Modification of surfaces with polymers

Abstract

A polymer formed by controlled radical polymerization includes groups that can be modified after controlled radical polymerization to form a radical. The polymer can be the reaction product of a controlled radical polymerization of radically polymerizable monomers, wherein at least one of the radically polymerizable monomers includes at least one group that can be modified after the controlled radical polymerization to form a radical.

What is claimed is: 
     
         1 . A polymer which is the reaction product, via a controlled radical polymerization of radically (co)polymerizable monomers, comprising at least one monomer comprising at least one group that can be modified after the controlled radical polymerization by application of energy to the polymer to form a radical. 
     
     
         2 . The polymer of  claim 1 , wherein the energy is light energy. 
     
     
         3 . The polymer of  claim 1  wherein the at least one group is an aryl ketone group. 
     
     
         4 . The polymer of  claim 3 , wherein the at least one aryl ketone group comprises one of the following radicals benzophenone-, acetophenone-, benzyl-, benzoin-, hydroxyalkylphenone-, phenyl cyclohexyl ketone-, anthraquinone-, trimethyl-benzoylphosphine oxide-, methylthiophenyl morpholine ketone-, aminoketone-, azobenzoin-, thioxanthone-, hexaarylbisimidazole-, triazine-, or fluoroenone-. 
     
     
         5 . The polymer of  claim 1  wherein the at least one group is modified by reaction after the controlled radical polymerization to convert the at least one group to a group that is modified by application of energy to the polymer to form a radical to tether the polymer to a substrate. 
     
     
         6 . The polymer of  claim 5  wherein the polymer is tethered to the substrate via covalent bonding. 
     
     
         7 . The polymer of  claim 5  wherein a deposited film of the polymer is both stabilized and tethered to the substrate by exposure to light. 
     
     
         8 . The polymer of  claim 5  wherein the substrate is a polymeric surface which comprises radically abstractable protons and a deposition of a film of the polymer results in a surface more polar that a surface of the substrate. 
     
     
         9 . The polymer of  claim 1  wherein the at least one group is also modifiable to effect crosslinking of the polymer after the controlled radical polymerization. 
     
     
         10 . The polymer of  claim 9  wherein crosslinking of the polymer stabilizes the polymer to provide for a layer of the polymer that allows formation of a stable tethered film of controlled thickness on the surface of a target substrate. 
     
     
         11 . The polymer of  claim 10  wherein a response of a layer of polymer to environmental conditions is controlled, at least in part, by controlling crosslinking density. 
     
     
         12 . The polymer of  claim 1  wherein the radically (co)polymerizable monomers include at least one other monomer selected to effect a desired property on the surface of the target substrate. 
     
     
         13 . The polymer of  claim 12  wherein the at least one other monomer is selected to effect at least one of hydrophilicity, hydrophobicity, biocompatibility, bioactivity, adhesion, adsorption, corrosion resistance, abrasion resistance, temperature insulation, electrical insulation, impact resistance, hardness, softness, swellability, and cushioning for improved ergonomics or thermal responsiveness. 
     
     
         14 . The polymer of  claim 13  wherein the at least one other monomer comprises at least one group that can be converted to a quaternary salt, an electrolyte, a betaine, a sulfonate or a phosphonate. 
     
     
         15 . The polymer of  claim 13  wherein the at least one other monomer is 2-(dimethylamino)ethyl methacrylate (DMAEMA), 4-vinyl pyridine, 2-vinyl pyridine, N-substituted acrylamides, N-acryloyl pyrrolidine, N-acryloyl piperidine, acryl-L-amino acid amides, acrylonitriles, methacrylonitriles vinyl acetates, 2-hydroxy ethyl methacrylate, p-chloromethyl styrene, a derivatives of such a monomer or a substituted varieties of such a monomer. 
     
     
         16 . The polymer of  claim 15  wherein the group of the at least one other monomer is an amino group that can be converted to a quaternary salt by a process comprising reaction of the group with an alkyl halide. 
     
     
         17 . The polymer of  claim 1  wherein the at least one group can be modified in an open air atmosphere. 
     
     
         18 . The polymer of  claim 1  wherein the polymer comprises a block copolymer wherein one segment can react directly with a target substrate and additionally attach a functional polymer segment to the substrate, and a second segment imparts a predetermined physiochemical property to the surface. 
     
     
         19 . The polymer of  claim 1  wherein the at least one monomer is incorporated into the backbone of the polymer, in at least one block of the polymer, in at least one graft on the polymer, or in at least one branch of the polymer. 
     
     
         20 . The polymer of  claim 19  wherein the polymer is a block copolymer and the at least one monomer comprising at least one group that can be modified after the controlled radical polymerization is incorporated into at least one block of the block copolymer. 
     
     
         21 . A polymer which is the reaction product of a controlled radical polymerization of radically (co)polymerizable monomers, wherein at least one of the radically (co)polymerizable monomers comprising at least one group that can be modified after the controlled radical polymerization to effect tethering of the polymer to a surface.