Novel Prepolymers for Improved Surface Modification of Contact Lenses

Abstract

Provided are novel reactive functionalized fumaric- and itaconic-containing prepolymers and compositions comprising the prepolymers used in the manufacture of medical devices. The prepolymers can be used to provide surface modified contact lenses formed from one or more fumaric- or itaconic-containing prepolymers having reactive functionality that is complimentary to reactive, hydrophilic polymers.

1 . A copolymer prepared by polymerizing a monomer mixture comprising, 
 (A) 20 to 80 weight % of at least one prepolymer selected from the group consisting of compounds having the following formula:      YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  and  CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2      wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are independently selected from the group consisting of alkyl groups, phenyl groups, alkyl groups substituted with halogen, phenyl groups substituted with halogen, alkyl groups containing ether linkages and phenyl groups containing ether linkages, W is O or NH, n is an integer between 1 and 10, m is an integer between 2 and 200, and Y is a residue having a reactive functional group selected from the group consisting of hydroxyl, carboxyl, oxazolone, epoxy and anhydride functional groups with the proviso that when W is O, Y is not a residue of diethanolamine, and    (B) 5 to 50 weight % of at least one copolymerizable device-forming monomer.    
     
     
         2 . The copolymer of  claim 1  wherein the monomer mixture comprises: 
 10 to 50 weight % of at least one additional silicone-containing monomer and 10 to 50 weight % of at least one copolymerizable device-forming hydrophilic monomer.    
     
     
         3 . The copolymer of  claim 1  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 200, W is O and Y is OH and is in a trans configuration.  
     
     
         4 . The copolymer of  claim 1  wherein component (A) has the following formula:  
         CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2    
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 200, W is O and Y is OH.  
     
     
         5 . The copolymer of  claim 1  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4 , m is an integer between 5 and 100, W is O and Y is OH and is in a cis configuration.  
     
     
         6 . The copolymer of  claim 2  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a trans configuration.  
     
     
         7 . The copolymer of  claim 2  wherein component (A) has the following formula:  
         CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2    
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH.  
     
     
         8 . The copolymer of  claim 2  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a cis configuration.  
     
     
         9 . A medical device comprising a copolymer prepared by polymerizing a monomer mixture comprising, as main components, 
 (A) 20 to 80 weight % of at least one prepolymer selected from the group consisting of compounds having the following formula:      YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  and  CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2      wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are independently selected from the group consisting of alkyl groups, phenyl groups, alkyl groups substituted with halogen, phenyl groups substituted with halogen, alkyl groups containing ether linkages and phenyl groups containing ether linkages, W is O or NH, n is an integer between 1 and 10, m is an integer between 2 and 200, and Y is a residue having a reactive functional group selected from the group consisting of hydroxyl, carboxyl, oxazolone, epoxy and anhydride functional groups with the proviso that when W is O, Y is not a residue of diethanolamine, and    (B) 5 to 50 weight % of at least one copolymerizable device-forming monomer.    
     
     
         10 . The medical device of  claim 9  wherein the monomer mixture comprises: 
 10 to 50 weight % of at least one additional silicone-containing monomer hydrophilic monomer and 10 to 50 weight % of at least one copolymerizable device-forming hydrophilic monomer.    
     
     
         11 . The medical device of  claim 9  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a trans configuration.  
     
     
         12 . The medical device of  claim 9  wherein component (A) has the following formula:  
         CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2    
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH.  
     
     
         13 . The medical device of  claim 9  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a cis configuration.  
     
     
         14 . The medical device of  claim 10  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a trans configuration.  
     
     
         15 . The medical device of  claim 10  wherein component (A) has the following formula:  
         CH 2 ═C(CH 2 COY)COW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOC(CH 2 COY)C═CH 2    
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH.  
     
     
         16 . The medical device of  claim 10  wherein component (A) has the following formula:  
         YCO—CH═CHCOW(R 1 ) n (SiR 2 R 3 O) m (SiR 2 R 3 )(R 1 ) n WOCCH═CH—COY  
       wherein R 1  is selected from the group consisting of alkylenes and alkylenes containing ether linkages, R 2  and R 3  are methyl, n is 3 or 4, m is an integer between 5 and 100, W is O and Y is OH and is in a cis configuration.  
     
     
         17 . The medical device of  claim 9  wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, contact lenses, intrauterine devices, vessel substitutes, artificial ureters and artificial breast tissue.  
     
     
         18 . The medical device of  claim 17  wherein the medical device is a contact lens.  
     
     
         19 . The medical device of  claim 18  wherein the medical device is a soft contact lens.  
     
     
         20 . The medical device of  claim 10  wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, contact lenses, intrauterine devices, vessel substitutes, artificial ureters and artificial breast tissue.  
     
     
         21 . The medical device of  claim 20  wherein the medical device is a contact lens.  
     
     
         22 . The medical device of  claim 21  wherein the medical device is a soft contact lens.