Polyimide substrates having an interpenetrating network morphology and methods relating thereto

• US 6,828,390 B2
• Filed: 12/30/2002
• Issued: 12/07/2004
• Est. Priority Date: 06/24/2002
• Status: Active Grant

• Current Assignee: Dupont-Toray Co., Ltd.
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Uhara, Kenji
• Primary Examiner(s): WOODWARD, ANA LUCRECIA
• Application Number:
  US10/331,234
• Publication Number:
  US 20030236359A1
• Time in Patent Office: 708 Days
• Field of Search: 525/436, 525/432
• US Class Current: 525/436
• CPC Class Codes: B29B 7/002 Methods chemical aspects C08J3/00
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/20 Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: H05K 1/0346 containing N

Abstract

A high modulus, dimensionally stable film formed via an interpenetrating polyimide network of two polyimide structures, interlocked and bonded on a molecular level. The polyimide components are made from a dianhydride and a diamine. The dianhydrides used are tetravalent aromatic structures represented by

where X is a divalent organic group selected from among —CO—, —O—, —S—, —SO₂—, —CH₂—, —C(CH₃)₂—, and —C(CF₃)₂— and diamines used are divalent aromatic structure represented by

wherein Y is a divalent organic group selected from the group consisting of —CO—, —O—, —S—, —SO₂—, —CH₂—, —C(CH₃)₂—, and —C(CF₃)₂—. The end capping agent is a carboxylic anhydride or a silylating agent. The second polyimide is polymerized in the presence of the first polymer thus forming a single phase system.

Claims

1. A polyimide film comprising:

(a) a first polyimide said first polyimide comprising the reaction product of components comprising a dianhydride component, a diamine component, and an end capping component,

wherein said dianhydride component of said first polyimide has a tetravalent aromatic group selected from the group consisting of;

wherein X is a divalent organic group selected from among —

CO—

, —

O—

, —

S—

, —

SO₂—

, —

CH₂—

, —

C(CH₃)₂—

, and —

C(CF₃)₂—

;

wherein said diamine component of said first polyimide has a divalent aromatic group selected from the group consisting of;

where in Y is a divalent organic group selected from the group consisting of —

CO—

, —

O—

, —

S—

, —

SO₂—

, —

CH₂—

, —

C(CH₃)₂—

, and —

C(CF₃)₂—

;

wherein said end capping component of said first polyimide is selected from the group consisting of;

a carboxylic anhydride and a silylating agent,

(b) a second polyimide said second polyimide comprising the reaction product of components comprising a dianhydride component, a diamine component, and an end capping component,

wherein said dianhydride component of said second polyimide has a tetravalent aromatic group selected from the group consisting of;

wherein X is a divalent organic group selected from among —

CO—

, —

O—

, —

S—

, —

SO₂—

, —

CH₂—

, —

C(CH₃)₂—

, and —

C(CF₃)₂—

;

wherein said diamine component of second polyimide has a divalent aromatic group selected from the group consisting of;

wherein Y is a divalent organic group selected from the group consisting of —

CO—

, —

O—

, —

S—

, —

SO₂—

, —

CH₂—

, —

C(CH₃)₂—

, and —

C(CF₃)₂—

;

wherein said end capping component of second polyimide is selected from the group consisting of;

a carboxylic anhydride, and a silylating agent,

wherein said first polyimide and said second polyimide are loosely, physically interlocked and bonded as an interpenetrating polyimide network, and

wherein said first polyimide and said second polyimide are formed into a single film using a chemical conversion process.

3. The interpenetrating polyimide of claim 1 or claim 2 wherein:

i. the end capping component of the first polyimide; and

ii. the end capping component of the second polyimide, is selected from the group consisting of phthalic anhydride and acetic anhydride.

4. The interpenetrating polyimide of claim 1 or claim 2 wherein the single film is formed using a thermal conversion process.

