Highly functional epoxidized resins and coatings

Patent metadata

Field	Value
Publication number	US-10329377-B2
Application number	US-201514801306-A
Country	US
Kind code	B2
Filing date	Jul 16, 2015
Priority date	Feb 6, 2010
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The invention provides highly functional epoxy resins that may be used themselves in coating formulations and applications but which may be further functionalized via ring-opening reactions of the epoxy groups yielding derivative resins with other useful functionalities. The highly functional epoxy resins are synthesized from the epoxidation of vegetable or seed oil esters of polyols having 4 or more hydroxyl groups/molecule. In one embodiment, the polyol is sucrose and the vegetable or seed oil is selected from corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof. Methods of making of the epoxy resin and each of its derivative resins are disclosed as are coating compositions and coated objects using each of the resins.

First claim

The claimed invention is:

1. An epoxy resin which is the reaction product of:
a) a polyol having 4 or more hydroxyl groups selected from copolymers of styrene and allyl alcohol; and
b) an ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof; and
wherein at least one ethylenically unsaturated group of the ethylenically unsaturated fatty acid is oxidized to an epoxy group,
wherein about 75% to about 96% of the hydroxyls on the polyol are esterified by the fatty acids b).

2. An epoxy resin of claim 1 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is a vegetable or seed oil fatty acid.

3. An epoxy resin of claim 2 , wherein:
b) the vegetable or seed oil is selected from corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof.

4. An epoxy resin of claim 1 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is a soybean oil fatty acid.

5. An epoxy resin of claim 1 , wherein about 75% of the hydroxyls on the polyol are esterified by the fatty acids b).

6. An epoxy resin of claim 5 , wherein 75% of the hydroxyls on the polyol are esterified by the fatty acids b).

7. An epoxy resin of claim 1 , having an epoxide functionality ranging from about 8 to about 15.

8. A curable coating composition comprising
a) an epoxy resin of claim 1 ; and
b) a cationic photoinitiator; and,
c) optionally, one or more diluents; and,
d) optionally, one or more pigments.

9. A coating composition of claim 8 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is soybean oil.

10. A coating composition of claim 8 , wherein said coating composition is cured by contacting said coating composition with UV light.

11. An object coated with the coating composition of claim 8 .

12. A method of making an epoxy resin of claim 1 comprising the steps of:
a) esterifying a polyol having 4 or more hydroxyl groups selected from copolymers of styrene and allyl alcohol by reaction with an ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof; and
b) oxidizing at least one ethylenically unsaturated group of the ethylenically unsaturated fatty acid to an epoxy group.

13. A method of making an epoxy resin of claim 12 , where:
b) the ethylenically unsaturated fatty acid, the optional saturated fatty acid, or the mixtures thereof is a vegetable or seed oil selected from corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof.

14. An ethylenically unsaturated resin which is the reaction product of an epoxy resin of claim 1 and an at least one ethylenically unsaturated acid.

15. An ethylenically unsaturated resin of claim 14 , wherein the ethylenically unsaturated acid is selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and mixtures thereof.

16. An ethylenically unsaturated resin of claim 14 , wherein the ethylenically unsaturated acid is acrylic acid or methacrylic acid.

17. An ethylenically unsaturated resin of claim 16 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is soybean oil.

18. An ethylenically unsaturated resin of claim 14 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is soybean oil.

19. A coating composition comprising a resin of claim 14 , an optional diluent, a free radical photoinitiator, and optionally, one or more pigments.

20. A coating composition of claim 19 , wherein said coating composition is cured by contacting said coating composition with UV light.

21. An object coated with the coating composition of claim 19 .

22. A resin having hydroxyl functionality which is the reaction product of:
an epoxy resin of claim 1 , and at least one organic acid; or
an epoxy resin of claim 1 , and at least one alcohol.

23. A resin of claim 22 , wherein the resin having hydroxyl functionality is the reaction product of:
the epoxy resin and an at least one organic acid selected from acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylhexanoic acid, and mixtures thereof.

24. A resin of claim 22 , wherein the resin having hydroxyl functionality is the reaction product of:
the epoxy resin and an at least one alcohol selected from methanol, ethanol, n-propanol, n-butanol, isopropanol, isobutanol, 2-ethyl-1-hexanol, and mixtures thereof.

25. A resin of claim 22 , wherein:
b) the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is soybean oil.

26. A thermoset coating composition comprising a resin of claim 22 , a polyisocyanate, an optional solvent, an optional catalyst, and optionally, one or more pigments.

27. An object coated with the thermoset coating composition of claim 26 .

28. A coating composition comprising an epoxy-anhydride composition of claim 22 , an optional solvent, and optionally, one or more pigments.

29. An object coated with the coating composition of claim 28 .

30. An epoxy-anhydride composition comprising an epoxy resin of claim 1 , an acid anhydride, and a curing catalyst.

31. An epoxy-anhydride composition of claim 30 , wherein in the ethylenically unsaturated fatty acid, optionally a saturated fatty acid, or mixtures thereof is soybean oil.

Assignees

• Ndsu Res Foundation

Inventors

• Webster Dean C
• Sengupta Partha Pratim
• Chen Zhigang
• Pan Xiao
• Paramarta Adlina

Classifications

• C09D163/08

  Epoxidised polymerised polyenes · CPC title

• C08G59/1455

  Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof · CPC title

• C08G59/34

  obtained by epoxidation of an unsaturated polymer · CPC title

• C08G59/4215

  cycloaliphatic · CPC title

• C09D163/00

  Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins · CPC title