Grafting of biocompatible hydrophilic polymers onto inorganic and metal surfaces

Claim 1

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxyl or oxide groups attached to a surface of said article; (b) exposing said surface to a silanated hydrophilic polymer that has the structure: ##STR14## wherein at least one of said R 4 , R 5 , and R 6 is a hydrolyzable group each containing 1 to 6 carbon atoms, with the other(s) being nonhydrolyzable alkyl groups each containing 1 to 4 carbons, X is selected from an alkyl group, aryl group that is unsubstitued or substituted by one or more C 1-20 alkyl groups, L is a linking moiety having one or more linking groups that is selected from amide (--C(O)NH--), ester (--C(O)O--), urea (--NHC(O)NH--), urethane (--OC(O)NH--), ether (--O--), thioether(--S--), thiocarbamate (--OC(S)NH--), amine (--NH--), and mixture thereof provided that when L comprises more than one linking group, each is separated from the next by --(CH 2 ) m --, wherein m is an integer from 1 to 20, μ is 0 or 1, and Y is a hydrophilic polymer; and (c) hydrolyzing the silanated hydrophilic polymer to form a silane layer; and (d) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the article.

Claim 2

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxyl or oxide groups attached to a surface of said article; (b) exposing said surface to a silanated hydrophilic polymer that has the structure: ##STR14## wherein at least one of said R 4 , R 5 , and R 6 is a hydrolyzable group each containing 1 to 6 carbon atoms, with the other(s) being nonhydrolyzable alkyl groups each containing 1 to 4 carbons, X is selected from an alkyl group, aryl group that is unsubstitued or substituted by one or more C 1-20 alkyl groups, L is a linking moiety having one or more linking groups that is selected from amide (--C(O)NH--), ester (--C(O)O--), urea (--NHC(O)NH--), urethane (--OC(O)NH--), ether (--O--), thioether(--S--), thiocarbamate (--OC(S)NH--), amine (--NH--), and mixture thereof provided that when L comprises more than one linking group, each is separated from the next by --(CH 2 ) m --, wherein m is an integer from 1 to 20, μ is 0 or 1, and Y is a hydrophilic polymer; and (c) hydrolyzing the silanated hydrophilic polymer to form a silane layer; and (d) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the article.

Claim 5

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxyl or oxide groups on a surface thereof; (b) exposing said surface to a silanated hydrophilic polymer selected from the group consisting of 8-(m-PEO)octyltrimethoxysilane, 8-(m-PEO)octyltriethoxysilane, 4-(m-PEO)butyltrimethoxysilane, 4-(m-PEO)butyltriethoxysilane, 3-(m-PEO)propyltrimethoxysilane, 3-(m-PEO)propyltriethoxysilane, triethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropylureidododecylureido m-PEO carbamate, triethoxysilylpropylureidodecylureido m-PEO carbamate, triethoxysilylpropyluredecylureido m-PEO carbamate, trimethoxysilylpropylureidodecylureido m-PEO carbamate, trimethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, trimethoxysilylpropylthioundecyl m-PEO 1,4-dicarbamatobutane, trimethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, trimethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, triethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, triethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, triethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, triethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, and mixtures thereof; (c) hydrolyzing the silanated hydrophilic polymer to form a silane layer; and (d) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the article.

Claim 6

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxyl or oxide groups on a surface thereof; (b) exposing said surface to a silanated hydrophilic polymer selected from the group consisting of 8-(m-PEO)octyltrimethoxysilane, 8-(m-PEO)octyltriethoxysilane, 4-(m-PEO)butyltrimethoxysilane, 4-(m-PEO)butyltriethoxysilane, 3-(m-PEO)propyltrimethoxysilane, 3-(m-PEO)propyltriethoxysilane, triethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropylureidododecylureido m-PEO carbamate, triethoxysilylpropylureidodecylureido m-PEO carbamate, triethoxysilylpropyluredecylureido m-PEO carbamate, trimethoxysilylpropylureidodecylureido m-PEO carbamate, trimethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, trimethoxysilylpropylthioundecyl m-PEO 1,4-dicarbamatobutane, trimethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, trimethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, triethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, triethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, triethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, triethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, and mixtures thereof; (c) hydrolyzing the silanated hydrophilic polymer to form a silane layer; and (d) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the article.

