Low VOC thermosetting polyester acrylic resin for gel coat
View Patent ↗Low VOC thermosetting polyester acrylic resins are made by esterification of unsaturated epoxide such as glycidyl methacrylate, and a polyacid which is the half-ester formed by reacting an acid or its anhydride with a polyol is disclosed. The obtained low viscosity resin is useful for making a low or zero VOC gel coat with excellent hydrolytic and weather resistance.
1. A thermosetting, crosslinkable resin composition suitable for preparing a gel coat, the composition comprising:
a polyester acrylic polymer having an average of more than two polymerizable carbon-carbon double bonds in each molecule, the carbon-carbon double bonds in the polyester acrylic polymer being from a reaction product of a saturated polyacid half-ester having an average acid functionality of 2 or more and an unsaturated epoxide monomer in about chemically equivalent amounts to furnish one epoxy group per carboxyl group, the saturated polyacid half-ester being the reaction product of one or more polyols having an average of at least two hydroxyl groups in the molecule with one or more saturated polycarboxylic acids or acid anhydrides; the polyester acrylic polymer containing less than 10 weight % aromatic content and having a number average molecular weight of 560-2500 and a viscosity less than 1500 cps at 70 wt. % NVM solids dispersed in 30 wt. % styrene based on the total weight of the polymer and the styrene;
the polyester acrylic polymer blended with a polymerizable vinyl monomer.
2. The resin composition of claim 1 , wherein the unsaturated epoxide monomer is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.
3. The resin composition of claim 1 , wherein the polyol has a hydroxyl number of from about 130 to 1200, and a number average molecular weight between about 190 and 1800.
4. The resin composition of claim 1 , wherein the polyol is selected from the group consisting of polyols which contain 2 to 20 carbon atoms, and polymeric polyols selected from the group consisting of polyester polyols, polyurethane polyols, polyether polyols and acrylic polyols, and mixtures thereof.
5. The resin composition of claim 1 , wherein the saturated polycarboxylic acid or acid anhydride, exclusive of the carbon atoms and anhydride moiety, contains from 2 to 20 carbon atoms.
6. The resin composition of claim 1 , wherein the polyester acrylic polymer has free secondary OH groups and unsaturated acrylate ester linkages.
7. The resin composition of claim 1 , wherein the polymerizable vinyl monomer is selected from the group consisting of aromatic compounds, unsaturated esters, unsaturated acids, halides, nitriles, diolefins, esters of polycarboxylic acids, and mixtures thereof.
8. A process for making a polyester acrylic polymer having an average of more than two polymerizable carbon-carbon double bonds in each molecule, comprising:
a. Preparing a saturated polyacid half-ester having an average acid functionality of 2 or more by reaction of a polyol with a saturated polycarboxylic acid or acid anhydride, the polyol having an average of at least two hydroxyl groups in the molecule, a hydroxyl number of from about 56 to 1830 and an average molecular weight of from about 92 to about 2,000; and
b. Esterification of the saturated polyacid half-ester with an unsaturated epoxide monomer in about chemically equivalent amounts to furnish one epoxy group per carboxyl group to produce the polyester acrylic polymer having said carbon-carbon double bonds, being from reaction of the saturated polyacid half-ester with the unsaturated epoxide monomer, the polyester acrylic polymer containing less than 10 weight % aromatic content.
9. The resin composition of claim 1 , wherein the resin composition further comprises a pigment.
10. A gel coat comprising the resin composition according to claim 1 , wherein the gel coat is combined with an initiator and coated on a composite molded substrate comprising a material selected from the group consisting of the resin composition according to claim 1 , unsaturated polyester resins (UPR), and vinyl esters.
11. An article having a gel coat thereon, the gel coat comprising the resin composition of claim 1 being partially or fully crosslinked.
12. The resin composition of claim 1 , wherein the composition comprises a weight ratio of the polyester acrylic polymer to the polymerizable vinyl monomer of about 90:10 to about 40:60.
13. The resin composition of claim 1 , wherein the polyester acrylic polymer has a number average molecular weight of 800-2000, and a viscosity of less than 1000.
14. The resin composition of claim 1 , wherein the polyol has a hydroxyl number of from about 56 to 1830, and a number average molecular weight between about 92 and 2000.
15. The resin composition of claim 5 , wherein the saturated polycarboxylic acid anhydride is selected from the group consisting of aliphatic anhydrides, cycloaliphatic anhydrides, and substituted aliphatic anhydrides.
16. The resin composition of claim 6 , wherein the free secondary OH groups of the polyester acrylic polymer are reacted with a diisocyanate, polyisocyanate, or isocyanate functional prepolymer.
17. The resin composition of claim 7 , wherein the polymerizable vinyl monomer is selected from the group consisting of styrene, alpha-methylstyrene, dichlorostyrene, vinyl naphthalene, vinyl phenol, acrylic and methacrylic esters, vinyl laurate, acrylic acids, alpha-alkylacrylic acids, butenoic acid, allylbenzoic acid, vinylbenzoic acid, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, butadiene, isoprene, methylpentadiene, diallyl phthalate, divinyl succinate, diallyl maleate, divinyl adipate, dichloroallyl tetrahydrophthalate, and mixtures thereof.
18. The process of claim 8 , wherein the carboxylic acid anhydride has at least one intramolecular carboxylic anhydride group.
19. The resin composition of claim 1 , wherein the acid to hydroxyl molar ratio is at least about 1.6.
20. The resin composition of claim 1 , wherein the saturated polyacid half-ester is the reaction product of the polyol and the saturated polycarboxylic acid or acid anhydride at an equivalent ratio of anhydride to hydroxyl on the polyol of at least about 0.8:1 or at a molar ratio of acid to hydroxyl on the polyol of at least about 1.6:1.
21. The resin composition of claim 1 , wherein the saturated polyacid half-ester has an average acid functionality of more than 2.
22. The resin composition of claim 1 , further comprising an initiator.