# US 2010/0168280 A1 · Process for preparing a self-healing composite material

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- Number: US 2010/0168280 A1
- Document ID: US20100168280A1
- Status: Published application
- Kind: A1
- Application number: 12/586,993
- Filed: 2009-09-30
- Published: 2010-07-01
- Earliest claimed: 2008-10-02
- Assignees: Alenia Aeronautica S.p.A.
- Inventors: Liberata Guadagno; Pasquale Longo; Marialuigia Raimondo; Annaluisa Mariconda; Carlo Naddeo; Andrea Sorrentino; Vittoria Vittoria; Generoso Iannuzzo; Salvatore Russo; Erika Calvi
- Web page: https://patentgrep.com/patent/US20100168280A1

## CPC

- C08F 283/10: on to polymers containing more than one epoxy radical per molecule {(C08F283/004 takes precedence)}
- C08G 59/4014: {Nitrogen containing compounds}
- C08G 59/50: Amines
- C08L 51/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- B01J 31/2208: {Oxygen, e.g. acetylacetonates}
- B01J 31/2273: {with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes}
- B01J 31/2278: {Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts}
- B01J 2231/543: alkene metathesis
- B01J 2531/821: Ruthenium
- B29C 73/163: {Sealing compositions or agents, e.g. combined with propellant agents}
- B29C 73/22: the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)

## Abstract

The process for preparing a self-healing composite material comprising a matrix of epoxy polymer, in which a catalyst of ring opening metathesis reaction and microcapsules containing a cyclic olefin having 7 to 40 carbon atoms are dispersed, comprises the steps of: preparing a mixture of a precursor of the epoxy polymer, having at least one oxirane ring, a curing agent chosen from the group consisting of tertiary amines, a Hoveyda-Grubbs II metathesis catalyst reaction, having the formula (I), wherein Ar=aryl having at least one halogen or alkyl substituent and “R=alkyl with 1 to 20 carbon atoms, and microcapsules containing a cyclic olefin having 7 to 40 carbon atoms; and heating the mixture at a temperature comprised between 25 and 130° C. for at least 1 hour, so as to obtain such matrix of epoxy polymer due to a reaction between precursor and curing agent, which reaction does not substantially involve either said catalyst or said microcapsules.

## Claims

### Claim 1

Process for preparing a self-healing composite material comprising a matrix of epoxy polymer, in which a catalyst of ring opening metathesis reaction and microcapsules containing a cyclic olefin having 7 to 40 carbon atoms are dispersed, said process comprising the steps of:
preparing a mixture of
a precursor of said epoxy polymer, having at least one oxirane ring,
a curing agent chosen from the group consisting of tertiary amines,
a Hoveyda-Grubbs II metathesis catalyst reaction, having the formula
wherein Ar=aryl having at least one halogen or alkyl substituent and “R=alkyl with 1 to 20 carbon atoms, and
microcapsules containing a cyclic olefin having 7 to 40 carbon atoms; and
heating said mixture at a temperature comprised between 25 and 130° C. for at least 1 hour, so as to obtain said matrix of epoxy polymer due to a reaction between precursor and curing agent, which reaction does not substantially involve either said catalyst or said microcapsules.

### Claim 2 (depends on 1)

Process according to claim 1, wherein in the formula (I) Ar are mesityl and/or “R is isopropyl.

### Claim 3 (depends on 1)

Process according to claim 1, wherein said catalyst is 1,3-dimesityl-imidazoline-2-ylidene-ortho-methoxyphenylmethylene ruthenium dichloride or 1,3-di(ortho-isopropylphenyl)imidazoline-2-ylidene-ortho-methoxyphenylmethylene ruthenium dichloride.

### Claim 4 (depends on 1)

Process according to claim 1, wherein said curing agent is chosen from the group consisting of 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, N,N-di-methylpiperidine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol.

### Claim 5 (depends on 1)

Process according to claim 1, wherein said heating step is performed at a temperature comprised between 60° C. and 80° C.

### Claim 6 (depends on 1)

Process according to claim 1, wherein said heating step has a duration comprised between 24 h and 1 h, and preferably between 15 h and 9 h.

### Claim 7 (depends on 1)

Process according to claim 1, wherein said precursor of epoxy polymer is chosen from the group consisting of diglycidyl ether of bisphenol A (DGEBA), diglycidyl ether of bisphenol F (DGEBF), polyglycidyl ether of phenol-formaldehyde novolac, polyglycidyl ether of o-cresol-formaldehyde novolac, N,N,N′,N′,-tetraglycidyl methylenedianiline, bisphenol A novolac, triglycidyl ether of trisphenol-methane, triglycidyl p-aminophenol, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

### Claim 8 (depends on 1)

Process according to claim 1, wherein the mixture to be heated contains 3 to 10 parts w/w of metathesis catalyst and 5 to 10 parts w/w of curing agent, referred to 100 parts w/w of precursor of epoxy polymer.

### Claim 9 (depends on 1)

Process according to claim 1, wherein the heating step at a temperature comprised between 25 and 130° C. is followed by a further heating step at a temperature comprised between 140 and 170° C.

### Claim 10 (depends on 1)

Process according to claim 1, wherein said cyclic olefin is chosen from the group consisting of 5-ethylidene-2-norbornene, substituted dicyclopentadienes, substituted norbornenes, and substituted cyclooctadienes.