Ultraviolet-curable polyurethane compositions
View Patent ↗Ultraviolet (UV)-curable polyurethane compositions are provided which are made by reacting an isocyanate with an ultraviolet (UV)-curable polyol that is made by co-polymerizing an alkylene oxide, an unsaturated carboxylic acid or anhydride and a hydroxy functional compound and which has an ultra-low level of unsaturation. The inventive ultraviolet (UV)-curable polyurethane compositions may find use in or as coatings, adhesives, sealants, elastomers and the like.
1. An ultraviolet (UV)-curable polyurethane composition comprising:
at least one isocyanate; and
at least one ultraviolet (UV)-curable polyol comprising a reaction product of
about 30 wt. % to about 70 wt. % of a hydroxy functional compound having a functionality of about 2 to about 3;
about 1 wt. % to about 10 wt. % of an unsaturated carboxylic acid or anhydride; and
about 20 wt. % to about 69 wt. % of an alkylene oxide, such that the sum of the percentages totals 100,
wherein the at least one ultraviolet (UV)-curable polyol has an unsaturation of less than about 0.01 meq/g.
2. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the hydroxy functional compound comprises about 30 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
3. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the hydroxy functional compound comprises about 40 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
4. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the hydroxy functional compound is chosen from polypropylene oxide, polyethylene oxide, polybutylene oxide, copolymers of propylene oxide and ethylene oxide, copolymers of propylene oxide and butylene oxide, copolymers of butylene oxide and ethylene oxide, and mixtures thereof.
5. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the unsaturated carboxylic acid or anhydride comprises about 1 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
6. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the unsaturated carboxylic acid or anhydride comprises about 2 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
7. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the unsaturated carboxylic acid or anhydride is chosen from cis-1,2,3,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, maleic acid, maleic anhydride and mixtures thereof.
8. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the alkylene oxide comprises about 20 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
9. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the alkylene oxide comprises about 25 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
10. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the alkylene oxide is chosen from propylene oxide, ethylene oxide, butylene oxide and mixtures thereof.
11. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the isocyanate is chosen from 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, 1,8-octylene diisocyanate, 1,5-diisocyanato-2,2,4-trimethylpentane, 3-oxo-1,5-pentane diisocyanate, isophorone diisocyanate, the cyclohexane diisocyanates, hydrogenated tetramethylxylylene diisocyanate, hydrogenated toluene diisocyanates, hydrogenated methylene diphenylene diisocyanates, toluene diisocyanates, methylene diphenylene diisocyanates, polymethylene polyphenylene polyisocyanates and isocyanate-terminated prepolymers.
12. The ultraviolet (UV)-curable polyurethane composition according to claim 1 further including at least one of a photoinitiator, photoactivator and a cross-linking agent.
13. The ultraviolet (UV)-curable polyurethane composition according to claim 1 , wherein the ultraviolet (UV)-curable polyol has an unsaturation of about 0.004 to about 0.008 meq/g.
14. One of a coating, adhesive, sealant and elastomer containing the ultraviolet (UV)-curable polyurethane composition according to claim 1 .
15. In a process for producing one of a coating, adhesive, sealant and elastomer, the improvement comprising including the ultraviolet (UV)-curable polyurethane composition according to claim 1 .
16. A process of making an ultraviolet (UV)-curable polyurethane composition comprising:
reacting
at least one isocyanate with
at least one ultraviolet (UV)-curable polyol comprising the reaction product of
about 30 wt. % to about 70 wt. % of a hydroxy functional compound having a functionality of about 2 to about 3,
about 1 wt. % to about 10 wt. % of an unsaturated carboxylic acid or anhydride, and
about 20 wt. % to about 69 wt. % of an alkylene oxide, such that the sum of the percentages totals 100,
wherein the at least one ultraviolet (UV)-curable polyol has an unsaturation of less than about 0.01 meq/g; and
curing the ultraviolet (UV)-curable polyurethane composition.
17. The process according to claim 16 , wherein the hydroxy functional compound comprises about 30 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
18. The process according to claim 16 , wherein the hydroxy functional compound comprises about 40 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
19. The process according to claim 16 , wherein the hydroxy functional compound is chosen from polypropylene oxide, polyethylene oxide, polybutylene oxide, copolymers of propylene oxide and ethylene oxide, copolymers of propylene oxide and butylene oxide, copolymers of butylene oxide and ethylene oxide, and mixtures thereof.
