BLOCKED BIO-BASED CARBOXYLIC ACIDS AND THEIR USE IN THERMOSETTING MATERIALS

• US 20150232691A1
• Filed: 09/17/2013
• Published: 08/20/2015
• Est. Priority Date: 09/17/2012
• Status: Abandoned Application

• Current Assignee: Ndsu-Research Foundation
• Original Assignee: Ndsu-Research Foundation
• Inventors: Webster, Dean C., Pavlacky, Erin, Kovash, Curtiss Jr.
• Application Number:
  US14/428,047
• Publication Number:
  US 20150232691A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07C 67/24 by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
• CPC Class Codes: C07C 69/34 Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
• CPC Class Codes: C07C 69/40 Succinic acid esters
• CPC Class Codes: C07C 69/42 Glutaric acid esters
• CPC Class Codes: C07C 69/44 Adipic acid esters
• CPC Class Codes: C07C 69/46 Pimelic acid esters
• CPC Class Codes: C07C 69/48 Azelaic acid esters
• CPC Class Codes: C07C 69/50 Sebacic acid esters
• CPC Class Codes: C07C 69/704 Citric acid esters
• CPC Class Codes: C07D 307/68 Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• CPC Class Codes: C08F 216/12 by an ether radical
• CPC Class Codes: C08F 222/02 Acids; Metal salts or ammonium salts thereof , e.g. maleic acid or itaconic acid
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 163/08 Epoxidised polymerised polyenes

Abstract

This invention relates to bio-based polyfunctional carboxylic acids reacted with vinyl ether compounds to form liquid vinyl-blocked bio-based polyfunctional carboxylic acids. These liquid vinyl-blocked bio-based polyfunctional carboxylic acids can be mixed with a polyfunctional vegetable oil-based epoxy resin to form a homogeneous curable coating composition. Upon curing at elevated temperature, thermoset coatings are formed which have excellent hardness, solvent resistance, adhesion, and flexibility. The invention also relates to the use of a curable coating composition comprising at least one polyfunctional vegetable oil-based epoxy resin and at least one vinyl-blocked bio-based polyfunctional carboxylic acid, which may be coated onto a substrate and cured thermally. Methods of making the vinyl-blocked bio-based polyfunctional carboxylic acids and curable coating compositions and substrates containing the same are also disclosed.

Claims

1. A vinyl-blocked bio-based polyfunctional carboxylic acid, comprising the reaction product of:

a) at least one bio-based polyfunctional carboxylic acid; and

b) at least one vinyl ether compound.

2. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one bio-based polyfunctional carboxylic acid is selected from dicarboxylic acids, tricarboxylic acids, or mixtures thereof.

3. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one bio-based polyfunctional carboxylic acid is saturated or ethylenically unsaturated.

4. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one bio-based polyfunctional carboxylic acid is optionally substituted.

5. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one bio-based polyfunctional carboxylic acid is aromatic or non-aromatic.

6. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one bio-based polyfunctional carboxylic acid is selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, citric acid, furan dicarboxylic acid, and tartaric acid.

7. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one vinyl ether compound is linear, branched, or cyclic.

8. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said at least one vinyl ether compound is selected from ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and isobutyl vinyl ether.

10. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein the molar ratio of vinyl groups in said at least one vinyl ether compound and carboxylic groups in said at least one bio-based polyfunctional carboxylic acid range from 1.0:

1.0 to 10;

1.

11. The vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, wherein said vinyl-blocked bio-based polyfunctional carboxylic acid is selected from one of the following:

12. A curable coating composition comprising:

a) at least one vinyl-blocked bio-based polyfunctional carboxylic acid compound of claim 1;

b) at least one polyfunctional vegetable oil-based epoxy resin;

c) at least one catalyst;

d) optionally, at least one solvent, at least one other additive, or mixture thereof; and

e) optionally, at least one pigment.

13. The curable coating composition of claim 12, wherein said at least one polyfunctional vegetable oil-based epoxy resin is prepared by the epoxidation of at least one vegetable oil fatty acid ester of a polyol having more than four hydroxyl groups per molecule.

14. The curable coating composition of claim 13, wherein said at least one vegetable oil fatty acid ester of a polyol is prepared by the reaction of at least one polyol with four or more hydroxyl groups per molecule with a mixture of fatty acids or esters of fatty acids with a low molecular weight alcohol.

15. The curable coating composition of claim 14, wherein said polyol with four or more hydroxyl groups per molecule is selected from pentaerythritol, di-trimethylolpropane, di-pentaerythritol, tri-pentaerythritol, sucrose, glucose, mannose, fructose, galactose, and raffinose.

17. The curable coating composition of claim 14, wherein said fatty acids are selected from ethylenically unsaturated fatty acids, saturated fatty acids, or mixtures thereof.

19. The curable coating composition of claim 13, wherein said at least one vegetable oil fatty acid ester of a polyol having more than four hydroxyl groups per molecule is sucrose soyate.

20. The curable coating composition of claim 12, wherein said at least one polyfunctional vegetable oil-based epoxy resin is an epoxidized vegetable oil, vegetable oil-based epoxy resin, or mixture thereof.

24. An object coated with the curable coating composition of claim 12.

25. A method of making a vinyl-blocked bio-based polyfunctional carboxylic acid of claim 1, comprising the step of reacting at least one bio-based polyfunctional carboxylic acid with at least one vinyl ether compound, at least one optional catalyst, and at least one optional solvent.

30. A method of making a curable coating composition of claim 12, comprising the step of mixing at least one vinyl-blocked bio-based polyfunctional carboxylic acid compound with at least one polyfunctional vegetable oil-based epoxy resin.

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