Claim 14

A device having a biocompatible surface that has hydrophilic polymers grafted onto the surface and having been fabricated by a process comprising the steps of: (a) providing a device having a plurality of hydroxyl or oxide groups on a surface thereof; (b) exposing said surface to a silanated hydrophic polymer selected from the group consisting of the group containing 8-(m-PEO)octyltrimethoxysilane, 8-(m-PEO)octyltriethoxysilane, 4-(m-PEO)butyltrimethoxysilane, 4-(m-PEO)butyltriethoxysilane, 3-(m-PEO)propyltrimethoxysilane, 3-(m-PEO)propyltriethoxysilane, triethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropylureidododecylureido m-PEO carbamate, triethoxysilylpropylureidodecylureido m-PEO carbamate, triethoxysilylpropylureidecylureido m-PEO carbamate, trimethoxysilylpropylureidodecylureido m-PEO carbamate, trimethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, trimethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, trimethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, trimethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, triethoxysilylpropylthioundecyl m-PEO 1,16-dicarbamatohexane, triethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, triethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, triethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, and mixtures thereof: and (c) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the device.

Claim 15

A device having a biocompatible surface that has hydrophilic polymers grafted onto the surface and having been fabricated by a process comprising the steps of: (a) providing a device having a plurality of hydroxyl or oxide groups on a surface thereof; (b) exposing said surface to a silanated hydrophic polymer selected from the group consisting of the group containing 8-(m-PEO)octyltrimethoxysilane, 8-(m-PEO)octyltriethoxysilane, 4-(m-PEO)butyltrimethoxysilane, 4-(m-PEO)butyltriethoxysilane, 3-(m-PEO)propyltrimethoxysilane, 3-(m-PEO)propyltriethoxysilane, triethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropyl m-PEO carbamate, trimethoxysilylpropylureidododecylureido m-PEO carbamate, triethoxysilylpropylureidodecylureido m-PEO carbamate, triethoxysilylpropylureidecylureido m-PEO carbamate, trimethoxysilylpropylureidodecylureido m-PEO carbamate, trimethoxysilylpropylthioundecyl m-PEO 1,6-dicarbamatohexane, trimethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, trimethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, trimethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, triethoxysilylpropylthioundecyl m-PEO 1,16-dicarbamatohexane, triethoxysilylpropylthioundecyl m-PEO, 1,4-dicarbamatobutane, triethoxysilylpropylthioundecyl m-PEO 1,8-dicarbamatooctane, triethoxysilylpropylthioundecyl m-PEO 1,12-dicarbamatododecane, and mixtures thereof: and (c) curing the silane layer to cause the silane layer to be covalently bonded to the surface of the device.

Claim 16

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxy or oxide groups attached to a surface of said article; (b) exposing said surface to trichlorovinylsilane to form a silane layer that is covalently bound to the surface; and (c) exposing the silane layer to a hydrophilic polymer selected from the group consisting of poly(ethylene oxide) (PEO), polyhydroxyethylmethacrylate (PHEMA), PEO-containing block copolymers, and mixtures thereof and causing the silane layer to react with the hydrophilic polymer to covalently bond to the silane layer.

Claim 17

A method of grafting hydrophilic polymers to a surface of an article comprising the steps of: (a) providing an article having a plurality of hydroxy or oxide groups attached to a surface of said article; (b) exposing said surface to trichlorovinylsilane to form a silane layer that is covalently bound to the surface; and (c) exposing the silane layer to a hydrophilic polymer selected from the group consisting of poly(ethylene oxide) (PEO), polyhydroxyethylmethacrylate (PHEMA), PEO-containing block copolymers, and mixtures thereof and causing the silane layer to react with the hydrophilic polymer to covalently bond to the silane layer.

Claim 18

A device having a biocompatible surface that has hydrophilic polymers grafted onto the surface and having been fabricated by a process comprising the steps of: (a) providing a device having a plurality of hydroxyl or oxide groups attached to a surface of said device; (b) exposing said surface to trichlorovinylsilane to form a silane layer that is covalently bound to the surface wherein the silane layer comprises a plurality of vinyl groups; and (c) exposing the silane layer to a hydrophilic polymer of poly(ethylene oxide) and causing the silane layer to react with poly(ethylene oxide) to covalently bond to the silane layer.

Claim 19

A device having a biocompatible surface that has hydrophilic polymers grafted onto the surface and having been fabricated by a process comprising the steps of: (a) providing a device having a plurality of hydroxyl or oxide groups attached to a surface of said device; (b) exposing said surface to trichlorovinylsilane to form a silane layer that is covalently bound to the surface wherein the silane layer comprises a plurality of vinyl groups; and (c) exposing the silane layer to a hydrophilic polymer of poly(ethylene oxide) and causing the silane layer to react with poly(ethylene oxide) to covalently bond to the silane layer.