Low volatile organic compound stable solvent-based polyurethane compositions for coatings
View Patent ↗Dual-crosslinkable urethanes including urethanes having air curable ethylenic unsaturation and at least one moisture curable functionalized group exhibit good strength, chemical stability, and hardness and can be made by incorporating moisture curable functionalized groups into ethylenically unsaturated urethanes.
1. A dual-crosslinkable urethane coating composition comprising:
an air curable urethane having an ethylenic unsaturated portion;
at least one moisture curable silane functionalized group; and
a catalyst for the air oxidation of the ethylenic unsaturation,
wherein said dual-crosslinkable urethane coating composition has an isocyanate content of zero, and
wherein the at least one moisture curable silane functionalized group is incorporated into the urethane through a reaction of an isocyanate-silane with a hydroxyl-terminated urethane polyol.
2. The dual-crosslinkable urethane coating composition of claim 1 , wherein the air curable ethylenic unsaturated portion of the urethane comprises air curable ethylenic unsaturation from a dry or semi-dry oil or fatty acid.
3. The dual-crosslinkable urethane coating composition of claim 1 , wherein the at least one moisture curable silane functionalized group comprises a terminal or pendent silane group.
4. The dual-crosslinkable urethane coating composition of claim 1 , wherein the solids content of the composition is not less than about 60 percent.
5. A method for coating a surface, comprising coating a surface with a composition comprising a dual-crosslinkable urethane coating composition according to claim 1 .
6. The dual-crosslinkable urethane coating composition of claim 1 ,wherein the at least one moisture curable silane functionalized group comprises a low molecular weight reactive silane, wherein the low molecular weight reactive silane comprises the formula
wherein R 1 is an alkyl group having 1 to 8 carbons or heterocyclic; R 2 is selected from the group consisting of a lower alkyl and an alkoxy; R 3 is a lower alkyl; and n is an integer greater than or equal to 2; and wherein the low molecular weight reactive silane comprises at least one isocyanate and/or epoxy functional group; and said dual-crosslinkable urethane coating composition has an isocyanate content of zero.
7. A dual-crosslinkable urethane coating composition comprising:
an air curable urethane having an ethylenic unsaturated portion;
at least one moisture curable silane functionalized group; and
a catalyst for the air oxidation of the ethylenic unsaturation,
wherein said dual-crosslinkable urethane coating composition has an isocyanate content of zero, and
wherein the at least one moisture curable silane functionalized group is incorporated into the urethane through a reaction of an epoxy-silane with carboxylic acid group in a urethane polymer.
8. The dual-crosslinkable urethane coating composition of claim 7 , wherein the air curable ethylenic unsaturated portion of the urethane comprises air curable ethylenic unsaturation from a dry or semi-dry oil or fatty acid.
9. The dual-crosslinkable urethane coating composition of claim 7 , wherein the at least one moisture curable silane functionalized group comprises a terminal or pendent silane group.
10. The dual-crosslinkable urethane coating composition of claim 7 , wherein the solids content of the composition is not less than about 60 percent.
11. A method for coating a surface, comprising coating a surface with a composition comprising a dual-crosslinkable urethane coating composition according to claim 7 .
12. The dual-crosslinkable urethane coating composition of claim 7 , wherein the at least one moisture curable silane functionalized group comprises a low molecular weight reactive silane, wherein the low molecular weight reactive silane comprises the formula
wherein R 1 is an alkyl group having 1 to 8 carbons or heterocyclic; R 2 is selected from the group consisting of a lower alkyl and an alkoxy; R 3 is a lower alkyl; and n is an integer greater than or equal to 2; and wherein the low molecular weight reactive silane comprises at least one isocyanate and/or epoxy functional group; and said dual-crosslinkable urethane coating composition has an isocyanate content of zero.
13. A method of forming a dual-crosslinked urethane, comprising:
reacting an isocyanate with a hydroxyl functional oil-ester to form an air curable urethane polymer having ethylenic unsaturation and incorporating at least one silane group into the urethane to provide a urethane having no isocyanate content; and
curing the air-curable urethane in the presence of moisture, oxygen and a catalyst for the air oxidation of the ethylenic unsaturation,
wherein the hydroxyl functional oil-ester is formed by the esterification of a polyfunctional alcohol with a fatty acid.
