Polyimide resin composition and varnish produced from terminal-modified imide oligomer prepared using 2-phenyl-4,4′-diaminodiphenyl ether and thermoplastic aromatic polyimide prepared using oxydiphthalic acid, polyimide resin composition molded article and prepreg having excellent heat resistance and mechanical characteristic, and fiber-reinforced composite material thereof

Patent metadata

Field	Value
Publication number	US-10017666-B2
Application number	US-201414890065-A
Country	US
Kind code	B2
Filing date	Apr 21, 2014
Priority date	May 10, 2013
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

An imide resin composition including a terminal-modified imide oligomer of General Formula (1) and a thermoplastic aromatic polyimide of General Formula (2). (In Formula (1), either R 1 or R 2 shows a phenyl group and the other shows a hydrogen atom; R 3 and R 4 show a divalent residue of aromatic diamine; R 5 and R 6 show a tetravalent residue of aromatic tetracarboxylic acid; m and n satisfy relationships of m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1; and an arrangement of repeating units may be either a block or random.) (In Formula (2), R 1 and R 2 show a divalent residue of aromatic diamine; R 3 shows a tetravalent residue of aromatic tetracarboxylic acid; m and n satisfy relationships of m≥1 and n≥0, and an arrangement of repeating units may be either a block or random).

First claim

The invention claimed is:

1. An imide resin composition comprising a terminal-modified imide oligomer represented by Formula (1) described below, and a thermoplastic aromatic polyimide having an oxybisphthalimide skeleton, represented by Formula (5) described below:

wherein one of R 1 and R 2 is a hydrogen atom, and the other of R 1 and R 2 is a phenyl group; R 3 and R 4 are the same or different, and each is a divalent residue of an aromatic diamine selected from the group consisting of 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6-diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,6-diamine, 4,4′-diaminodiphenyl ether (4,4′-ODA), 3,4′-diaminodiphenyl ether (3,4′-ODA), 3,3′-diaminodipbenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl methane, 4,4′-diaminodiphenyl methane, bis(2,6-diethyl-4-aminophenyl)methane, 4,4′-methylene-bis(2,6-diethyl aniline), bis(2-ethyl-6-methyl-4-aminophenyl)methane, 4,4′-methylene-bis(2-ethyl-6-methylaniline), 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, benzidine, 3,3′-dimethylbenzidine, 2,2-bis(4-aminophenoxy)propane, 2,2-bis(3-aminophenoxy)propane, 2,2-bis[4′-(4″-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-(4-aminophenoxy)phenyl)fluorene and mixtures thereof; R 5 and R 6 are the same or different, and each is a tetravalent aromatic tetracarboxylic acid residue; m and n satisfy relationships of m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1; and the arrangement of repeating units in Formula (1) is either a block or random;

wherein R 1 and R 2 are the same or different, and each is a divalent aromatic diamine residue; R 3 is at least one tetravalent aromatic tetracarboxylic acid residue selected from the group consisting of 3,3′-oxydiphthalic anhydride residue and 4,4′-oxydiphthalic anhydride residue; m and n satisfy relationships of m≥1 and n≥0, and the arrangement of repeating units in Formula (5) is either a block or random.

2. The imide resin composition according to claim 1 , wherein the tetravalent aromatic tetracarboxylic acid residue, represented by R 5 or R 6 , is a tetravalent residue of 1,2,4,5-benzene tetracarboxylic acid, and the terminal-modified imide oligomer is a compound represented by Formula (3) described below:

