Segmented reactive block copolymers

Abstract

This invention is directed toward reactive segmented block copolymers useful to treat the surface of a substrate by means of reactive functionalities of the reactive segmented block copolymer material reacting with complementary surface reactive functionalities of the polymer substrate.

1 . A reactive segmented block copolymer comprising a chemical binding unit block and a hydrophilic block. 
   
   
       2 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit is selected from the group consisting of monomers comprising a functionality selected from the group consisting of epoxides, carboxylic acids, anhydrides, oxazolinones, lactams, lactones, amines, hydroxys, hydrazines, hydrazides, thiols, nucleophilic groups, electrophilic groups, carboxylic esters, imide esters, orthoesters, carbonates, isocyanates, isothiocyanates, aldehydes, ketones, thiones, alkenyls, acrylates, methacrylates, acrylamides, sulfones, maleimides, disulfides, iodos, sulfonates, thiosulfonates, silanes, alkoxysilanes, halosilanes, phosphoramidate and alcohol functionality. 
   
   
       3 . The reactive segmented block copolymer of  claim 1  wherein the hydrophilic block comprises monomers selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, N,N′-dimethylmethacrylamide, N,N′-dimethylacrylamide; ethylenically unsaturated poly(alkylene oxide)s, cyclic lactams, N-vinyl-2-pyrrolidone, hydrophilic vinyl carbonate, hydrophilic vinyl carbamate monomers, 2-hydroxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, glyceryl(meth)acrylate, poly(ethylene glycol (meth)acrylate), tetrahydrofurfuryl(meth)acrylate, N-vinyl acetamide, copolymers, derivatives and combinations thereof. 
   
   
       4 . The reactive segmented block copolymer of  claim 1  wherein the block of the chemical binding unit comprises between 1 and about 1,000 units. 
   
   
       5 . The reactive segmented block copolymer of  claim 1  wherein the block of the chemical binding unit comprises between 1 and about 100 units. 
   
   
       6 . The reactive segmented block copolymer of  claim 1  wherein the block of the chemical binding unit comprises between 1 and about 30 units. 
   
   
       7 . The reactive segmented block copolymer of  claim 1  wherein the hydrophilic block comprises between 1 and about 10,000 units. 
   
   
       8 . The reactive segmented block copolymer of  claim 1  wherein the hydrophilic block comprises between about 10 and about 1,000 units. 
   
   
       9 . The reactive segmented block copolymer of  claim 1  wherein the hydrophilic block comprises between about 20 and about 300 units. 
   
   
       10 . A reactive segmented block copolymer having the following generic formula (I):
   R1-[(A)m]p-[(B)n]q-X   (I)   
     wherein R1 is a reactive residue of a moiety capable of acting as an initiator for Atom Transfer Radical Polymerization, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and X is a halogen capping group of an initiator for Atom Transfer Radical Polymerization or a derivatized reaction product. 
   
   
       11 . A reactive segmented block copolymer having the following generic formula (II):
   R1-[(A)m]p-[(B)n]q-R2   (II)   
     wherein R1 is a radical forming residue of a RAFT agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is I to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl fragment of the chain transfer agent or a derivatized reaction product. 
   
   
       12 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit block is an epoxy containing vinylic monomer. 
   
   
       13 . The reactive segmented block copolymer of  claim 12  wherein the epoxy containing vinylic monomer is glycidyl methacrylate. 
   
   
       14 . The reactive segmented block copolymer of  claim 12  wherein the epoxy containing monomer is glycidyl vinyl carbamate or glycidyl vinyl carbonate. 
   
   
       15 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit is glycidyl methacrylate and the hydrophilic block comprises N,N-dimethylacrylamide. 
   
   
       16 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit block comprises glycidyl vinyl carbonate or glycidyl vinyl carbamate and the hydrophilic block comprises n-vinyl pyrolidone. 
   
   
       17 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit is about 15 units of glycidyl methacrylate and the hydrophilic block comprises about 100 units of N,N-dimethylacrylamide. 
   
   
       18 . The reactive segmented block copolymer of  claim 1  wherein the chemical binding unit block is about 15 units of glycidyl vinyl carbonate or glycidyl vinyl carbamate and the hydrophilic block comprises about 100 units of n-vinyl pyrolidone. 
   
   
       19 . A reactive segmented block copolymer having the following generic formula (III):
   R1-[(B)n]q-[(A)m]p-R2-[(A)m]p-[(B)n]q-R1   (III)   
     wherein R1 is a radical forming residue of a RAFT agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl thio group. 
   
   
       20 . The reactive segmented block copolymer of  claim 10  wherein one of the chemical binding unit block or the hydrophilic block is a statistical copolymerization or compositionally heterogeneous block. 
   
   
       21 . The reactive segmented block copolymer of  claim 11  wherein one of the chemical binding unit block or the hydrophilic block is a statistical copolymerization or compositionally heterogeneous block. 
   
   
       22 . The reactive segmented block copolymer of  claim 19  wherein one of the chemical binding unit block or the hydrophilic block is a statistical copolymerization or compositionally heterogeneous block. 
   
   
       23 . The reactive segmented block copolymer of  claim 10  further comprising at least one block selected from the group consisting of nonbinding blocks, nonhydrophilic blocks and combinations thereof. 
   
   
       24 . The reactive segmented block copolymer of  claim 11  further comprising at least one block selected from the group consisting of nonbinding blocks, nonhydrophilic blocks and combinations there. 
   
   
       25 . The reactive segmented block copolymer of  claim 19  further comprising at least one block selected from the group consisting of nonbinding blocks, nonhydrophilic blocks and combinations thereof.