14. The method of claim 13 , wherein the isocyanate comprises a diisocyanate selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, bis (4-isocyanatocyclohexyl) methane, 1 -isocyanato-3 -isocyanatomethyl-3,5,5,-trimethylcyclohexane, m- and p-phenylene diisocyanate, 2,6-and 2,4-tolyene diisocyanate, xylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 4,4′-bisphenylene diisocyanate, 4,4′-methylene diphenylisocyante, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate, 1,12-dodecyldiisocyanate, norbornyl diisocyanate, 2-methyl-1,5-pentane diisocyanate and mixtures thereof.
15. The method of claim 13 , wherein the polyfunctional alcohol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propane diol, 1,3 butylene diol, bisphenol-A, hydrogenated bisphenol-A, trimethylolpropane, trimethylol-ethane, pentaerythritol, glycerin, neopentyl glycol, cyclohexane dimethanol, 2-methyl-1,3-propanediol, 1,6-hexanediol di-pentaerythritol, di-ethylene glycol, tri-ethylene glycol, di-trimethylolpropane, and mixtures thereof.
16. The method of claim 13 , wherein the fatty acid is selected from the group consisting of linoleic acids, palmitoleic acids, linolenic acids, eleostearic acids, arachidonic acids, ricinoleic acids, and mixtures thereof.
17. The method of claim 13 , wherein the oil-ester is modified with a polyacid selected from the group consisting of isophthalic acid, terephthalic acid, 5-(sodiosulfo)-isophthalic acid, trimellitic anhydride, adipic acid, 1,4-cyclohexyl dicarboxylic acid, succinic anhydride, maleic acid, fumaric acid, succinic acid, azaleic acid, sebacic acid, methyl succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and phthalic anhydride.
18. The method of claim 13 , wherein the hydroxyl functional oil-ester has a hydroxyl value of between about 100 and about 250.
19. The method of claim 13 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with a modified silane having the formula
wherein R 1 is an alkyl group having 1 to 8 carbons; R 2 is selected from the group consisting of a lower alkyl and an alkoxy; R 3 is a lower alkyl; and A is a selected from the group consisting of substituted or unsubstituted isocyanate groups and oxirane groups.
20. The method of claim 13 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with a silane selected from the group consisting of an isocyanate-silane and an oxirane silane.
21. The method of claim 13 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with oxirane group selected from the group consisting of glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexyl ethyltrimethoxysilane, and mixtures thereof.
22. The method of claim 13 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with an isocyanato-silane selected from the group consisting of isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, and mixtures thereof.
23. A method of forming a dual-crosslinked urethane, comprising:
reacting an isocyanate with a hydroxyl functional oil-ester to form an air curable urethane polymer having ethylenic unsaturation and incorporating at least one silane group into the urethane to provide a urethane having no isocyanate content; and
curing the air-curable urethane in the presence of moisture, oxygen and a catalyst for the air oxidation of the ethylenic unsaturation,
wherein the hydroxyl functional oil-ester is formed by the transesterification of a polyfunctional alcohol with an oil, wherein at least a portion of the oil is unsaturated.
24. The method of claim 23 , wherein the polyfunctional alcohol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propane diol, 1,3 butylene diol, bisphenol-A, hydrogenated bisphenol-A, trimethylolpropane, trimethylol-ethane, pentaerythritol, glycerin, neopentyl glycol, cyclohexane dimethanol, 2-methyl-1,3-propanediol, 1,6-hexanediol di-pentaerythritol, di-ethylene glycol, tri-ethylene glycol, di-trimethylolpropane, and mixtures thereof.
25. The method of claim 23 , wherein the hydroxyl functional oil-ester has a hydroxyl value of between about 100 and about 250.
26. The method of claim 23 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with a modified silane having the formula
wherein R 1 is an alkyl group having 1 to 8 carbons; R 2 is selected from the group consisting of a lower alkyl and an alkoxy; R 3 is a lower alkyl; and A is a selected from the group consisting of substituted or unsubstituted isocyanate groups and oxirane groups.
27. The method of claim 23 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with a silane selected from the group consisting of an isocyanate-silane and an oxirane silane.
28. The method of claim 23 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with oxirane group selected from the group consisting of glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexyl ethyltrimethoxysilane, and mixtures thereof.
29. The method of claim 23 , wherein incorporating at least one silane group into the urethane comprises reacting the urethane with an isocyanato-silane selected from the group consisting of isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, and mixtures thereof.