Radiation-curable polymers containing pendant unsaturated peptide groups derived from azlactone polymers

Claim 1

A composition comprising a radiation-curable polymer, said polymer being crosslinkable and having pendant ethylenically unsaturated peptide groups and the following structural formula ##STR12## wherein M is a unit from one or more free radically polymerizable ethylenically unsaturated monomers; R 1 is hydrogen or methyl; R 2 is selected from a single bond, --R 3 -- and ##STR13## in which R 3 is alkylene having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and W is --O--, --S-- or --NH--; R 4 and R 7 are independently selected from a single bond and methylene, or substituted methylene having 1 to 12 carbon atoms; R 5 and R 6 are independently alkyl or cycloalkyl having 1 to 12 carbon atoms, aryl or aralkyl having 6 to 12 carbon atoms or R 5 and R 6 taken together with the carbon to which they are joined form a 5- or 6-membered carbocyclic ring, or may be H when at least one of R 4 and R 7 is methylene; n is 1, 2 or 3; X is --O--, --NH-- or --S--; A is a polymerizable, ethylenically unsaturated group selected from (a) ##STR14## in which R 8 is an alkylene group having 1 to 12 carbon atoms, an arylene group having 1 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an oxyalkylene group, --OR-- p in which R is a lower alkylene group having 2 to 4 carbon atoms and p is 1 to 4; R 9 and R 10 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms or (b) --R 8 WY in which R 8 is as defined under the definition for A, W as defined under the definition for R 2 , and Y is an ethylenically unsaturated acyl group selected from the group including acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl and crotonoyl; a and b are independent whole integer numbers, and b is at least 1, sufficient to provide a polymer wherein the distribution of M units and ##STR15## units is random throughout the polymer.

Claim 15

The method of preparing a radiation-curable polymer, said polymer being crosslinkable and having pendant ethylenically unsaturated peptide groups and the following structural formula ##STR16## wherein M is a unit from one or more free radically polymerizable ethylenically unsaturated monomers; R 1 is hydrogen or methyl; R 2 is selected from a single bond, --R 3 -- and ##STR17## in which R 3 is alkylene having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and W is --O--, --S-- or NH--; R 4 and R 7 are independently selected from a single bond and methylene, or substituted methylene having 1 to 12 carbon atoms; R 5 and R 6 are independently alkyl or cycloalkyl having 1 to 12 carbon atoms, aryl or aralkyl having 6 to 12 carbon atoms or R 5 and R 6 taken together with the carbon to which they are joined form a 5- or 6-membered carbocyclic ring, or may be H when at least one of R 4 and R 7 is methylene; n is 1, 2 or 3; X is --O--, --NH-- or --S--; A is a polymerizable, ethylenically unsaturated group selected from (a) ##STR18## in which R 8 is an alkylene group having 1 to 12 carbon atoms, an arylene group having 1 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an oxyalkylene group, --OR-- p in which R is a lower alkylene group having 2 to 4 carbon atoms and p is 1 to 4; R 9 and R 10 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms or (b) --R 8 WY in which R 8 is as defined under the definition for A, W as defined under the definition for R 2 , and Y is an ethylenically unsaturated acyl group selected from the group including acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl and crotonoyl; a and b are independent whole integer numbers, and b is at least 1, sufficient to provide a polymer wherein the distribution of M units and ##STR19## units is random throughout the polymer, which method includes the steps of a. blending together in a non-nucleophilic solvent (1) an ethylenically unsaturated nucleophilic compound of the formula HXA wherein H is hydrogen; X is --O--, --NH-- or --S--; A is a polymerizable, ethylenically unsaturated group selected from (a) ##STR20## in which R 8 is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an oxyalkylene group, --OR-- p in which R is a lower alkylene group having 2 to 4 carbon atoms and p is 1 to 3; R 9 and R 10 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms or (b) --R 8 --WY in which R 8 is as defined under the definition for R 2 , and Y is an ethylenically unsaturated acryl group selected from the group including acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl and crotonoyl, and (2) a polymer having pendant azlactone groups, said polymer resulting from interpolymerization of (a) 10 to 100 percent by weight of units from one or more ethylenically unsaturated azlactone monomers, and (b) 90 to 0 percent by weight of one or more vinyl monomers, and (3) 0 to 5 percent by weight of a Lewis acid catalyst and b. reacting components (1) and (2).

Claim 16

The method of preparing a radiation-curable polymer, said polymer being crosslinkable and having pendant ethylenically unsaturated peptide groups and the following structural formula ##STR16## wherein M is a unit from one or more free radically polymerizable ethylenically unsaturated monomers; R 1 is hydrogen or methyl; R 2 is selected from a single bond, --R 3 -- and ##STR17## in which R 3 is alkylene having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and W is --O--, --S-- or NH--; R 4 and R 7 are independently selected from a single bond and methylene, or substituted methylene having 1 to 12 carbon atoms; R 5 and R 6 are independently alkyl or cycloalkyl having 1 to 12 carbon atoms, aryl or aralkyl having 6 to 12 carbon atoms or R 5 and R 6 taken together with the carbon to which they are joined form a 5- or 6-membered carbocyclic ring, or may be H when at least one of R 4 and R 7 is methylene; n is 1, 2 or 3; X is --O--, --NH-- or --S--; A is a polymerizable, ethylenically unsaturated group selected from (a) ##STR18## in which R 8 is an alkylene group having 1 to 12 carbon atoms, an arylene group having 1 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an oxyalkylene group, --OR-- p in which R is a lower alkylene group having 2 to 4 carbon atoms and p is 1 to 4; R 9 and R 10 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms or (b) --R 8 WY in which R 8 is as defined under the definition for A, W as defined under the definition for R 2 , and Y is an ethylenically unsaturated acyl group selected from the group including acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl and crotonoyl; a and b are independent whole integer numbers, and b is at least 1, sufficient to provide a polymer wherein the distribution of M units and ##STR19## units is random throughout the polymer, which method includes the steps of a. blending together in a non-nucleophilic solvent (1) an ethylenically unsaturated nucleophilic compound of the formula HXA wherein H is hydrogen; X is --O--, --NH-- or --S--; A is a polymerizable, ethylenically unsaturated group selected from (a) ##STR20## in which R 8 is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an oxyalkylene group, --OR-- p in which R is a lower alkylene group having 2 to 4 carbon atoms and p is 1 to 3; R 9 and R 10 are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms or (b) --R 8 --WY in which R 8 is as defined under the definition for R 2 , and Y is an ethylenically unsaturated acryl group selected from the group including acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl and crotonoyl, and (2) a polymer having pendant azlactone groups, said polymer resulting from interpolymerization of (a) 10 to 100 percent by weight of units from one or more ethylenically unsaturated azlactone monomers, and (b) 90 to 0 percent by weight of one or more vinyl monomers, and (3) 0 to 5 percent by weight of a Lewis acid catalyst and b. reacting components (1) and (2).