Shape memory epoxy materials using aromatic alcohol cure agents
View Patent ↗Embodiments of the present disclosure are directed to a cured epoxy shape memory material by reacting a mixture comprising multifunctional epoxide reagent, triglycidyl ether diluent, catalyst, and at least one aromatic alcohol curing agent of Formula I: wherein R1 and R5 are H, alkyl, aryl, or alkoxy, but not —CH 2 OH and R2, R3 or R4 are H, OH, alkyl, aryl, alkoxy or —Y—OH with the proviso that at least one of R2, R3 or R4 is —Y—OH, wherein Y is an alkylene.
1. A method of making a cured epoxy shape memory material comprising: producing the cured epoxy shape memory material by reacting a mixture comprising: multifunctional epoxide reagent; a triglycidyl ether diluent different from said multifunctional epoxide reagent; and at least one aromatic alcohol curing agent of Formula I, in the presence of a catalyst:
wherein:
each of R1 and R5 is independently H, alkyl, aryl, or alkoxy, but not —CH 2 OH; and
each of R2, R3 and R4 is independently H, OH, alkyl, aryl, alkoxy or —Y—OH with the proviso that at least one of R2, R3 and R4 is —Y—OH, wherein Y is an alkylene.
2. The method of claim 1 wherein Y is —CH 2 .
3. The method of claim 1 wherein at least one of R1 and R5 is an alkoxy.
4. The method of claim 1 wherein R3 is —Y—OH.
5. The method of claim 1 wherein Formula I is chosen from:
or combinations thereof.
6. The method of claim 1 wherein the cured epoxy shape memory material has a glass transition temperature (Tg) of 60° C. or below.
7. The method of claim 1 wherein the mixture comprises 30-99% by wt of multifunctional epoxide, 0.1-20% by wt of triglycidyl ether diluent, 1-30% by wt of the aromatic alcohol curing agent of Formula I, and 0.1-10% by wt. of the catalyst.
8. The method of claim 1 wherein the mixture comprises 10-25% by wt of the aromatic alcohol curing agent of Formula I.
9. The method of claim 1 wherein the catalyst is selected from the group consisting of: bis(triphenylphosphoranylidene)ammonium chloride, bis(triphenylphosphoranylidene)ammonium bromide, bis(triphenylphosphoranylidene)ammonium acetate, and combinations thereof.
10. The method of claim 1 wherein the multifunctional epoxide reagent is at least one diglycidyl ether of a compound selected from the group consisting of resorcinol, hydroquinone, 4,4′-isopropylidene bisphenol (bisphenol A), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bisphenol F), 4,4′-sulfonyldiphenol (bisphenol S), 4,4′-(9-fluorenylidene)diphenol, 4,4′-dihydroxydiphenylethylmethane, 3,3′-dihydroxydiphenyldiethylmethane, 3,4′-dihydroxydiphenylmethylpropylmethane, 4,4′-dihydroxydiphenyloxide, 4,4′-dihydroxydiphenylcyanomethane, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybenzophenone (bisphenol K), 4,4′-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, catechol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, and ethylene glycol.
11. The method of claim 1 wherein the triglycidyl ether diluent is selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylol ethane triglycidyl ether, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerine triglycidyl ether, and combinations thereof.
12. The method of claim 1 wherein the mixture further comprises additional curing agent.
13. The method of claim 1 , wherein the cured epoxy shape memory material has elongation of about 300 to about 600% at a temperature of 120° C.
14. A cured epoxy shape memory material comprising: a cured mixture of multifunctional epoxide reagent; a triglycidyl ether diluent different from said multifunctional epoxide reagent; and at least one aromatic alcohol curing agent of Formula I:
wherein:
each of R1 and R5 is independently H, alkyl, aryl, or alkoxy, but not CH 2 OH; and
each of R2, R3 and R4 is independently H, OH, alkyl, aryl, alkoxy or —Y—OH with the proviso that at least one of R2, R3 and R4 is —Y—OH, wherein Y is an alkylene.
15. The cured epoxy shape memory material of claim 14 wherein Y is —CH 2 .
16. The cured epoxy shape memory material of claim 14 wherein the cured epoxy shape memory copolymer material has a glass transition temperature (Tg) of 60° C. or below.
17. The cured epoxy shape memory material of claim 14 wherein at least one of R1 and R5 is an alkoxy.
18. The cured epoxy shape memory material of claim 14 wherein R3 is —CH 2 OH.
19. The cured epoxy shape memory material of claim 14 wherein Formula I is chosen from:
or combinations thereof.
20. The cured epoxy shape memory material of claim 14 wherein the mixture comprises 30-99% by wt of multifunctional epoxide, 0.1-20% by wt of triglycidyl ether diluent, and 1-30% by wt of the aromatic alcohol curing agent of Formula I.
21. The cured epoxy shape memory material of claim 14 wherein the mixture comprises 10-25% by wt of an alcohol curing agent of Formula I.
22. The cured epoxy shape memory material of claim 14 wherein the mixture is cured in the presence of a catalyst selected from the group consisting of bis(triphenylphosphoranylidene) ammonium chloride, bis(triphenylphosphoranylidene)ammonium bromide, bis(triphenylphosphoranylidene)ammonium acetate, and combinations thereof.
23. The cured epoxy shape memory material of claim 14 wherein the multifunctional epoxide reagent is at least one diglycidyl ether of a compound selected from the group consisting of resorcinol, hydroquinone, 4,4′-isopropylidene bisphenol (bisphenol A), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bisphenol F), 4,4′-sulfonyldiphenol (bisphenol S), 4,4′-(9-fluorenylidene)diphenol, 4,4′-dihydroxydiphenylethylmethane, 3,3′-dihydroxydiphenyldiethylmethane, 3,4′-dihydroxydiphenylmethylpropylmethane, 4,4′-dihydroxydiphenyloxide, 4,4′-dihydroxydiphenylcyanomethane, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybenzophenone (bisphenol K), 4,4′-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, catechol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, and ethylene glycol.
24. The cured epoxy shape memory material of claim 14 wherein the triglycidyl ether diluent is selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylol ethane triglycidyl ether, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerine triglycidyl ether, and combinations thereof.
25. The cured epoxy shape memory material of claim 14 wherein the mixture further comprises additional curing agent.
26. A composite mandrel comprising the cured epoxy shape memory material of claim 14 .
27. The cured epoxy shape memory material of claim 14 , wherein the epoxy shape memory material has elongation of about 300 to about 600% at a temperature of 120° C.