Brush polymer coating by in situ polymerization from photoreactive surface

Abstract

The invention provides compositions that include crosslinking agents having multiple photoactivatable groups, such as diaryl ketones, or a diaryl ketone, such as benzophenone, and at least one polymerizable monomer, such as a zwitterionic monomer. The compositions are useful as surface coating agents that provide brush type polymeric coatings. These polymeric coatings can be used on medical devices, such as artificial joints, to reduce wear and tear between the components of the joint and thus reduce or eliminate debris generated by friction between the joint components.

1 - 11 . (canceled) 
     
     
         12 . A medical article coating composition comprising a cross-linking compound, the crosslinker comprising at least two (2) pendent photoactive groups and having a formula:
   (CorePA) n  
   wherein “core” is a linear or branched alkyl group, a linear or branched alkyl group with heteroatom(s), a linear or branched alkyenyl group, a linear or branched alkyenyl group with heteroatom(s), an aryl group, an aryl group with heteroatom(s), a sugar substrate, a polysaccharide substrate, a peptide, a protein, a nucleic acid, an oligonucleotide, polyacrylics, urea(s), uracil(s), ketal(s), glycol(s), polyvinyls, nylons, polyurethanes, or polyethers;   “PA” is a photoactivatable group that can be an aryl ketone, an azide or nitrene generator, a free radical generator, a carbene generator or a diazo moiety;   “n” is an integer from at least 2 to about 5,000; and   a polymerizable monomer,   
       wherein the composition is applied to the medical article. 
     
     
         13 . The medical article coating composition of  claim 12 , wherein the polymerizable monomer has an acrylate, allylic, methacrylate, vinyl or diarylketone containing moiety. 
     
     
         14 . The medical article coating composition of  claim 13 , wherein the acrylate, allylic, methacrylate, vinyl or diarylketone polymerizable monomer further includes a zwitterionic moiety. 
     
     
         15 . The medical article coating composition of  claim 14  wherein the polymerizable monomer is N,Ndimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nmethacryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethyl methacryloyl-S-(sulfopropyl)-sulfoniumbetaine, 2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methyl phosphate, 2-(acryloyloxyethyl)-2′-(trimethylammonium)ethyl phosphate, [(2-acryloylethyl)dimethylammonio]methyl phosphonic acid, 2-[(3-acrylamidopropyl)dimethylammonio]ethyl 2′-isopropyl phosphate (AAPI), 1-vinyl-3-(3-sulfopropyl)imidazolium hydroxide, (2-acryloxyethyl)carboxymethylmethylsulfonium chloride, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-sulfobutyl)-N-methyl-N,N-diallylamine ammoniumbetaine (MDABS), 2-methacryloyloxyethyl phosphorylcholine, or N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine. 
     
     
         16 . The medical article coating composition of  claim 12 , further comprising a photoinitiator, wherein the initiator is benzophenone, an acetophenone derivative, a benzoin derivative, a benzilketal, a hydroxyalkylphenone, an aminoalkylphenone, an O-acyl oximoketone, an acylphosphonate, a thiobenzoic S-ester, a triazine, a 1,2 diketone, a quinone, a coumarins, a xanthone, or mixtures thereof. 
     
     
         17 . The medical article coating composition of  claim 12  wherein the medical article is selected from the group consisting of catheters, wound drainage tubes, arterial grafts, soft tissue patches, gloves, shunts, stents, tracheal catheters, wound dressings, sutures, guide wires, prosthetic devices, microscope slide, biosensors, and artificial joints. 
     
     
         18 . A coating composition comprising a cross-linking compound, the crosslinker comprising at least two (2) pendent photoactive groups and having a formula:
   (CorePA) n  
   wherein “core” is a linear or branched alkyl group, a linear or branched alkyl group with heteroatom(s), a linear or branched alkyenyl group, a linear or branched alkyenyl group with heteroatom(s), an aryl group, an aryl group with heteroatom(s), a sugar substrate, a polysaccharide substrate, a peptide, a protein, a nucleic acid, an oligonucleotide, polyacrylics, urea(s), uracil(s), ketal(s), glycol(s), polyvinyls, nylons, polyurethanes, or polyethers;   “PA” is a photoactivatable group that can be an aryl ketone, an azide or nitrene generator, a free radical generator, a carbene generator or a diazo moiety;   “n” is an integer from at least 2 to about 5,000; and   a polymerizable monomer,   
       wherein the composition is applied to a surface of a substrate. 
     
     
         19 . The coating composition of  claim 18 , wherein the polymerizable monomer has an acrylate, allylic, methacrylate, vinyl or diarylketone containing moiety. 
     
     
         20 . The coating composition of  claim 19 , wherein the acrylate, allylic, methacrylate, vinyl or diarylketone polymerizable monomer further includes a zwitterionic moiety. 
     
     
         21 . The coating composition of  claim 20  wherein the polymerizable monomer is N,Ndimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nmethacryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-Nacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-Nmethacrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethyl methacryloyl-S-(sulfopropyl)-sulfoniumbetaine, 2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methyl phosphate, 2-(acryloyloxyethyl)-2′-(trimethylammonium)ethyl phosphate, [(2-acryloylethyl)dimethylammonio]methyl phosphonic acid, 2-[(3-acrylamidopropyl)dimethylammonio]ethyl 2′-isopropyl phosphate (AAPI), 1-vinyl-3-(3-sulfopropyl)imidazolium hydroxide, (2-acryloxyethyl)carboxymethylmethylsulfonium chloride, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-sulfobutyl)-N-methyl-N,N-diallylamine ammoniumbetaine (MDABS), 2-methacryloyloxyethyl phosphorylcholine, or N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine. 
     
     
         22 . The coating composition of  claim 18 , further comprising a photoinitiator, wherein the initiator is benzophenone, an acetophenone derivative, a benzoin derivative, a benzilketal, a hydroxyalkylphenone, an aminoalkylphenone, an O-acyl oximoketone, an acylphosphonate, a thiobenzoic S-ester, a triazine, a 1,2 diketone, a quinone, a coumarins, a xanthone, or mixtures thereof. 
     
     
         23 . The coating composition of  claim 18  wherein the composition is applied to a microscope slide or a chip for biomolecule immobilization.