20. The process according to claim 16 , wherein the unsaturated carboxylic acid or anhydride comprises about 1 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
21. The process according to claim 16 , wherein the unsaturated carboxylic acid or anhydride comprises about 2 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
22. The process according to claim 16 , wherein the unsaturated carboxylic acid or anhydride is chosen from cis-1,2,3,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, maleic acid, maleic anhydride and mixtures thereof.
23. The process according to claim 16 , wherein the alkylene oxide comprises about 20 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
24. The process according to claim 16 , wherein the alkylene oxide comprises about 25 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
25. The process according to claim 16 , wherein the alkylene oxide is chosen from propylene oxide, ethylene oxide, butylene oxide and mixtures thereof.
26. The process according to claim 16 , wherein the isocyanate is chosen from 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, 1,8-octylene diisocyanate, 1,5-diisocyanato-2,2,4-trimethylpentane, 3-oxo-1,5-pentane diisocyanate, isophorone diisocyanate, the cyclohexane diisocyanates, hydrogenated tetramethylxylylene diisocyanate, hydrogenated toluene diisocyanates, hydrogenated methylene diphenylene diisocyanates, toluene diisocyanates, methylene diphenylene diisocyanates, polymethylene polyphenylene polyisocyanates and isocyanate-terminated prepolymers.
27. The process according to claim 16 further including adding at least one of a photoinitiator, photoactivator and a cross-linking agent.
28. The process according to claim 16 , wherein the ultraviolet (UV)-curable polyol has an unsaturation of about 0.004 to about 0.008 meq/g.
29. One of a coating, adhesive, sealant and elastomer containing the ultraviolet (UV)-curable polyurethane composition made by the process according to claim 16 .
30. In a process for producing one of a coating, adhesive, sealant and elastomer, the improvement comprising including the ultraviolet (UV)-curable polyurethane composition made by the process according to claim 16 .
31. A coated substrate comprising a substrate having applied thereto an ultraviolet (UV)-curable polyurethane composition comprising, at least one isocyanate and at least one ultraviolet (UV)-curable polyol comprising a reaction product of about 30 wt. % to about 70 wt. % of a hydroxy functional compound having a functionality of about 2 to about 3, about 1 wt. % to about 10 wt. % of an unsaturated carboxylic acid or anhydride and about 20 wt. % to about 69 wt. % of an alkylene oxide, such that the sum of the percentages totals 100, wherein the at least one ultraviolet (UV)-curable polyol has an unsaturation of less than about 0.01 meq/g.
32. The coated substrate according to claim 31 , wherein the hydroxy functional compound comprises about 30 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
33. The coated substrate according to claim 31 , wherein the hydroxy functional compound comprises about 40 wt. % to about 60 wt. % of the at least one ultraviolet (UV)-curable polyol.
34. The coated substrate according to claim 31 , wherein the hydroxy functional compound is chosen from polypropylene oxide, polyethylene oxide, polybutylene oxide, copolymers of propylene oxide and ethylene oxide, copolymers of propylene oxide and butylene oxide, copolymers of butylene oxide and ethylene oxide, and mixtures thereof.
35. The coated substrate according to claim 31 , wherein the unsaturated carboxylic acid or anhydride comprises about 1 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
36. The coated substrate according to claim 31 , wherein the unsaturated carboxylic acid or anhydride comprises about 2 wt. % to about 5 wt. % of the at least one ultraviolet (UV)-curable polyol.
37. The coated substrate according to claim 31 , wherein the unsaturated carboxylic acid or anhydride is chosen from cis-1,2,3,6-tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, maleic acid, maleic anhydride and mixtures thereof.
38. The coated substrate according to claim 31 , wherein the alkylene oxide comprises-about 20 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
39. The coated substrate according to claim 31 , wherein the alkylene oxide comprises about 25 wt. % to about 50 wt. % of the at least one ultraviolet (UV)-curable polyol.
40. The coated substrate according to claim 31 , wherein the alkylene oxide is chosen from propylene oxide, ethylene oxide, butylene oxide and mixtures thereof.
41. The coated substrate according to claim 31 , wherein the isocyanate is chosen from 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, 1,8-octylene diisocyanate, 1,5-diisocyanato-2,2,4-trimethylpentane, 3-oxo-1,5-pentane diisocyanate, isophorone diisocyanate, the cyclohexane diisocyanates, hydrogenated tetramethylxylylene diisocyanate, hydrogenated toluene diisocyanates, hydrogenated methylene diphenylene diisocyanates, toluene diisocyanates, methylene diphenylene diisocyanates, polymethylene polyphenylene polyisocyanates and isocyanate-terminated prepolymers.
42. The coated substrate according to claim 31 further including at least one of a photoinitiator, photoactivator and a cross-linking agent.