Novel compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility

Patent metadata

Field	Value
Publication number	US-2016168306-A1
Application number	US-201514973265-A
Country	US
Kind code	A1
Filing date	Dec 17, 2015
Priority date	Aug 17, 2010
Publication date	Jun 16, 2016
Grant date	—

Abstract

Compositions and methods for forming condensates and resin compositions are provided. In one embodiment, a condensate is formed from a reaction mixture including a triazine monomer, an arylhydroxy monomer, an aldehyde monomer and an acid catalyst having a pKa value of greater than 3.8. The condensates contain up to 28 wt. % of nitrogen and have a melt viscosity of 3,000 cps or less at 175° C. The condensates may have a solubility of at least 80 wt. % solids dissolved in an organic solvent for 120 hours or greater. Also disclosed are methods for the manufacture of the condensate as well as the condensate's use in fire-retardant epoxy resin compositions suitable for the manufacture of laminates for electronic applications. There is also disclosed a glycidylated triazine-arylhydroxy-aldehyde condensate of this invention.

First claim

1 . A condensation product of a reaction mixture, comprising:
a triazine monomer; an arylhydroxy monomer selected from the group consisting of phenol, xylenols, bis-phenols, alkylated bisphenols, alkoxyphenols, dihydroxy benzene, naphthols, biphenols, alkylated biphenols, trisphenols, and combinations thereof; an aldehyde monomer; an acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises an organic acid, wherein the condensation product comprises greater than 10 wt. % to about 28 wt. % of nitrogen and a melt viscosity from about 1100 cps to less than 3,000 cps at 175° C.

2 . The condensation product of claim 1 , wherein the organic acid is selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, and combinations thereof.

3 . The condensation product of claim 2 , wherein the organic acid is selected from the group consisting of acetic acid, adipic acid, ascorbic acid, benzoic acid, cinnamic acid, adipamic acid, o-aminobenzoic acid, p-aminobenzoic acid, anisic acid, anisylpropionic acid, barbituric acid, butyric acid, isobutyric acid, caproic acid, isocapropic acid, chlorobutyric acid, chlorocinnamic acid, chlorophenylacetic acid, (chlorophenyl)propionic acid, trans-cinnamic acid, trans-crotonic acid, dihydroxybenzoic acid (3,4 and 3,5), ethylbenzoic acid, ethylphenylacetic acid, trans-furmaric acid, gallic acid, glutaramic acid, heptanoic acid, hexahydrobenzoic acid, hexanoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, hydroxybutyric acid, mesitylenic acid, naphthoic acid, o-nitrophenylacetic acid, nonanic acid, octanoic acid, phenylacetic acid, propionic acid, iso-propylbenzoic acid, pyridinecarboxylic acid, suberic acid, toluic acid (meta and para), trimethylacetic acid, valeric acid, vinylacetic acid, succinic acid, glutaric acid, methylsuccinic acid, and combinations thereof.

4 . The condensation product of claim 1 , wherein the reaction mixture comprises:
the triazine monomer; from about 3 to about 30 moles of the arylhydroxy monomer for each mole of the triazine monomer; from about 1 to about 6 moles of the aldehyde monomer for each mole of the triazine monomer; and the acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises from greater than 0.1 wt. % to less than 1 wt. % based on the weight of the arylhydroxy monomer.

5 . The condensation product of claim 1 , wherein the condensation product maintains a Gardner number of less than 3 for 150 days or greater.

6 . The condensation product of claim 1 , wherein the condensation product comprises a melt viscosity from about 1100 cps to about 1700 cps at 175° C.

7 . The condensation product of claim 1 , wherein the triazine monomer comprises a structure having the formula:

wherein R 1 and R 2 are each independently a hydrogen atom or a functional group selected from the group consisting of an amino group, an alkyl group having 1 to 4 carbon atoms, phenyl group, a vinyl group, and combinations thereof.

8 . The condensation product of claim 1 , wherein the triazine monomer and the aldehyde monomer comprise an aldehyde modified triazine monomer.

