Thermosetting compositions based on unsaturated polyesters and phenolic resins

Patent metadata

Field	Value
Publication number	US-2016115348-A1
Application number	US-201414524514-A
Country	US
Kind code	A1
Filing date	Oct 27, 2014
Priority date	Oct 27, 2014
Publication date	Apr 28, 2016
Grant date	—

Abstract

A thermosetting composition having:
I) an unsaturated curable polyester comprising the residues of an α,β-unsaturated polycarboxylic acid compound, said α,β-unsaturated polycarboxylic acid compound having at least two carboxylic acid groups or at least one anhydride group, and having at least one unsaturation in a position that is α,β relative to a carbonyl group and not located on an aromatic ring; and II) a phenolic resin having at least one methylol group.

The unsaturated curable polyester resin can be dispersed in water or dissolved in a solvent and is suitable for waterborne or solventborne coating compositions. Phenolic based crosslinking coating compositions that contain these unsaturated curable polyester resins are curable at elevated temperatures.

First claim

What we claim is:

1 . A thermosetting composition comprising:
I) an unsaturated curable polyester comprising the residues of an α,β-unsaturated polycarboxylic acid compound, said α,β-unsaturated polycarboxylic acid compound having at least two carboxylic acid groups or at least one anhydride group, and having at least one unsaturation in a position that is α,β relative to a carbonyl group and not located on an aromatic ring; and II) a phenolic resin having at least one methylol group.

2 . The thermosetting composition of claim 1 , comprising:
I) an unsaturated curable polyester comprising the residues of:
a) polyhydroxy compounds comprising:
(i) a diol in an amount of 70 mole %-100 mole %; and
(ii) a polyhydroxyl compound having 3 or more hydroxyl groups in an amount of 0 to 30 mole %;
wherein the mole % is based on 100% of all moles of all polyhydroxyl compounds; and

b) polycarboxylic compounds comprising
(i) an α,β-unsaturated polycarboxylic acid compound; and
(ii) a polycarboxylic acid compound other than the (b)(i) α,β-unsaturated polycarboxylic acid compound.

II) a phenolic resin substituted with at least one methylol group.

3 . The thermosetting composition of claim 1 , wherein at least a portion of the methylol groups are in the ortho position relative to a phenolic hydroxyl group.

4 . The thermosetting composition of claim 1 , wherein the phenolic resin is obtained by the reaction of phenolic compounds and an aldehyde at an aldehyde:phenol ratio of at least 1.1:1.

5 . The thermosetting composition of claim 1 , wherein the phenolic resin has at least one methylol substituent in the ortho position relative to the phenolic hydroxyl group.

6 . The thermosetting composition of claim 1 , wherein the phenolic resin contains an average of one o-methylol substituent per phenolic hydroxyl group.

7 . The thermosetting composition of claim 4 , wherein the phenolic resin is the reaction product of phenolic compounds with formaldehyde.

8 . The thermosetting composition of claim 1 , wherein the phenolic resin is not made by the addition of bisphenol A, F, or S.

9 . The thermosetting composition of claim 1 , wherein the phenolic resin is not made by the addition of a polyhydric phenol.

10 . The thermosetting composition of claim 1 , wherein α,β-unsaturated polycarboxylic acid compound comprises maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anahydride, oxalocitraconic acid, oxalocitraconic anhydride, mesaconic acid, mesaconic anhydride, beta-acylacrylic acid, beta-acylacrylic anhydride, phenyl maleic acid, phenyl maleic anhydride, t-butyl maleic acid, t-butyl maleic anhydride, monomethyl fumarate, monobutyl fumarate, methyl maleic acid, methyl maleic anhydride, or mixtures thereof.

11 . The thermosetting composition of claim 1 , wherein the α,β-unsaturated polycarboxylic acid compound comprises maleic acid or maleic anhydride.