wherein one of R 1 and R 2 is a hydrogen atom, and the other of R 1 and R 2 is a phenyl group; R 3 and R 4 are the same or different, and each is a divalent residue of an aromatic diamine selected from the group consisting of 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6-diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,6-diamine, 4,4′-diaminodiphenyl ether (4,4′-ODA), 3,4′-diaminodiphenyl ether (3,4′-ODA), 3,3′-diaminodipbenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl methane, 4,4′-diaminodiphenyl methane, bis(2,6-diethyl-4-aminophenyl)methane, 4,4′-methylene-bis(2,6-diethyl aniline), bis(2-ethyl-6-methyl-4-aminophenyl)methane, 4,4′-methylene-bis(2-ethyl-6-methylaniline), 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, benzidine, 3,3′-dimethylbenzidine, 2,2-bis(4-aminophenoxy)propane, 2,2-bis(3-aminophenoxy)propane, 2,2-bis[4′-(4″-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-(4-aminophenoxy)phenyl)fluorene and mixtures thereof; m and n satisfy relationships of m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1; and the arrangement of repeating units in Formula (3) is either a block or random.

3. The imide resin composition according to claim 1 , wherein the tetravalent aromatic tetracarboxylic acid residue, represented by R 5 or R 6 , is a tetravalent residue of 3,3′,4,4′-biphenyl tetracarboxylic acid, and the terminal-modified imide oligomer is a compound represented by Formula (4) described below:

wherein one of R 1 and R 2 is a hydrogen atom, and the other of R 1 and R 2 is a phenyl group; R 3 and R 4 are the same or different, and each is a divalent residue of an aromatic diamine selected from the group consisting of 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6-diethyl-1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,6-diamine, 4,4′-diaminodiphenyl ether (4,4′-ODA), 3,4′-diaminodiphenyl ether (3,4′-ODA), 3,3′-diaminodipbenyl ether, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl methane, 4,4′-diaminodiphenyl methane, bis(2,6-diethyl-4-aminophenyl)methane, 4,4′-methylene-bis(2,6-diethyl aniline), bis(2-ethyl-6-methyl-4-aminophenyl)methane, 4,4′-methylene-bis(2-ethyl-6-methylaniline), 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, benzidine, 3,3′-dimethylbenzidine, 2,2-bis(4-aminophenoxy)propane, 2,2-bis(3-aminophenoxy)propane, 2,2-bis[4′-(4″-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-(4-aminophenoxy)phenyl)fluorene and mixtures thereof; m and n satisfy relationships of m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1; and the arrangement of repeating units in Formula (4) is either a block or random.

4. The imide resin composition according to claim 1 , wherein in the terminal-modified imide oligomer represented by Formula (1), a part of m groups R 5 and n groups R 6 is a tetravalent residue of 1,2,4,5-benzene tetracarboxylic acid and the rest thereof is a tetravalent residue of 3,3′,4,4′-biphenyl tetracarboxylic acid.

5. A varnish comprising the imide resin composition according to claim 1 dissolved in an organic solvent.

6. A powdery imide resin composition obtained by removing an organic solvent from the varnish according to claim 5 .

7. An imide resin composition molded article obtained by heating the powdery imide resin composition according to claim 6 in a melted state, thereby making a molecular weight of the terminal-modified imide oligomer component larger.

8. A film-shaped imide resin composition molded article obtained by coating a support with the varnish according to claim 5 , and removing an organic solvent from the varnish.

9. An imide resin composition molded article obtained by heating the film-shaped imide resin composition molded article according to claim 8 in a melted state, thereby making a molecular weight of the terminal-modified imide oligomer component larger.

10. The imide resin composition molded article according to claim 8 , which is colored and transparent.

11. The imide resin composition molded article according to claim 8 , which has a glass transition temperature (Tg) of 250° C. or higher.

12. The imide resin composition molded article according to claim 8 , which has a tensile elongation at break of 10% or more.

13. An imide resin composition molded article obtained by thermally curing the varnish according to claim 5 .

Assignees

• Kaneka Corp
• Japan Aerospace Exploration

Inventors

• Miyauchi Masahiko
• Ishida Yuichi
• Ogasawara Toshio
• Yokota Rikio

Classifications

• C08J2379/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08J5/24 Primary

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title

• C08G73/1071

  Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• B29K2079/08

  PI, i.e. polyimides or derivatives thereof · CPC title