9 . The condensation product of claim 1 , wherein the condensation product comprises a solubility from about 33% to at least about 80 wt. % solids dissolved for 120 hours or greater in one or more organic solvents having one or more functionalities selected from the group consisting of an ether functionality, a ketone functionality, an alcohol functionality, an ester functionality, and combinations thereof.

10 . The condensation product of claim 1 , wherein the reaction mixture further comprises a stabilizer selected from the group consisting of cresol, N-methyl pyrrolidone, hydroquinone, triethylcitrate, butyrolactone, glycerol, and combinations thereof.

11 . A flame-retardant epoxy resin composition, comprising:
an epoxy resin; and a condensation product of a reaction mixture comprising:
a triazine monomer;
an arylhydroxy monomer;
an aldehyde monomer;
an acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises an organic acid; and
a stabilizer of a non-reactive diluent selected from the group consisting of esters, hydroxyaryl moieties, dihydroxyaryl moieties, amides, alcohols, ketones, and combinations thereof, wherein the condensation product comprises greater than 10 wt. % to about 28 wt. % of nitrogen and a melt viscosity from about 1100 cps to less than 3,000 cps at 175° C.

12 . The epoxy resin composition of claim 11 , wherein the epoxy resin composition is free of a separate amine catalyst or a phosphorous containing catalyst.

13 . The epoxy resin composition of claim 11 , further comprising a phenolic-formaldehyde novolac curing agent selected from the group consisting of phenol novolac, cresol novolac, naphthol novolac, bisphenol A novolac, phenol-glyoxal condensate, and combinations thereof and co-polymers thereof.

14 . The epoxy resin composition of claim 11 , wherein the organic acid is selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, and combinations thereof.

15 . The epoxy resin composition of claim 14 , wherein the organic acid is selected from the group consisting of acetic acid, adipic acid, ascorbic acid, benzoic acid, cinnamic acid, adipamic acid, o-aminobenzoic acid, p-aminobenzoic acid, anisic acid, anisylpropionic acid, barbituric acid, butyric acid, isobutyric acid, caproic acid, isocapropic acid, chlorobutyric acid, chlorocinnamic acid, chlorophenylacetic acid, (chlorophenyl)propionic acid, trans-cinnamic acid, trans-crotonic acid, dihydroxybenzoic acid (3,4 and 3,5), ethylbenzoic acid, ethylphenylacetic acid, trans-furmaric acid, gallic acid, glutaramic acid, heptanoic acid, hexahydrobenzoic acid, hexanoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, hydroxybutyric acid, mesitylenic acid, naphthoic acid, o-nitrophenylacetic acid, nonanic acid, octanoic acid, phenylacetic acid, propionic acid, iso-propylbenzoic acid, pyridinecarboxylic acid, suberic acid, toluic acid (meta and para), trimethylacetic acid, valeric acid, vinylacetic acid, succinic acid, glutaric acid, methylsuccinic acid, and combinations thereof.

16 . The epoxy resin composition of claim 11 , wherein the reaction mixture comprises:
the triazine monomer; from about 3 to about 30 moles of the arylhydroxy monomer for each mole of the triazine monomer; from about 1 to about 6 moles of the aldehyde monomer for each mole of the triazine monomer; and the acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises from greater than 0.1 wt. % to less than 1 wt. % based on the weight of the arylhydroxy monomer.

17 . The epoxy resin composition of claim 11 , wherein the triazine monomer comprises a structure having the formula:

wherein R 1 and R 2 are each independently a hydrogen atom or a functional group selected from the group consisting of an amino group, an alkyl group having 1 to 4 carbon atoms, phenyl group, a vinyl group, and combinations thereof.

18 . The epoxy resin composition of claim 11 , wherein the reaction mixture further comprises a stabilizer selected from the group consisting of cresol, N-methyl pyrrolidone, hydroquinone, triethylcitrate, butyrolactone, glycerol, and combinations thereof.

19 . The

Assignees

• Hexion Inc

Inventors

• Viswanathan Ganapathy S
• Malhotra Vinay

Classifications

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08G14/10 Primary

  Melamines · CPC title

• C08K5/05

  Alcohols; Metal alcoholates · CPC title

• C08G59/68

  characterised by the catalysts used · CPC title

• C08L61/34

  Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20 · CPC title