12 . The thermosetting composition of claim 1 , wherein said unsaturated curable polyester contains at least one non-terminal ethylenically unsaturated bond in an α,β position relative to an ester group in the polymer.

13 . The thermosetting composition of claim 1 , wherein the unsaturated curable polyester contains ethylenically unsaturated carbons pendant to the polymer backbone.

14 . The thermosetting composition of claim 1 , wherein the unsaturated curable polyester contains ethylenically unsaturated carbons that are within the linear polymer backbone.

15 . The thermosetting composition of claim 1 , wherein the unsaturated curable polyester does not contain terminal or vinyl unsaturation.

16 . The thermosetting composition of claim 1 , wherein said unsaturated polyester is not made with a monocarboxylic acid compound having a vinyl group.

17 . The thermosetting composition of claim 1 , wherein the unsaturated polyester contains residues of α,β-unsaturated polycarboxylic acid compound in an amount of at least 5 mole % based on the total moles of the components of the polyester.

18 . The thermosetting composition of claim 1 , wherein the unsaturated curable polyester contains residues of α,β-unsaturated polycarboxylic acid compound in an amount of 10 to 25 mole % based on the total moles of the components of the unsaturated curable polyester.

19 . The thermosetting composition of claim 2 , wherein the amount of α,β-unsaturated polycarboxylic acid compound is 30 to 40 mole %, based on 100 mole % of all polycarboxylic compounds (b).

20 . The thermosetting composition of claim 2 , wherein the polycarboxylic acid compounds (bii) comprise isophthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate, phthalic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, succinic anhydride, succinic acid, or mixtures thereof.

21 . The thermosetting composition of claim 20 , wherein the polycarboxylic acid compounds (bii) comprise isophthalic acid, dimethyl isophthalate, phthalic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, adipic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, or mixtures thereof.

22 . The thermosetting composition of claim 2 , wherein the polycarboxylic acid compounds (b)(ii) do not include terephthalic acid or a derivative of terephthalic acid.

23 . The thermosetting composition of claim 1 , wherein the unsaturated polyester contains residues of polycarboxylic compounds, other than α,β-unsaturated polycarboxylic acid compounds, present in an amount of 10 to 25 mole % based on the total moles of the components of the unsaturated curable polyester.

24 . The thermosetting composition of claim 2 , wherein the amount of polycarboxylic compounds (b)(ii) is 50 to 80 mole %, based on 100% of all moles of the polycarboxylic compounds (b).

25 . The thermosetting composition of claim 2 , wherein all of the polyhydroxyl compounds (a) are hydrocarbons and do not contain atoms other than hydrogen, carbon and oxygen.

26 . The thermosetting composition of claim 2 , wherein the diols (a)(i) comprise 2,2,4,4-tetraalkylcyclobutane-1,3-diol (TACD).

27 . The thermosetting composition of claim 2 , wherein the diols (a)(i) comprise 2,2-dimethyl-1,3-propanediol (neopentyl glycol).

28 . The thermosetting composition of claim 2 , wherein the diols (a)(i) are present in an amount of 80 to 98 mole %, based on 100 mole % of all polyhydroxyl compounds (a).

29 . The thermosetting composition of claim 1 , wherein the unsaturated polyester contains residues of the diols in an amount of 37 to 49 mole % based on the total moles of the components of the unsaturated polyester.

30 . The thermosetting composition of claim 2 , wherein the polyhydroxyl compounds comprise polyhydroxyl compounds (a)(ii) having 3 or more hydroxyl groups, said polyhydroxyl compounds (a)(ii) comprising 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, or mixtures thereof.

31 . The thermosett

Assignees

• Eastman Chem Co

Inventors

• Kuo Thauming
• Hall Phillip Bryan

Classifications

• C08J2367/07

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C08J2367/06

  Unsaturated polyesters · CPC title

• C08L67/06

  Unsaturated polyesters · CPC title

• C09D167/06 Primary

  Unsaturated polyesters having carbon-to-carbon unsaturation · CPC title