# US 9,434,810 B2 · Shape memory epoxy materials using aromatic alcohol cure agents

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- Number: US 9,434,810 B2
- Document ID: US9434810B2
- Status: Granted
- Kind: B2
- Application number: 14/450,995
- Filed: 2014-08-04
- Published: 2014-11-20
- Granted: 2016-09-06
- Earliest claimed: 2013-08-02
- Assignees: Spirit AeroSystems, Inc.
- Applicants: Spirit AeroSystems, Inc.
- Inventors: Teresa Havens
- Web page: https://patentgrep.com/patent/US9434810B2

## CPC

- C08G 59/022: {characterised by the preparation process or apparatus used}
- C08G 59/621: {Phenols}
- C08G 59/68: characterised by the catalysts used
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

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 —CH2OH 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.

## Claims

### Claim 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 —CH2OH; 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.

### Claim 2 (depends on 1)

The method of claim 1 wherein Y is —CH2.

### Claim 3 (depends on 1)

The method of claim 1 wherein at least one of R1 and R5 is an alkoxy.

### Claim 4 (depends on 1)

The method of claim 1 wherein R3 is —Y—OH.

### Claim 5 (depends on 1)

The method of claim 1 wherein Formula I is chosen from:
or combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1 wherein the cured epoxy shape memory material has a glass transition temperature (Tg) of 60° C. or below.

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

The method of claim 1 wherein the mixture comprises 10-25% by wt of the aromatic alcohol curing agent of Formula I.

### Claim 9 (depends on 1)

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.

### Claim 10 (depends on 1)

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.

### Claim 11 (depends on 1)

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.

### Claim 12 (depends on 1)

The method of claim 1 wherein the mixture further comprises additional curing agent.

### Claim 13 (depends on 1)

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.

### Claim 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 CH2OH; 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.

### Claim 15 (depends on 14)

The cured epoxy shape memory material of claim 14 wherein Y is —CH2.

### Claim 16 (depends on 14)

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.

### Claim 17 (depends on 14)

The cured epoxy shape memory material of claim 14 wherein at least one of R1 and R5 is an alkoxy.

### Claim 18 (depends on 14)

The cured epoxy shape memory material of claim 14 wherein R3 is —CH2OH.

### Claim 19 (depends on 14)

The cured epoxy shape memory material of claim 14 wherein Formula I is chosen from:
or combinations thereof.

### Claim 20 (depends on 14)

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.

### Claim 21 (depends on 14)

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.

### Claim 22 (depends on 14)

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.

### Claim 23 (depends on 14)

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.

### Claim 24 (depends on 14)

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.

### Claim 25 (depends on 14)

The cured epoxy shape memory material of claim 14 wherein the mixture further comprises additional curing agent.

### Claim 26 (depends on 14)

A composite mandrel comprising the cured epoxy shape memory material of claim 14.

### Claim 27 (depends on 14)

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.