Novel prepolymers useful in biomedical devices

Abstract

A novel polyurethane based prepolymer useful in biomedical devices which provides high oxygen permeability and superior physical properties.

1 . A prepolymer material described by the general chemical formulae  
         E(*D*A*D*G) a *D*A*D*E′ or  E(*D*G*D*A) a *D*G*D*E′ 
       where 
 A denotes a divalent polymeric radical chosen from the group of  
                     
 wherein  
 R P  denotes a straight or branched alkyl group with 1 to 6 carbon atoms and n provides for a moiety weight of the radical between 2000 and 10,000;  
 R F  denotes a fluorinated straight or branched alkyl radical with 1 to 6 carbon atoms and m provides a moiety weight of between 400 and 10,000;  
 R S  denotes an alkyl radical or a short chain fluorinated alkyl radical with 1 to 3 carbon atoms; and  
 p provides a moiety weight of 400 to 10,000;  
 D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an alkylaryl diradical or an aryl diradical, with 6 to 30 carbon atoms;  
 G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aromatic diradical or an alkylaromatic diradical with 1 to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain;  
 * denotes a urethane or ureido linkage; and  
 E and E′ denote polymerizable unsaturated organic radicals represented by the general chemical formula  
                     
 wherein 
 R 1  denotes a divalent alkylene radical with 1 to 10 carbon atoms;  
 R 2  denotes a —H or —CH 3  radical;  
 R 3  denotes a —H radical or an alkyl radical with 1 to 6 carbon atoms or a  
                     
 radical where  
 Y is —O—, —S— or —NH— and R 4  denotes an alkyl radical with 1 to 12 carbon atoms;  
 X denotes  
                     
 Ar denotes an aromatic radical with 6 to 30 carbon atoms;  
 a is at least 1;  
 w is 0 to 6;  
 x is 0 or 1;  
 y is 0 or 1; and  
 z is 0 or 1.  
 
 
     
     
         2 . The prepolymer of  claim 1  wherein the polymeric radical, A, is a polyethylene radical with a molecular weight of at least about 2000.  
     
     
         3 . The prepolymer of  claim 2  wherein the D radical is formed from the group of diisocyanates consisting of isophorone diisocyanate, toluene diisocyanate and H 12 -methylene diisocyanate.  
     
     
         4 . The prepolymer of  claim 3  wherein the G radical is formed from the group of diols consisting of neopentylglycol, 1,4-butanediol, diethyleneglycol and triethylene glycol.  
     
     
         5 . The prepolymer of  claim 1  wherein the polymeric radical, A, is a dialkyl endcapped polydimethylsiloxane radical with a molecular weight of at least 400.  
     
     
         6 . The prepolymer of  claim 5  wherein the D radical is formed from the group of diisocyanate consisting of isophorone diisocyanate, toluene diisocyanate, and H 12 -methylene diisocyanate.  
     
     
         7 . The prepolymer of  claim 6  wherein the G radical is formed from the group of diols consisting of neopentylglycol, 1,4-butanediol, diethylene glycol and triethylene glycol.  
     
     
         8 . The prepolymer of  claim 1  wherein the polymeric radical, A, is a dialkyl endcapped polydifluoroalkyl-siloxane polymer with a molecular weight of at least 400.  
     
     
         9 . The prepolymer of  claim 8  wherein the D radical is formed from the group of diisocyanates consisting of isophorone diisocyanate, toluene diisocyanate, and H 12 -methylene diisocyanate.  
     
     
         10 . The prepolymer of  claim 9  wherein the G radical is formed from the group of diols consisting of neopentyl glycol, 1,4-butanediol, diethylene glycol and triethylene glycol.  
     
     
         11 . The prepolymer of  claim 1  wherein the polymeric radical, A, is a fluoroalkyl ether with a molecular weight of at least about 400.  
     
     
         12 . The prepolymer of  claim 11  wherein the D radical is formed from the group of diisocyanates consisting of isophorone diisocyanate, toluene diisocyanate and H 12 -methylene diisocyanate.  
     
