Resole phenolic resins curable with functional polyesters

Patent metadata

Field	Value
Publication number	US-2016115347-A1
Application number	US-201514922846-A
Country	US
Kind code	A1
Filing date	Oct 26, 2015
Priority date	Apr 10, 2015
Publication date	Apr 28, 2016
Grant date	—

Abstract

This invention relates to a resole phenolic resin comprising the residues of
(a) from about 50 to 100 mole % of a meta-substituted phenol [phenolic component (a)], (b) from 0 to about 50 mole % of at least one phenolic component [phenolic component (b)] other than said meta-substituted phenol, and (c) from about 150 to about 300 mole % of at least one aldehyde, wherein the mole percentages of said phenolic components (a) and (b) are based on the total moles of phenolic components (a) and (b); wherein the mole percentages of said aldehyde component is based on the total moles of said phenolic components (a) and (b), and wherein said resole phenolic resin is soluble in an organic solvent and curable with a functional polyester.

First claim

What we claim is:

1 . A resole phenolic resin comprising the residues of
(a) from about 50 to 100 mole % of a meta-substituted phenol [phenolic component (a)], (b) from 0 to about 50 mole % of at least one phenolic component [phenolic component (b)] other than said meta-substituted phenol, and (c) from about 150 to about 300 mole % of at least one aldehyde,
wherein the mole percentages of said phenolic components (a) and (b) are based on the total moles of phenolic components (a) and (b);
wherein the mole percentages of said aldehyde component is based on the total moles of said phenolic components (a) and (b), and
wherein said resole phenolic resin is soluble in an organic solvent and curable with a functional polyester.

2 . The resole phenolic resin of claim 1 , wherein the meta-substituted phenol is one or more selected from the group comprising m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, m-octylphenol, m-alkylphenol, m-phenylphenol, m-alkoxyphenol, 3,5-xylenol, 3,5-diethyl phenol, 3,5-dibutyl phenol, 3,5-dialkylphenol, 3,5-dialkoxyphenol, 3,5-dicyclohexyl phenol, 3,5-dimethoxy phenol, and 3-alkyl-5-alkyoxy phenol.

3 . The resole phenolic resin of claim 1 , wherein the meta-substituted phenol of phenolic compound (a) is m-cresol.

4 . The resole phenolic resin of claim 1 , wherein the phenolic component (b) is ortho-substituted, para-substituted, or unsubstituted phenol, or a mixture thereof.

5 . The resole phenolic resin according to claim 1 or 3 comprising phenolic component (b) which is selected from ortho-substituted, or para-substituted phenol, or a mixture thereof.

6 . The resole phenolic resin of claim 1 , wherein the phenolic component (b) is one or more selected from the group comprising o-cresol, o-ethylphenol, o-propylphenol, o-n-butylphenol, o-t-butyl phenol, o-octylphenol, o-phenylphenol, p-cresol, p-ethylphenol, p-propylphenol, p-n-butylphenol, p-t-butyl phenol, p-octylphenol, p-phenylphenol, 2,3-xylenol, 2,3-diethyl phenol, 2,3-dibutyl phenol, 2,5-xylenol, 2,5-diethyl phenol, 2,5-dibutyl phenol, 3,4-xylenol, 3,4-diethyl phenol, and 3,4-dibutyl phenol.

7 . The resole phenolic resin of claim 1 , wherein the phenolic component (b) is selected from o-cresol, p-cresol, and a mixture thereof.

8 . The resole phenolic resin of claim 1 , wherein the aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, benzaldehyde, and a mixture thereof.

9 . The resole phenolic resin of claim 1 , wherein the aldehyde is formaldehyde.

10 . The resole phenolic resin of claim 1 , which is soluble in one or more organic solvents selected from the group comprising xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, Aromatic 100 Fluid (ExxonMobil), and Aromatic 150 Fluid (ExxonMobil).

11 . The resole phenolic resin of claim 1 , wherein the meta-substituted phenol (a) is present in the amount of from 70 to 100 mole % and the phenolic component (b) is present in the amount of from 0 to 30 mole %.

12 . The resole phenolic resin of claim 1 , wherein the meta-substituted phenol (a) is present in the amount of from 90 to 100 mole % and the phenolic component (b) is present in the amount of from 0 to 10 mole %.

13 . The resole phenolic resin of claim 1 , wherein the meta-substituted phenol (a) is present in the amount of 100 mole %.

14 . The resole phenolic resin of claim 1 , wherein the aldehyde is present in the amount of from 170 to 270 mole % of an aldehyde, based on the total moles of phenolic components, (a) and (b).

15 . The resole phenolic resin of claim 1 , which contains an average of at least 0.5 methylol groups (including either or both of —CH 2 OH and —CH 2 OR) per one phenolic hydroxyl group.

16 . The resole phenolic resin of claim 1 , which contains an average of at least 0.7 methylol groups (including either or both of —CH 2 OH and —CH 2 OR) per one phenolic hydroxyl group.

17 . The resole phenolic resin of claim 1 , wherein the functional polyester has a functionality selected from hydroxyl, carboxyl, α,β-unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, maleimide, and a combination thereof.

18 . A thermosetting composition comprising:
I) the resole phenolic resin of claim 1 and II) a curable polyester which has one or more functionalities selected from the group comprising hydroxyl, carboxyl, α,β-unsaturated dicarboxylate, beta-ketoacetate, carbamate, phenol, amino, and maleimide groups.

19 . The thermosetting composition of claim 18 further comprising one or more acid catalysts selected from the group comprising p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid, and phosphoric acid.

20 . The thermosetting composition of claim 18 further comprising phosphoric acid catalyst.

21 . The thermosetting composition of claim 18 further comprising phosphoric acid catalyst in an amount ranging from 0.8 to 1.2 weight % based on the total weight of the resole phenolic resin (I) and the curable polyester (II).

22 . The thermosetting composition of claim 18 , wherein the resole phenolic resin (I) is present in an amount from 20 to 50 weight % and the curable polyester (II) is from 50 to 80 weight % based on the total weight of (I) and (II).

23 . The thermosetting composition of claim 18 , wherein the curable polyester has a cumulative hydroxyl number and acid number in a range of 3 to 280 mg KOH/g.

24 . The thermosetting composition of claim 18 , wherein the curable polyester has a cumulative hydroxyl number and acid number in a range of 30 to 150 mg KOH/g.

25 . The thermosetting composition of claim 18 , wherein the curable polyester has a hydroxyl number ranging from 30 to 150 mg KOH/g.

26 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising α,β-unsaturated dicarboxylate group.

27 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising beta-ketoacetate group.

28 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising carbamate group.

29 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising phenol group.

30 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising amino group.

31 . The thermosetting composition of claim 18 , wherein the curable polyester has functionalities comprising maleimide group.

32 . The thermosetting composition of claim 18 , wherein the curable polyester comprises the residues of
a) polyhydroxyl compounds comprising:
(i) diol compounds in the amount of 70 mole % to 100 mole and
(ii) polyhydroxyl compounds having 3 or more hydroxyl groups in the amount of 0 to 30 mole %,
wherein

Assignees

• Eastman Chem Co

Inventors

• Kuo Thauming
• Liu Junjia
• Hall Phillip Bryan

Classifications

• C08G8/08 Primary

  of formaldehyde, e.g. of formaldehyde formed in situ · CPC title

• C08L2201/56

  Non-aqueous solutions or dispersions · CPC title

• C08L61/06 Primary

  of aldehydes with phenols · CPC title

• C08L2201/54

  Aqueous solutions or dispersions · CPC title

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title