BIOBASED HYDROXYL OR CARBOXYL POLYESTER RESINS

• US 20170291989A1
• Filed: 09/10/2015
• Published: 10/12/2017
• Est. Priority Date: 09/12/2014
• Status: Active Grant

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Delmas, Gregory A., Cogordan, Frank, Ozeray, Herve W., Riondel, Alain F.
• Granted Patent: US 10,457,771 B2
• Time in Patent Office: Days
• CPC Class Codes: C08G 63/12 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/16 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/668 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/672 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C09D 167/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C09D167/06 takes precedence

Abstract

The present invention relates to a linear or branched structured hydroxylated or carboxylated polyester resin that is free of unsaturated fatty acids, that is made from an acid component and an alcohol component, said acid component comprising at least one C4 to C6 carboxylic polyacid or anhydride, and at least one C5 to C54 carboxylic polyacid or anhydride, and with said alcohol component comprising at least one biobased polyol having a functionality of at least 2 bearing a 1,4:3,6-dianhydrohexitol unit, and at least one of two polyols b2) and b3).

Claims

1. A polyester resin having a linear or branched structure and free of unsaturated fatty acids, which is hydroxylated or carboxylated, optionally hydroxylated and carboxylated, which is derived from:

a) an acid component a) comprising;

a1) at least one C₄ to C6 polycarboxylic acid or anhydride,

a2) at least one C₈ to C54 polycarboxylic acid or anhydride,

a3) optionally, at least one C₂ to C₂₂ saturated monoacid, which can optionally bear a hydroxyl group,

b) an alcohol component b) comprising;

b1) at least one biobased polyol having a functionality f_b1 of at least 2, bearing a 1,4;

3,6-dianhydrohexitol unit,

and at least one of the following two polyols b2) and b3);

b2) at least one polyol different than b1) and having a functionality f_b2 of at least 2,

b3) at least one polyol different than b1) and than b2) having a functionality f_b3 of at least 3.

2. The resin of claim 1, wherein said unit of polyol b1) is isosorbide (1,4:

3,6-dianhydro-D-sorbitol), isomannide (1,4;

3,6-dianhydro-D-mannitol) or isoidide (1,4;

3,6-dianhydro-L-iditol).

3. The resin of claim 1 wherein a fraction of at least 50%, by weight of said resin is biobased.

4. The resin of claim 1 wherein said component b) comprises b2) and b3) and that at least 50% by weight, of said component b) is biobased.

5. The resin of claim 1 wherein the components a) and b) are 100% biobased.

6. The resin of claim 1 wherein said polyol b2) is biobased and is chosen from the group consisting of 1,3-propylenediol, 1,2-propylenediol, 1,4-butanediol, and diols derived from saturated fatty acids.

7. The resin of claim 1 wherein said polyol b3) is biobased and chosen from glycerol and ether-polyol derivatives thereof.

8. The resin of claim 1 wherein said polyacid a1) is a biobased aliphatic diacid chosen from the group consisting of succinic acid, tartaric acid, citric acid, malic acid, itaconic acid, glutaric acid, glutamic acid, fumaric acid, furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid and tetrahydrofuran-3,5-dicarboxylic acid.

9. The resin of claim 1 wherein said polyacid a2) is biobased and chosen from the group consisting of azelaic acid (C₉), sebacic acid (C₁₀), undecanedioic acid, dodecanedioic acid, and respectively C₃₆ and C₅₄ fatty acid dimers and trimers.

10. The resin of claim 1 wherein said monoacid a3) is present in the composition of said resin and selected from the group consisting of acetic acid, pyruvic acid, lactic acid or rosin (meaning abietic acid and C₂₀ isomers), and a C₁₂ to C₂₂ saturated fatty acid.

11. The resin of claim 1 wherein said polyol b1) represents at least 30% by weight of said resin.

12. The resin of claim 1 having an OH and/or carboxylic acid functionality corresponding to an OH and/or acid number ranging from 10 to 200 mg KOH/g.

13. The resin of claim 1 having a carboxyl functionality corresponding to an acid number of less than 20 mg KOH/g and an OH functionality corresponding to an OH number ranging from 10 to 200 mg KOH/g.

14. The resin of claim 1 having a number-average molecular weight Mn ranging from 500 to 20 000.

15. The resin of claim 1 having a Tg ranging from −

10°

C. to 100°

C.

16. A solution of resin in an organic solvent, comprising at least one resin of claim 1.

17. The solution of claim 16 wherein said solvent is selected from the group consisting of methyl esters and ethyl esters of C₂ to C₄ monocarboxylic acids, esters of said monocarboxylic acids with methoxy or ethoxy monoethers of C₂ to C₄ diols, methyl and ethyl diesters of C₄ to C₆ dicarboxylic acids, terpenes, polyhydroxyalkanoates, methyl and ethyl esters of fatty acid oils, and esters of lactic acid with C₁ to C₈ alcohols.

18. A coating composition comprising at least one resin of claim 1.

19. The coating composition of claim 18 which is a crosslinkable composition comprising, in addition to said resin, at least one crosslinking agent, bearing groups which are reactive with the hydroxyl and/or carboxyl groups borne by said resin.

20. The coating composition of claim 18 wherein said crosslinking agent is selected from the group consisting of melamine, polyisocyanate, polyanhydride, and polysilane, when said resin is hydroxylated, or said crosslinking agent is selected from the group consisting of polyepoxides and polyols when said resin is carboxylated.

21. The composition of claim 17 which is a coating composition in an organic solvent medium which is a paint or varnish composition.

28. The resin of claim 1, wherein said at least one C₄ to C₆ polycarboxylic acid or anhydride has a functionality f_a1 ranging from 2 to 4 and the at least one C₈ to C₅₄ polycarboxylic acid or anhydride has a functionality f_a2 ranging from 2 to 4.

29. The resin of claim 1, wherein the said polyol b2) is a polyol in C₃-C_36.

30. The resin of claim 1, wherein f_a1=2, fa₂=2, f_b1=2, and f_b2=2 and f_b3=3.

22. (canceled)

23. (canceled)

24. (canceled)

25. (canceled)

26. (canceled)

27. (canceled)