Latent epoxy resin formulations for liquid impregnation processes for production of fibre-reinforced composites

Patent metadata

Field	Value
Publication number	US-10155840-B2
Application number	US-201615375668-A
Country	US
Kind code	B2
Filing date	Dec 12, 2016
Priority date	Dec 11, 2015
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

Epoxy compositions containing at least one resin component and at least one hardener component, are suitable as a thermoset matrix for production of semi-finished fiber matrix products and cured fiber matrix laminates.

First claim

The invention claimed is:

1. A composition, comprising:
an epoxy resin composition, and
optionally a further additive, wherein
said epoxy resin composition comprises:
A) at least one epoxy compound;
B) a hardener composition comprising:
B1) 20%-40% by weight of at least one diamine and/or polyamine based on triacetonediamine,
and
B2) 60%-80% by weight of at least one further diamine and/or polyamine,
wherein the stoichiometric ratio of the epoxy groups of A) and the number of active hydrogen atoms of the functional group(s) of B) varies from 1:0.5 to 1:1,
and

C) 0.1% to 10% by weight of at least one curing accelerator,
D) optionally, at least one latent hardener,
wherein the amounts of A)-D) add up to 100% by weight of said epoxy resin composition.

2. The composition according to claim 1 , wherein epoxy compound A) is at least one member selected from the group consisting of
a saturated epoxy compound, an unsaturated epoxy compound, an aliphatic epoxy compound, a cycloaliphatic epoxy compound, an aromatic epoxy compound, and a heterocyclic epoxy compound, and
wherein the epoxy compound optionally has a hydroxyl group.

3. The composition according to claim 1 , wherein
epoxy compound A) is at least one member selected from the group consisting of a glycidyl ether, a glycidyl ester, an aliphatic epoxide, a diglycidyl ether based on at least one of bisphenol A and bisphenol F, and a glycidyl methacrylate.

4. The composition according to claim 1 , wherein
the epoxy compound A) is at least one member selected from the group consisting of
an epoxy resin based on bisphenol A diglycidyl ether, an epoxy resin based on bisphenol F diglycidyl ether, 4,4′-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], hexanediol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, propane-1,2,3-triol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl hexahydrophthalate, an aliphatic epoxy resin, and a cycloaliphatic epoxy resin.

5. The composition according to claim 1 , wherein component B1) comprises at least one member selected from the group consisting of
2,2,6,6-tetramethyl-4-aminopiperidine (TAD),
hexamethylenebis(4-amino-2,2,6,6-tetramethylpiperidine),
N-butyl-4-amino-2,2,6,6-tetramethylpiperidine,
N,N-dimethylaminopropyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-propyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-isopropyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-hydroxyethyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-methoxyethyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-methoxyethyl-4-amino-2,2,6,6-tetramethylpiperidine,
N′,N′-dimethylaminoethyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-morpholinoethyl-4-amino-2,2,6,6-tetramethylpiperidine,
N-piperazinoethyl-4-amino-2,2,6,6-tetramethylpiperidine, and
4-morpholino-2,2,6,6-tetramethylpiperidine.

6. The composition according to claim 1 , wherein
component B2) comprises at least one member selected from the group consisting of a primary diamine, a secondary diamine, a primary polyamine, and a secondary polyamine.

7. The composition according to claim 1 , wherein component B2) comprises at least one of:
a) an aliphatic amine;
b) at least one oxyalkylenepolyamine selected from the group consisting of polyoxypropylenediamine and polyoxypropylenetriamine, 1,13-diamino-4,7,10-trioxatridecane, and 4,7-dioxadecane-1,10-diamine;
c) at least one cycloaliphatic amine selected from the group consisting of isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine), 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, N-cyclohexyl-1,3-propanediamine, 1,2-diaminocyclohexane, 3-(cyclohexylamino)propylamine, piperazine, N-aminoethylpiperazine, TCD diamine (3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane), and 4-methylcyclohexane-1,3-diamine;
d) an araliphatic amine;
e) at least one aromatic amine selected from the group consisting of phenylenediamines, phenylene-1,3-diamine, phenylene-1,4-diamine, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, and 2,2′-diaminodiphenylmethane, alone or in mixtures of the isomers;
f) an adduct hardener which is the reaction product of an epoxy compound with excess amine;
g) a polyamidoamine hardener which is obtained by condensation of a mono- and/or polycarboxylic acid with a polyamine;
h) a Mannich base hardener which is obtained by reaction of a mono- and/or polyhydric phenol with an aldehyde and a polyamine; and
i) a Mannich base.

8. The composition according to claim 7 , wherein said Mannich base is based on phenol and/or resorcinol, formaldehyde and m-xylylenediamine, N-aminoethylpiperazine and blends of N-aminoethylpiperazine with nonylphenol and/or benzyl alcohol, phenalkamines which are obtained in a Mannich reaction from cardanols, aldehydes and amines.

9. The composition according to claim 1 , wherein component B2) comprises at least one member selected from the group consisting of
isophoronediamine;
4,4′-diaminodicyclohexylmethane;
2,4′-diaminodicyclohexylmethane;
2,2′-diaminodicyclohexylmethane;
a mixture of at least two of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, and 2,2′-diaminodicyclohexylmethane;
polyoxypropylenediamine;
polyoxypropylenetriamine;
a mixture of poly oxypropylenediamine and polyoxypropylenetriamine;
at least one adduct based on a reaction product of an epoxy compound and at least one member selected from the group consisting of isophoronediamine; 4,4′-diaminodicyclohexylmethane; 2,4′-diaminodicyclohexylmethane; 2,2′-diaminodicyclohexylmethane; a mixture of at least two of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, and 2,2′-diaminodicyclohexylmethane; polyoxypropylenediamine; polyoxypropylenetriamine; and a mixture of polyoxypropylenediamine and polyoxypropylenetriamine.

10. The composition according to claim 1 , wherein component B2) comprises at least one member selected from the group consisting of
a) isophoronediamine,
b) 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane, a combination of at least two of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane, a combination of isophoronediamine and a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, or a combination of isophoronediamine with a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine and at least one of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, and 2,2′-diaminodicyclohexylmethane, and
c) an adduct hardener based on a reaction product of an epoxy compound and a) or b).

11. The composition according to claim 1 , wherein component B2) comprises at least one member selected from the group consisting of
isophoronediamine;
at least one of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane;
a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine; and
an adduct based on a reaction product of epoxy compound and at least one member selected from the group consisting of isophoronediamine; at least one of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane; and a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine.

12. The composition according to claim 1 , wherein component B) is a mixture of:
B1) 25%-35% by weight of triacetonediamine; and
B2) 65%-75% by weight of a mixture of

Assignees

• Evonik Degussa Gmbh

Inventors

• Ortelt Martina
• Langkabel Eike
• Fuchsmann Dirk
• Kohlstruk Britta
• Karns Katharina

Classifications

• C08L63/00 Primary

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

• C08J2363/00

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

• C08J2363/02

  Polyglycidyl ethers of bis-phenols · CPC title

• B29L2031/3067

  Ships · CPC title

• B29C70/44

  using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding · CPC title