2. An interpenetrating polyimide network comprising:

(a) a first polyimide said first polyimide comprising the reaction product of components comprising a dianhydride component, a diamine component, and an end capping component,

said dianhydride component of said first polyimide selected from the group consisting of, pyromellitic dianhydride and biphenyltetracarboxylic dianhydride,

said diamine component of said first polyimide selected from the group consisting of 3,4′

-diaminodiphenyl ether, 4,4′

-diaminodiphenyl either, and phenylene diamine, and

said end capping component of said first polyimide selected from the group consisting of a carboxylic anhydride and a silylating agent,

(b) a second polyimide said second polyimide comprising the reaction product of components comprising a dianhydride component, a diamine component, and an end capping component,

said dianhydride component of said second polyimide selected from the group consisting of, pyromellitic dianhydride and biphenyltetracarboxylic dianhydride,

said diamine component of said second polyimide selected from the group consisting of, 3,4′

-diaminodiphenyl ether, 4,4′

-diaminodiphenyl either, and phenylenediamine, and

said end capping component of said second polyimide selected from the group consisting of a carboxylic anhydride and a silylating agent,

wherein said first polyimide and said second polyimide are loosely, physically interlocked and bonded as an interpenetrating polyimide network, and

wherein said first polyimide and said second polyimide are formed into a single film using a chemical conversion process.

5. A method of manufacturing an interpenetrating polyimide film the method comprising the steps:

(a) reacting substantially equimolar amounts of a first diamine and a first dianhydride to form a first polyamic acid,

(b) adding an end capping component to said first polyamic acid at a mole ratio of 0.001% to 2.0% with respect to the solids content of the total polymer,

(c) adding substantially non-equimolar amounts of a second diamine and a second dianhydride to said first polyamic acid,

(d) reacting the second diamine and the second dianhydride in the presence of the first polyamic acid to give a second polyamic acid thus formed in-situ, forming a physically, loosely interlocked and bonded interpenetrating polyamic acid network,

(e) adding a catalyst agent to said interpenetrating polyamic acid network,

(f) adding a dehydrating agent to said interpenetrating polyamic acid network,

(g) casting or extruding the interpenetrating polyamic acid of step (f) onto a surface to form a interpenetrating polyamic acid-polyimide gel film, and

(h) heating the interpenetrating polyamic acid-polyimide gel film to a temperature range of 200°

to 500°

C. to convert the interpenetrating polyamic acid-polyimide gel film into an interpenetrating polyimide film.

7. The method of claim 5 or claim 6 wherein the first diamine and the second diamine is selected from the group consisting of phenylenediamine and diaminodiphenyl ether.

8. The method of claim 5 or claim 6 wherein the first dianhydride and the second dianhydride is selected from the group consisting of pyromellitic dianhydride and 3,3′

,4,4′

-biphenyltetracarboxylic dianhydride.

9. The method of claim 5 or claim 6 wherein the first diamine is selected from the group consisting of 4,4′

-diaminodiphenyl ether and 3,4′

-diaminodiphenyl ether.

10. The method of claim 5 or claim 6 wherein the first diamine is selected from the group consisting of p-phenylene diamine.

11. The method of claim 5 or claim 6 wherein the second diamine is selected from the group consisting of 4,4,′

-diaminodiphenyl ether and 3,4′

-diaminodiphenyl ether.

12. The method of claim 5 or claim 6 wherein the second diamine is selected from the group consisting of p-phenylene diamine.

6. A method of manufacturing an interpenetrating polyimide film, the method comprising the steps:

(a) reacting substantially equimolar amounts of a first diamine and a first dianhydride to form a first polyamic acid,

(b) adding an end capping component to said first polyamic acid at a mole ratio of 0.001% to 2.0% with respect to the solids content of the total polymer,

(c) adding substantially equimolar amounts of a second diamine and a second dianhydride to said first polyamic acid,

(d) reacting the second diamine and the second dianhydride in the presence of the first polyamic acid to give a second polyamic acid thus formed in-situ, forming a physically, loosely interlocked and bonded interpenetrating polyamic acid network,

(e) adding a catalyst agent to said interpenetrating polyamic acid network,

(f) adding a dehydrating agent to said interpenetrating polyamic acid network,

(g) casting or extruding the interpenetrating polyamic acid of step (f) onto a surface to form a interpenetrating polyamic acid-polyimide gel film, and

(h) heating the interpenetrating polyamic acid-polyimide gel film to a temperature range of 200°

to 500°

C. to convert the interpenetrating polyamic acid-polyimide gel film into an interpenetrating polyimide film.