Formulation methodology for distortional thermosets

Patent metadata

Field	Value
Publication number	US-9938372-B2
Application number	US-201615390844-A
Country	US
Kind code	B2
Filing date	Dec 27, 2016
Priority date	Aug 9, 2013
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Methods and formulations for distortional thermosets are disclosed that display enhanced composite mechanical performances and robust sorption resistance. The composition includes an epoxy resin of formula (I):

and a diamine curing agent. The resultant distortional thermoset compositions possess superior out-life requirements and advantageous reaction kinetics for preparing prepreg compositions and materials.

First claim

What is claimed is:

1. A composition, comprising one or more reaction products of an amount of:
an epoxy resin of formula (I):

and
a first diamine curing agent comprising at least one electron-withdrawing moiety selected from —SO 2 , —SO 3 H, —NO 2 , —CN, —CR 3 , —CHO, and —CO 2 H, wherein R is a halide,
wherein the composition has:
an absorption of methyl ethyl ketone fluid being no more than about 1% by weight after 30 days, and
a von Mises strain of at least 0.300, as determined using a 10 degree lamina coupon.

2. The composition of claim 1 , wherein the epoxy resin of formula (I) is

3. The composition of claim 1 , wherein the epoxy resin of formula (I) is

4. The composition of claim 1 , wherein the epoxy resin of formula (I) is

5. The composition of claim 1 , wherein the epoxy resin of formula (I) is

6. The composition of claim 1 , wherein the epoxy resin of formula (I) is

7. The composition of claim 1 , wherein the epoxy resin of formula (I) is

8. The composition of claim 1 , wherein the epoxy resin of formula (I) is in stoichiometric excess relative to the diamine curing agent.

9. The composition of claim 1 , wherein the diamine curing agent has a Fukui electrophilic index between about 0.04 and about 0.06 by Mulliken-based correlations.

10. The composition of claim 1 , further comprising a second diamine curing agent.

11. The composition of claim 10 , wherein the second diamine curing agent is selected from the group consisting of formulas (II)-(XXV):

and combinations thereof.

12. The composition of claim 10 , wherein the second diamine curing agent is 4,4′-sulfonyldianiline.

13. The composition of claim 10 , wherein the second diamine curing agent has a curing reaction control value between about 1 and about 55 as relative reactivity compared to 4,4′-sulfonyldianiline by Mulliken-based correlations.

14. The composition of claim 10 , wherein the second diamine curing agent has a curing reaction control value between about 1 and about 24 as relative reactivity compared to 4,4′-sulfonyldianiline by Mulliken-based correlations.

15. The composition of claim 14 , wherein the second diamine curing agent has a curing reaction control value between about 1 and about 8 as relative reactivity compared to 4,4′-sulfonyldianiline by Mulliken-based correlations.

16. The composition of claim 15 , wherein the first diamine curing agent has a curing reaction control value between about 24 and about 55 as relative reactivity compared to 4,4′-sulfonyldianiline by Mulliken-based correlations.

17. The composition of claim 10 , wherein the second diamine curing agent comprises at least one electron-withdrawing moiety.

18. The composition of claim 17 , wherein the at least one electron-withdrawing moiety of the second diamine curing agent is selected from the group consisting of: —SO 2 , —SO 3 H, —NO 2 , —CN, —CR 3 , —CHO, and —CO 2 H, wherein R is a halide.

19. The composition of claim 1 , wherein the first diamine curing agent has three ring groups.

20. The composition of claim 10 , wherein the second diamine curing agent is selected from the group consisting of 4,4′-methylenedianiline, 4,4′-oxydianiline, 3,3′-(1,3-phenylenebis(oxy))-dianiline, 4,4′-(1,3-phenylenebis(oxy))-dianiline, 4,4′-methylenebis(2-ethyl-aniline), 3,3′-((2,2-dimethylpropane-1,3-diyl)bis(oxy))dianiline, 4,4′-(1,4-phenylenebis-(propane-2,2-diyl))dianiline, 3-(4-(4-aminobenzyl)-benzyl)aniline, 4,4′-(1,4-phenylenebis(propane-2,2-diyl))bis(2,6-dimethylaniline), 4,4′-(1,4-phenylenebis(oxy))-dianiline, 3,3′-((propane-2,2-diylbis-(4,1-phenylene))bis(oxy))-dianiline, 3,3′-sulfonyldianiline, 4,4′-methylenebis(cyclo-hexan-1-amine), 4,4′-(pentane-1,5-diylbis-(oxy))dianiline, 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))dianiline, 4,4′-(1,3-phenylenebis-(propane-2,2-diyl))bis(2,6-diisopropylaniline), and 4,4′-(1,3-phenylenebis-(propane-2,2-diyl))dianiline.

21. The composition of claim 1 , further comprising one or more fibers.

22. The composition of claim 21 , wherein the one or more fibers is selected from the group consisting of graphite, fiberglass, nylon, aramids, aramid polymers, and polyethylene.

23. The composition of claim 1 , wherein the at least one electron-withdrawing moiety is selected from —SO 3 H, —NO 2 , —CR 3 , —CHO, and —CO 2 H, wherein R is a halide.

Assignees

• Boeing Co

Inventors

• Christensen Stephen
• Tucker Samuel J
• Wiggins Jeffrey S

Classifications

• C08G59/5026

  cycloaliphatic · CPC title

• C08J2377/06

  Polyamides derived from polyamines and polycarboxylic acids (C08J2377/10 takes precedence) · CPC title

• C08L63/00

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

• C08G59/5033 Primary

  aromatic · CPC title

• C08G59/504

  containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen · CPC title