     
         13 . The prepolymer of  claim 11  wherein the G radical is formed from the group of diols consisting of neopentyl glycol, 1,4-butanediol, diethylene glycol and triethylene glycol.  
     
     
         14 . A copolymer material formed by polymerizing a comonomer mixture comprised of: 
 (I) the prepolymer described by the general chemical formulae      E(*D*A*D*G) a *D*A*D*E′ or  E(*D*G*D*A) a *D*G*D*E′   where    A denotes a divalent polymeric radical chosen from the group of                          wherein    R P  denotes a straight or branched alkyl group with 1 to 6 carbon atoms and n provides for a moiety weight of the radical between 2000 and 10,000;    R F  denotes a fluorinated straight or branched alkyl radical with 1 to 6 carbon atoms and m provides a moiety weight of between 400 and 10,000;    R S  denotes an alkyl radical or a short chain fluorinated alkyl radical with 1 to 3 carbon atoms; and    p provides a moiety weight of 400 to 10,000;    D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an alkylaryl diradical or an aryl diradical, with 6 to 30 carbon atoms;    G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aromatic diradical or an alkylaromatic diradical with 1 to 40 carbon atoms;    * denotes a urethane or ureido linkage; and    E and E′ denote polymerizable unsaturated organic radicals represented by the general chemical formula:                          wherein    R 1  denotes a divalent alkylene radical with 1 to 10 carbon atoms    R 2  denotes a —H or —CH 3  radical;    R 3  denotes a —H radical or an alkyl radical with 1 to 6 carbon atoms or a                          radical where    Y is —O—, —S— or —NH—; and R 4  denotes an alkyl radical with 1 to 12 carbon atoms;    X denotes                          Ar denotes an aromatic radical with 6 to 30 carbon atoms;    a is at least L;    w is 0 to 6;    x is 0 or 1;    y is 0 or 1;    z is 0 or 1; and    (II) a hydrophilic comonomer.    
     
     
         15 . The copolymer of  claim 14  wherein the polymeric radical of component (I), A, is polyethylene radical with a molecular weight of at least about 2000.  
     
     
         16 . The copolymer of  claim 15  wherein component (I) comprises 15 to 95 weight percent of the comonomer mixture and said hydrophilic monomer comprises 5 to 85 weight percent of said comonomer mixture.  
     
     
         17 . The copolymer of  claim 16  which further comprises a diethylenically reactive crosslinker.  
     
     
         18 . The copolymer of  claim 17  wherein said hydrophilic monomer is chosen from the group of hydrophilic monomers consisting of 2-hydroxyethyl methacrylate, N-vinyl-2-pyrrolidinone, methacrylic acid, dimethyl acrylamide, and glycerol methacrylate.  
     
     
         19 . The copolymer of  claim 14  wherein the polymeric radical of component (I), A, is a dialkyl endcapped polydimethylsiloxane radical with a molecular weight of at least 400.  
     
     
         20 . The copolymer of  claim 19  wherein component (I) comprises 15 to 95 weight percent of the comonomer mixture and said hydrophilic comonomer comprises 5 to 85 weight percent of said comonomer mixture.  
     
     
         21 . The copolymer of  claim 20  wherein said hydrophilic comonomer is chosen from the group consisting of 2-hydroxy-ethyl methacrylate, N-vinyl-2-pyrrolidinone, methacrylic acid, dimethyl acrylamide and glycerol methacrylate.  
     
     
         22 . The copolymer of  claim 21  which further comprises 5 to 40 weight percent organosilicon comonomer.  
     
     
         23 . The copolymer of  claim 14  wherein the polymeric radical of component (I), A, is a poly(fluoroalkyl)ether with a molecular weight of at least 400.  
     
