Claims
- 1. A thermosetting composition comprising a co-reactable solid, particulate mixture of:(a) a polycarboxylic acid functional polymer prepared by atom transfer radical polymerization initiated in the presence of an initiator having at least one radically transferable group, and in which said polymer contains at least one of the following polymer chain structures: —[—(M)p—(G)q—]x—and—[—(G)q—(M)p—]x—wherein M is a residue, that is free of carboxylic acid functionality, of at least one ethylenically unsaturated radically polymerizable monomer; G is a residue, that has carboxylic acid functionality, of at least one ethylenically unsaturated radically polymerizable monomer; p and q represent average numbers of residues occurring in a block of residues in each polymer chain structure; and p, q and x are each individually selected for each structure such that said polycarboxylic acid functional polymer has a number average molecular weight of at least 250 and polydispersity index of less than 2.5; and(b) epoxide functional crosslinking agent having at least two epoxide groups.
- 2. The composition of claim 1 wherein said polycarboxylic acid functional polymer is selected from the group consisting of linear polymers, branched polymers, hyperbranched polymers, star polymers, graft polymers and mixtures thereof.
- 3. The composition of claim 1 wherein said polycarboxylic acid functional polymer has a number average molecular weight of from 500 to 16,000, and a polydispersity index of less than 2.0.
- 4. The composition of claim 1 wherein said initiator is selected from the group consisting of linear or branched aliphatic compounds, cycloaliphatic compounds, aromatic compounds, polycyclic aromatic compounds, heterocyclic compounds, sulfonyl compounds, sulfenyl compounds, esters of carboxylic acids, polymeric compounds and mixtures thereof, each having at least one radically transferable halide.
- 5. The composition of claim 4 wherein said initiator is selected from the group consisting of halomethane, methylenedihalide, haloform, carbon tetrahalide, 1-halo-2,3-epoxypropane, p-methanesulfonyl halide, p-toluenesulfonyl halide, methanesulfenyl halide, p-toluenesulfenyl halide, 1-phenylethyl halide, C1-C6-alkyl ester of 2-halo-C1-C6-carboxylic acid, p-halomethylstyrene, mono-hexakis(α-halo-C1-C6-alkyl)benzene, diethyl-2-halo-2-methyl malonate, ethyl 2 -bromoisobutyrate and mixtures thereof.
- 6. The composition of claim 1 wherein said polycarboxylic acid functional polymer has a carboxylic acid equivalent weight of from 100 to 10,000 grams/equivalent.
- 7. The composition of claim 1 wherein M is derived from at least one of vinyl monomers, allylic monomers and olefins.
- 8. The composition of claim 7 wherein M is derived from at least one of alkyl (meth)acrylates having from 1 to 20 carbon atoms in the alkyl group, vinyl aromatic monomers, vinyl halides, vinyl esters of carboxylic acids and olefins.
- 9. The composition of claim 1 wherein said epoxide functional crosslinking agent (b) is selected from the group consisting of epoxide functional polyesters, epoxide functional polymers prepared by free radical polymerization methods, epoxide functional polyethers, epoxide functional isocyanurates and mixtures thereof.
- 10. The composition of claim 9 wherein said epoxide functional crosslinking agent (b) is tris(2,3-epoxypropyl)isocyanurate.
- 11. The composition of claim 1 wherein the equivalent ratio of carboxylic acid equivalents in said polycarboxylic acid functional polymer (a) to epoxy equivalents in said epoxide functional crosslinking agent (b) is within the range of 0.7:1 to 2:1.
- 12. The composition of claim 1 wherein said polycarboxylic acid functional polymer (a) is present in said thermosetting composition in an amount of from 50 to 98 percent by weight, based on total resin solids weight, and said epoxide functional crosslinking agent (b) is present in said thermosetting composition in an amount of from 2 to 50 percent by weight, based on total resin solids weight.
- 13. The composition of claim 1 wherein G is derived from: alkyl (meth)acrylate, which after polymerization is hydrolyzed; or at least one hydroxy functional ethylenically unsaturated radically polymerizable monomer, which after polymerization is post-reacted with a cyclic anhydride.
- 14. The composition of claim 13 wherein G is derived from: C1-C4 alkyl (meth)acrylate, which after polymerization is hydrolyzed; or at least one of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, which after polymerization is post-reacted with a cyclic anhydride.
- 15. The composition of claim 1 wherein said polycarboxylic acid functional polymer (a) has at least one of the following polymer chain structures:φ−[[(M)p−(G)q]x−(M)r−T]zandφ−[[(G)q−(M)p]x−(G)s−T]zwherein φ is or is derived from the residue of said initiator free of said radically transferable group; T is or is derived from said radically transferable group of said initiator; x is independently from 1 to 100 for each structure; p and q are each independently within the range of 0 to 100 for each x-segment and for each structure, the sun of p and q being at least 1 for each x-segment, and q being at least 1 for at least one x-segment; r and s are each independently for each structure within the range of 0 to 100; z is independently for each structure at least 1; and said polycarboxylic acid functional polymer has a polydispersity index of less than 2.0.
- 16. The composition of claim 15 wherein said polycarboxylic acid functional polymer has a number average molecular weight of from 500 to 16,000, and a polydispersity index of less than 1.8.
- 17. The composition of claim 15 wherein p is independently selected for each structure within the range of 1 to 20; and q is independently selected for each structure within in the range of 1 to 20.
- 18. The composition of claim 15 wherein x is independently selected for each structure within the range of 1 to 50.
- 19. The composition of claim 15 wherein T is halide.
- 20. The composition of claim 19 wherein T is derived from a dehalogenation post-reaction.
- 21. The composition of claim 20 wherein said dehalogenation post-reaction comprises contacting a precursor of said polycarboxylic acid functional polymer that is substantially free of carboxylic acid functionality with a limited radically polymerizable ethylenically unsaturated compound.
- 22. The composition of claim 21 wherein said limited radically polymerizable ethylenically unsaturated compound is selected from the group consisting of 1,1-dimethylethylene, 1,1-diphenylethylene, isopropenyl acetate, alpha-methyl styrene, 1,1-dialkoxy olefin and combinations thereof.
- 23. The composition of claim 1 further comprising polycarboxylic acid functional polyester.
- 24. The composition of claim 23 wherein said polycarboxylic acid functional polyester has a carboxylic acid equivalent weight of from 290 grams/equivalent to 3,000 grams/equivalent, and is present in said composition in an amount of from 1 percent by weight to 40 percent by weight, based on the total weight of resin solids.
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application Ser. No. 60/098603, filed Aug. 31, 1998, which is hereby incorporated by reference.
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Provisional Applications (1)
|
Number |
Date |
Country |
|
60/098603 |
Aug 1998 |
US |