Compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility
View Patent ↗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.
1. A condensation product of a reaction mixture, comprising:
a triazine monomer;
an arylhydroxy monomer selected from the group consisting of phenol, xylenols, bisphenols, alkylated bisphenols, alkoxyphenols, dihydroxy benzene, naphthols, biphenols, alkylated biphenols, trisphenols, and combinations thereof;
an aldehyde monomer; and
an acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises an organic acid selected from the group of benzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, ethylbenzoic acid, hexahydrobenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, iso-propylbenzoic acid, meta-toluic acid, para-toluic acid, 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.
2. 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.
3. The condensation product of claim 2 , wherein the the reaction mixture comprises from 0.1 wt. % to 2 wt. % of the reaction mixture of the stabilizer.
4. The condensation product of claim 2 , wherein the cresol comprises o-cresol, p-cresol, or combinations thereof.
5. 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
from greater than 0.1 wt. % to less than 1 wt. %, based on the weight of the arylhydroxy monomer, of the acid catalyst.
6. The condensation product of claim 1 , wherein the condensation product maintains a Gardner number of less than 3 for 150 days or greater.
7. 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.
8. 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.
9. The condensation product of claim 1 , wherein the triazine monomer and the aldehyde monomer comprise an aldehyde modified triazine monomer.
10. The condensation product of claim 1 , wherein the reaction mixture further comprises 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.
11. A method for the preparation of the condensation product of claim 1 , comprising:
charging to a reaction vessel to form a reaction mixture:
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; and
heating the reaction mixture to a temperature of about 120° C. to about 165° C. and substantially completing reaction of the arylhydroxy monomer in the reaction mixture.
12. The method of claim 11 , wherein the triazine monomer and the aldehyde monomer comprise an aldehyde modified triazine monomer.
13. The method of claim 12 , wherein the aldehyde modified triazine monomer comprises hexamethoxymethylmelamine.
14. The method of claim 11 , further comprising charging a stabilizer or one or more organic solvents selected from the group consisting of cresol, N-methyl pyrrolidone, hydroquinone, triethylcitrate, butyrolactone, glycerol, and combinations thereof.
15. The method of claim 11 , further comprising charging a base catalyst to the reaction vessel before heating the reaction mixture.
16. 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.
17. 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 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; and
an acid catalyst having a pKa value range from 4 to 6, wherein the acid catalyst comprises an organic acid selected from the group of benzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, ethylbenzoic acid, hexahydrobenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, iso-propylbenzoic acid, meta-toluic acid, para-toluic acid, 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.
18. The epoxy resin composition of claim 17 , wherein the epoxy resin composition is free of a separate amine catalyst or a phosphorous containing catalyst.
19. The epoxy resin composition of claim 17 , 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.
20. The epoxy resin composition of claim 19 , wherein the cresol comprises o-cresol, p-cresol, or combinations thereof.
21. The epoxy resin composition of claim 17 , 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
from greater than 0.1 wt. % to less than 1 wt. %, based on the weight of the arylhydroxy monomer, of the acid catalyst.
22. The epoxy resin composition of claim 17 , 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.
23. The epoxy resin composition of claim 17 , 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.
24. The epoxy resin composition of claim 17 , 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.