 a fluoromonomer of the general formula CGJ═CL(OCH 2 CH 2 ) n OR, wherein n is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine; and    a second fluoromonomer of the general formula CF 2 CXY, wherein n is an integer, and wherein X and Y are selected from the group consisting of hydrogen, halogens, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         26 . The copolymer according to  claim 25  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         27 . The copolymer according to  claim 26  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         28 . The copolymer according to  claim 27  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         29 . A copolymer, comprising: 
 a fluoromonomer of the general formula CGJ═CL(OCH 2 CH 2 ) n OR, wherein n is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine; and    a second fluoromonomer of the general formula CFXCYZ, wherein X, Y and Z are selected from the group consisting of hydrogen, halogens, hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         30 . The copolymer according to  claim 29  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         31 . The copolymer according to  claim 30  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         32 . The copolymer according to  claim 31  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         33 . A copolymer, comprising: 
 a fluoromonomer having a general formula CGJ═CL(OCH 2 CH 2 ) n OR, wherein n is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine; and    a second monomer having a generic formula CXYCAB, wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         34 . The copolymer according to  claim 33  wherein said copolymer is selected from the group consisting of random, block, alternating, branched and graft copolymers.  
     
     
         35 . The copolymer according to  claim 34  wherein said copolymer is one of a random and alternating copolymer prepared by a process of free radical bulk polymerization.  
     
     
         36 . The copolymer according to  claim 35  wherein said copolymer is one of a random and alternating copolymer prepared by a process of redox emulsion polymerization.  
     
     
         37 . A terpolymer, comprising; 
 a first fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR   wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group;    a second fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR′   wherein n is an integer greater than or equal to 1 and R′ represents an unsubstituted or inertly substituted hydrocarbyl group;    a third fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR″   wherein n is an integer greater than or equal to 1 and R″ represents an unsubstituted or inertly substituted hydrocarbyl group, wherein R, R′ and R″ are different from each other.    
     
     
         38 . A terpolymer comprising; 
 a first fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR   wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group;    a second fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR′   wherein n is an integer greater than or equal to 1 and R′ represents an unsubstituted or inertly substituted hydrocarbyl group, wherein R and R′ are different; and    a third fluoromonomer of the general formula CF 2 CXY, wherein X and Y are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         39 . A terpolymer comprising; 
 a first fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR   wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group;    a second fluoromonomer of the general formula CF 2 ═CF(OCH 2 CH 2 ) n OR′, wherein n is an integer greater than or equal to 1 and R′ represents an unsubstituted or inertly substituted hydrocarbyl group, wherein R and R′ are different; and    a third fluoromonomer of the general formula CFXCYZ, wherein X, Y and Z are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl and inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         40 . A terpolymer comprising; 
 a first fluoromonomer of the following general formula   CF 2 ═CF(OCH 2 CH 2 ) n OR   wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group;    a second fluoromonomer having a general formula CF 2 ═CF(OCH 2 CH 2 ) n OR′, wherein n is an integer greater than or equal to 1 and R′ represents an unsubstituted or inertly substituted hydrocarbyl group wherein R and R′ are different; and    a third monomer having a generic formula CXYCAB, wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.    
     
     
         41 . A graft copolymer, comprising: 
 a polymer graft and a polymer backbone, said backbone comprising a polymer selected from the group consisting of polystyrene, polyurethane, polyester, polyether, polyethylene, polypropylene, poly(carbonate), poly(anhydride), poly(vinyl chloride), poly(acrylonitrile), poly(α-hydroxyesters), poly(tetrafluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino acid), poly(arylate), poly(acrylate), poly(acetate) and any combination thereof; and    said polymer graft comprising a fluoropolymer of the following general formula   —[CF 2 CF{(OCH 2 CH 2 ) n OR}] m —   wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group.    
     
     
         42 . A fluoropolymer blend, comprising 
 fluoromonomer of the following general formula (I), comprising;   CF 2 ═CF(OCH 2 CH 2 ) n OR  (I)   wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group; and    a polymer selected from the group consisting of polystyrene, polyurethane, polyester, polyether, polyethylene, polypropylene, poly(carbonate), poly(anhydride), poly(vinyl chloride), poly(acrylonitrile), poly(α-hydroxyesters), poly(tetrafluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino acid), poly(acrylate), poly(acetate) and any combination thereof.    
     
     
         43 . A fluoropolymer blend, comprising 
 fluoropolymer of the following general formula   —[CF 2 CF{(OCH 2 CH 2 ) n OR}] m —   wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group; and    a polymer selected from the group consisting of polystyrene, polyurethane, polyester, polyether, polyethylene, polypropylene, poly(carbonate), poly(anhydride), poly(vinyl chloride), poly(acrylonitrile), poly(α-hydroxyesters), poly(tetrafluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino acid), poly(acrylate), poly(acetate) and any combination thereof.    
     
     
         44 . Biologically useful materials exhibiting low protein absorption, comprising; 
 fluoropolymers blended with physiologically acceptable polymer, the fluoropolymers being selected from the group consisting of —[CF 2 CF{(OCH 2 CH 2 ) n OR}] m —, wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group.