Thermosetting solution composition and prepreg

• US 7,807,014 B2
• Filed: 07/24/2008
• Issued: 10/05/2010
• Est. Priority Date: 05/31/2005
• Status: Active Grant

• Current Assignee: UBE Corporation
• Original Assignee: UBI Industries Limited
• Inventors: Yamaguchi, Hiroaki, Aoki, Fumio
• Primary Examiner(s): Tucker; Philip C
• Assistant Examiner(s): Orlando; Michael N
• Application Number:
  US12/178,855
• Publication Number:
  US 20090036601A1
• Time in Patent Office: 803 Days
• Field of Search: 156/307.1, 156/325, 524/607, 528/353
• US Class Current: 156/325
• CPC Class Codes: C08G 73/1003 Preparatory processes
• CPC Class Codes: C08G 73/1042 Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• CPC Class Codes: C08G 73/1078 wholly aromatic in the diamino moiety
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/243 using carbon fibres
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix

Abstract

A thermosetting solution composition composed of a biphenyltetracarboxylic acid compound containing a partial lower aliphatic alkyl ester of 2,3,3′,4′-biphenyltetracarboxylic acid and/or a partial lower aliphatic alkyl ester of 2,2′,3,3′-biphenyltetracarboxylic acid, an aromatic diamine compound in a molar amount larger than a molar amount of the biphenyltetracarboxylic acid compound, a partial lower aliphatic alkyl ester of 4-(2-phenylethynyl)phthalic acid compound in a molar amount as much as 1.8-2.2 times a molar amount corresponding to a difference between the molar amount of the aromatic diamine compound and the molar amount of the biphenyltetracarboxylic acid compound, and an organic solvent composed of a lower aliphatic alcohol is of value for manufacture of a prepreg.

Claims

1. A process for preparing a thermosetting solution composition comprising a biphenyltetracarboxylic acid compound containing at least 15 mol % of a partial lower aliphatic alkyl ester of 2,3,3′

,4′

-biphenyltetracarboxylic acid and/or a partial lower aliphatic alkyl ester of 2,2′

,3,3′

-biphenyltetracarboxylic acid, an aromatic diamine compound in a molar amount larger than a molar amount of the biphenyltetracarboxylic acid compound, said aromatic diamine compound being selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 1,3-bis(4-aminophenoxy)benzene and a mixture thereof, and a partial lower aliphatic alkyl ester of 4-(2-phenylethynyl)phthalic acid compound in a molar amount as much as 1.8-2.2 times a molar amount corresponding to a difference between the molar amount of the aromatic diamine compound and the molar amount of the biphenyltetracarboxylic acid compound dissolved in an organic solvent comprising a lower aliphatic alcohol, in which a total amount of the biphenyltetracarboxylic acid compound, 4-(2-phenylethynyl)phthalic acid compound and aromatic diamine compound is in the range of 30 to 80 wt. % based on an amount of the thermosetting solution composition, which comprises the steps of;

placing a biphenyltetracarboxylic acid compound containing at least 15 molar % of 2,3,3′

,4′

-biphenyltetracarboxylic dianhydride and/or 2,2′

,3,3′

-biphenyltetracarboxylic dianhydride, and 4-(2-phenylethynyl)phthalic anhydride in the organic solvent, to give a suspension;

heating the suspension to give a solution in which the partial lower aliphatic alkyl ester of the biphenyltetracarboxylic acid compound and the partial lower aliphatic alkyl ester of 4-(2-phenylethynyl)phthalic acid are dissolved; and

mixing the aromatic diamine compound with the solution obtained above.

2. The process of claim 1, in which each of the partial lower aliphatic alkyl esters is methyl ester and the lower aliphatic alcohol is methanol.

3. The process of claim 1, in which each of the partial lower aliphatic alkyl ester is ethyl esters and the lower aliphatic alcohol is ethanol.

4. The process of claim 1, in which the aromatic diamine compound is p-phenylenediamine, 1,3-bis(4-aminophenoxy)-benzene or a mixture thereof.

5. The process of claim 1, in which the aromatic diamine compound comprises a mixture of p-phenylenediamine and 1,3-bis(4-aminophenoxy)benzene wherein p-phenylenediamine is present in an amount of 50 to 70 molar %.

6. The process of claim 1, in which a total amount of the biphenyltetracarboxylic acid compound, the aromatic diamine compound, and 2-(2-phenylethynyl)phthalic acid compound is in the range of 30 to 80 wt. %, per the amount of the solution composition.

7. A process for preparing a thermosetting solution composition comprising a biphenyltetracarboxylic acid compound containing at least 15 mol % of a partial methyl ester of 2,3,3′

,4′

-biphenyltetracarboxylic acid and/or a partial methyl ester of 2,2′

,3,3′

-biphenyltetracarboxylic acid, an aromatic diamine compound in a molar amount larger than a molar amount of the biphenyltetracarboxylic acid compound, said aromatic diamine compound being selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 1,3-bis(4-aminophenoxy)benzene and a mixture thereof, and a partial methyl ester of 4-(2-phenylethynyl)phthalic acid compound in a molar amount as much as 1.8-2.2 times a molar amount corresponding to a difference between the molar amount of the aromatic diamine compound and the molar amount of the biphenyltetracarboxylic acid compound dissolved in ethanol, in which a total amount of the biphenyltetracarboxylic acid compound, 4-(2-phenylethynyl)phthalic acid compound and aromatic diamine compound is in the range of 30 to 80 wt. % based on an amount of the thermosetting solution composition, which comprises the steps of;

placing a biphenyltetracarboxylic acid compound containing at least 15 molar % of 2,3,3′

,4′

-biphenyltetracarboxylic dianhydride and/or 2,2′

,3,3′

-biphenyltetracarboxylic dianhydride, and 4-(2-phenylethynyl)phthalic anhydride in methanol, to give a suspension;

heating the suspension to give a methanol solution in which the partial methyl ester of the biphenyltetracarboxylic acid compound and the partial methyl ester of 4-(2-phenylethynyl)phthalic acid are dissolved;

mixing the aromatic diamine compound with the solution obtained above, whereby giving a thermosetting methanol solution in which the partial methyl ester of the biphenyltetracarboxylic acid compound, the partial methyl ester of 4-(2-phenylethynyl)phthalic acid and the aromatic diamine compound are dissolved;

drying the thermosetting methanol solution, whereby giving a thermosetting powdery composition; and

dissolving the thermosetting powdery composition in ethanol, whereby giving a thermosetting solution composition.

8. The process of claim 7, in which the aromatic diamine compound is p-phenylenediamine, 1,3-bis(4-aminophenoxy)benzene or a mixture thereof.

9. The process of claim 7, in which the aromatic diamine compound comprises a mixture of p-phenylenediamine and 1,3-bis(4-aminophenoxy)benzene wherein p-phenylenediamine is present in an amount of 50 to 70 molar %.