Rapid curing thiol epoxy resin with improved compression strength performance

Patent metadata

Field	Value
Publication number	US-10035873-B2
Application number	US-201715449093-A
Country	US
Kind code	B2
Filing date	Mar 3, 2017
Priority date	Nov 3, 2015
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

Aspects described herein generally describe epoxy resins and methods of epoxy resin formation. In some embodiments, a resin includes the reaction product of one or more polythiols, one or more polyepoxides, one or more fillers and one or more amine catalysts. Polythiols have between two and about ten thiol moieties. Polyepoxides have between two and about ten epoxy moieties. One or more amine catalysts of the formula NR 1 R 2 R 3 , wherein each of R 1 , R 2 , and R 3 is independently linear or branched C1-20 alkyl or two or more of R 1 , R 2 , and R 3 combine to form cycloalkyl. The resin has a compressive strength of at least 14 ksi at 2% offset at 70° F. and at least 8 ksi at 2% offset at 190° F.

First claim

What is claimed is:

1. A resin that is the reaction product of:
one or more polythiols having between two and about ten thiol moieties;
one or more polyepoxides having between two and about ten epoxy moieties at a molar ratio of polyepoxides to polythiols of about 0.9; and
one or more amine catalysts of the formula NR 1 R 2 R 3 , wherein each of R 1 , R 2 , and R 3 is independently linear or branched C1-20 alkyl or two or more of R 1 , R 2 , and R 3 combine to form cycloalkyl.

2. The resin of claim 1 , wherein the resin has a compressive strength of at least 14 ksi at 2% offset at 70° F. and at least 8 ksi at 2% offset at 190° F.

3. The resin of claim 1 , further comprising one or more solid particulate fillers.

4. The resin of claim 3 , wherein the one or more solid particulate fillers is between about 50% wt to about 55% wt of the resin.

5. The resin of claim 1 , wherein at least one of the one or more polythiols is of the formula SH—R—SH, wherein R is selected from the group consisting of alkyl, cycloalkyl, thiol-substituted alkyl, and thiol-substituted cycloalkyl.

6. The resin of claim 1 , wherein each instance of the polythiol is independently selected from the group consisting of 1,2,3-propanetrithiol, 1,2,4-tris(2-mercaptoethyl) cyclohexane, and 1,3,5-tris(2-mercaptoethyl) cyclohexane.

7. The resin of claim 1 , wherein each instance of the solid particulate fillers is independently selected from the group consisting of crystalline silica, fumed silica, methylated fumed silica, alumina, mica, silicate, talc, aluminosilicate, barium sulfate, diatomite, calcium carbonate, calcium sulfate, carbon, and wollastonite.

8. The resin of claim 1 , wherein each instance of the one or more amine catalysts is independently selected from the group consisting of diisopropylethylamine, N-alkyl-piperidine, N-alkyl-piperazine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, trimethylamine, triethylamine, tripropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylpentylamine, N,N-dimethylhexylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dim ethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-dimethyleicosylamine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-diethylpentylamine, N,N-diethylhexylamine, N,N-diethylheptylamine, N,N-diethyloctylamine, N,N-diethylnonylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N,N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethyltetradecylamine, N,N-diethylpentadecylamine, N,N-diethylhexadecylamine, N,N-diethylheptadecylamine, N,N-diethyloctadecylamine, N, N-diethylnonadecylamine, N,N-diethyleicosylamine, N,N-dipropylbutylamine, N,N-dipropylpentylamine, N,N-dipropylhexylamine, N,N-dipropylheptylamine, N,N-dipropyloctylamine, N,N-dipropylnonylamine, N,N-dipropyldecylamine, N,N-dipropylundecylamine, N,N-dipropyldodecylamine, N,N-dipropyltridecylamine, N,N-dipropyltetradecylamine, N,N-dipropylpentadecylamine, N,N-dipropylhexadecylamine, N,N-dipropylheptadecylamine, N,N-dipropyloctadecylamine, N,N-dipropylnonadecylamine, and N,N-dipropyleicosylamine.

9. The resin of claim 8 , wherein the one or more amine catalysts is N,N-dimethyltetradecylamine.

10. The resin of claim 1 , wherein the one or more amine catalysts is a salt.

11. The resin of claim 1 , wherein the one or more amine catalysts is between about 0.1% wt to about 10% wt of the resin.

12. The resin of claim 1 , wherein the one or more amine catalysts is between about 1% wt to about 3% wt of the resin.

13. The resin of claim 1 , wherein at least one of the one or more polyepoxides has between four and about ten epoxy moieties.

14. The resin of claim 1 , wherein each instance of the one or more polyepoxides is independently selected from the group consisting of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, poly[(phenyl glycidyl ether)-codicyclopentadiene], tetraphenylolethane glycidyl ether, and tris(4-hydroxyphenyl)methane triglycidyl ether.

15. The resin of claim 14 , wherein at least one of the one or more polyepoxides is tetraphenylolethane glycidyl ether or tris(4-hydroxyphenyl)methane triglycidyl ether.

16. The resin of claim 14 , wherein the one or more amine catalysts is N,N-dimethyltetradecylamine.

17. A resin that is the reaction product of:
a polythiol having an equivalent molecular weight of between about 20 to about 115; and
a polyepoxide having between four and about ten epoxy moieties;
a solid particulate filler;
wherein the resin has a compressive strength of at least 14 ksi at 2% offset at 70° F. and at least 8 ksi at 2% offset at 190° F.

18. The resin of claim 17 , wherein the molar ratio of polyepoxide to polythiol is about 0.9.

19. The resin of claim 17 , wherein the polythiol is 1,2,4-tris(2-mercaptoethyl)cyclohexane and the polyepoxide is of the formula:

20. A composition comprising:
one or more polythiols having between two and about ten thiol moieties; and
one or more polyepoxides having between two and about ten epoxy moieties at a molar ratio of polyepoxides to polythiols of about 0.9.

21. The composition of claim 20 , further comprising a solid particulate filler.

22. The composition of claim 21 , further comprising an amine catalyst.

Assignees

• Boeing Co

Inventors

• Nowak Andrew Paul
• RODRIGUEZ April Rose
• Boundy Thomas Ian
• Pajel Carissa Ann
• Adjorlolo Alain A

Classifications

• C08J2363/00

  Characterised by the use of epoxy resins; Derivatives of epoxy resins · CPC title

• C08G59/686

  containing nitrogen · CPC title

• C08G59/66

  Mercaptans · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08G59/10 Primary

  of polyamines with epihalohydrins or precursors thereof · CPC title