     
         24 . A copolymer formed by polymerizing a comonomer mixture comprised of: 
 (I) the prepolymer described by the general chemical formulae      E(*D*A*D*G) a *D*A*D*E′ or  E(*D*G*D*A) a *D*G*D*E′   where    A denotes a divalent polymeric radical chosen from the group of                          wherein    R P  denotes a straight or branched alkyl group with 1 to 6 carbon atoms and n provides for a moiety weight of the radical between 2000 and 10,000;    R F  denotes a fluorinated straight or branched alkyl radical with 1 to 6 carbon atoms and m provides a moiety weight of between 400 and 10,000;    R S  denotes an alkyl radical or a short chain fluorinated alkyl radical with 1 to 3 carbon atoms; and    p provides a moiety weight of 400 to 10,000;    D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an alkylaryl diradical or an aryl diradical, with 6 to 30 carbon atoms;    G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aromatic diradical or an alkylaromatic diradical with 1 to 40 carbon atoms;    * denotes a urethane or ureido linkage; and    E and E′ denote polymerizable unsaturated organic radicals represented by the general chemical formula:                          wherein    R 1  denotes a divalent alkylene radical with 1 to 10 carbon atoms    R 2  denotes a —H or —CH 3  radical;    R 3  denotes a —H radical or an alkyl radical with 1 to 6 carbon atoms or a                          radical where    Y is —O—, —S— or —NH—; and R 4  denotes an alkyl radical with 1 to 12 carbon atoms;    X denotes                          Ar denotes an aromatic radical with 6 to 30 carbon atoms;    a is at least 1;    w is 0 to 6;    x is 0 or 1;    y is 0 or 1;    z is 0 or 1; and    (II) a hydrophilic comonomer.    
     
     
         25 . The copolymer of  claim 24  wherein said organosilicon monomer is tris(trimethylsiloxy)silyl-propyl methacrylate.  
     
     
         26 . The copolymer of  claim 25  which comprises 20-50 wt % prepolymer (I), 20-40 weight percent tris(trimethylsiloxy)-silyl propyl methacrylate.  
     
     
         27 . The copolymer of  claim 26  which further comprises 10-35 weight percent of the hydrophilic comonomer, dimethylacrylamide.  
     
     
         28 . The copolymer of  claim 26  which further comprises from 10-35 weight percent of the hydrophilic comonomer glycerol methacrylate.  
     
     
         29 . The copolymer of  claim 26  which further comprises from 10-35 weight percent of the hydrophilic comonomer 2-hydroxyethyl methacrylate.  
     
     
         30 . The copolymer of  claim 26  which further comprises from 10-35 weight percent of the hydrophilic monomer N-vinyl-2-pyrrolidinone.  
     
     
         31 . A copolymer formed by polymerizing a comonomer mixture comprised of: 
 (I) the prepolymer described by the general chemical formulae      E(*D*A*D*G) a *D*A*D*E′ or  E(*D*G*D*A) a *D*G*D*E′   where    A denotes a divalent polymeric radical chosen from the group of                          wherein    R P  denotes a straight or branched alkyl group with 1 to 6 carbon atoms and n provides for a moiety weight of the radical between 2000 and 10,000;    R F  denotes a fluorinated straight or branched alkyl radical with 1 to 6 carbon atoms and m provides a moiety weight of between 400 and 10,000;    R S  denotes an alkyl radical or a short chain fluorinated alkyl radical with 1 to 3 carbon atoms; and    p provides a moiety weight of 400 to 10,000;    D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an alkylaryl diradical or an aryl diradical, with 6 to 30 carbon atoms;    G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aromatic diradical or an alkylaromatic diradical with 1 to 40 carbon atoms;    * denotes a urethane or ureido linkage; and    E and E′ denote polymerizable unsaturated organic radicals represented by the general chemical formula:                          wherein    R 1  denotes a divalent alkylene radical with 1 to 10 carbon atoms    R 2  denotes a —H or —CH 3  radical;    R 3  denotes a —H radical or an alkyl radical with 1 to 6 carbon atoms or a                          radical where    Y is —O—, —S— or —NH—; and R 4  denotes an alkyl radical with 1 to 12 carbon atoms;    X denotes                          Ar denotes an aromatic radical with 6 to 30 carbon atoms;    a is at least I;    w is  0  to  6 ;    x is  0  or  1 ;    y is  0  or  1 ;    z is  0  or  1 ; and    (II) a fluoroorgano comonomer.    
     
     
         32 . A biomedical device made from a polymer comprising the prepolymer of  claim 1.