Polyimides, process for the preparation thereof and polyimide resin compositions

• US 5,288,843 A
• Filed: 11/05/1990
• Issued: 02/22/1994
• Est. Priority Date: 05/20/1987
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Toatsu Chemicals Incorporated (Mitsui Chemicals)
• Inventors: Ohta, Masahiro, Yamaguchi, Akihiro, Yoshikawa, Masao, Tamai, Shoji, Oikawa, Hideaki, Ohkoshi, Kouji, Kawashima, Saburo, Iiyama, Katsuaki
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): HAMPTON HIGHTOWER, PATRICIA
• Application Number:
  US07/608,727
• Time in Patent Office: 1,205 Days
• Field of Search: 528/125, 528/126, 528/128, 528/171, 528/172, 528/173, 528/179, 528/185, 528/188, 528/220, 528/229, 528/350, 528/351, 528/353
• US Class Current: 528/353
• CPC Class Codes: C08G 73/1042 Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• CPC Class Codes: C08G 73/105 with oxygen only in the diamino moiety
• CPC Class Codes: C08G 73/1071 Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08L 81/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Abstract

In one aspect, the present invention relates to polyimides having excellent thermal resistance and process for preparing the same comprising carrying out condensation of 4,4'"'"'-bis(3-aminophenoxy)biphenyl with pyromellitic dianhydride in the presence of a different diamine compound and optionally with a different tetracarboxylic acid dianhydride.

In a second aspect, the present invention relates to a heat resistant resin composition consisting essentially of an aromatic polyetherimide and a defined polyimide.

In a third aspect, the present invention relates to a polyimide resin composition comprised on a defined polyimide and a separate high-temperature engineering polymer.

In a fourth aspect, the present invention relates to a resin composition comprised of a defined polyimide and an aromatic polyamideimide.

Claims

1. A process for preparing a polyimide having a melt viscosity of not more than 40,000 poise at 380°

C. comprising carrying out condensation of 4,4'"'"'-bis(3-aminophenoxy)biphenyl of the formula;

##STR42## with pyromellitic dianhydride of the formula;

##STR43## in the presence of at least one diamine compound in an amount of from about 1 to 100% by mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl, said at least one diamine compound being selected from;

(a) aminobenzylamine, phenylenediamine, diaminocyclohexane and ethylene diamine;

(b) 4,4'"'"'-diaminobiphenyl, 3,4'"'"'-diaminobiphenyl, 3,3'"'"'-diaminobiphenyl, 4,4'"'"'-diaminobenzophenone, 3,3'"'"'-diaminobenzophenone, 3,4'"'"'-diaminobenzophenone, bis(3-aminophenyl)ether, (3-aminophenyl)(4-aminophenyl)ether, bis(3-aminophenyl)sulfide, (3-aminophenyl)(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfoxide, (3-aminophenyl)(4-aminophenyl)sulfoxide, bis(4-aminophenyl)sulfoxide, bis(3-aminophenyl)sulfone, (3-aminophenyl)(4-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, 3,3'"'"'-diaminodiphenylmethane, 3,4'"'"'-diaminodiphenylmethane, 4,4'"'"'-diaminodiphenylmethane and diaminonaphthalene;

(c) 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene;

(d) bis-[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl ether;

(e) 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'"'"'-bis[3-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'"'"'bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4'"'"'-bis[4-(4-amino-α

,α

-dimethylbenzyl)phenoxy]benzophenone, 4,4'"'"'-bis[4-(4-amino-α

,α

-dimethylbenzyl)phenoxy]diphenyl sulfone and bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone.

2. The process of claim 1 wherein the condensation is carried out further in the presence of a tetracarboxylic acid dianhydride of the formula:

##STR44## wherein R₂ is a tetravalent group selected from the group consisting of an aliphatic group, an alicyclic group, a monocyclic aromatic group, a fused polycyclic aromatic group and a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member with the proviso that the tetracarboxylic acid dianhydride is not pyromellitic dianhydride.

3. The process of claim 2 wherein said polyimide is non-crystalline and said diamine compound is present in an amount of from about 1 to about 100% by mole per mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl and said tetracarboxylic acid dianhydride is present in an amount of from about 1 to about 100% by mole per mole of said pyromellitic dianhydride.

4. The process of claim 2 wherein said polyimide is crystalline and wherein said diamine compound is present in an amount of from about 1 to about 30% by mole per mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl and said tetracarboxylic acid dianhydride is present in an amount of from about 1 to about 30% by mole per mole of said pyromellitic dianhydride.

5. The process of claim 2 wherein said tetracarboxylic acid dianhydride is a compound wherein R₂ is a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member.

6. The process of claim 2 wherein said tetracarboxylic acid dianhydride is 3,3'"'"',4,4'"'"'-biphenyltetracarboxylic dianhydride.

7. The process of claim 1 further comprising a dicarboxylic acid anhydride.

8. The process of claim 7 wherein said dicarboxylic acid anhydride is present in an amount of from 0.001 to 1.0 mole per total moles of said 4,4-bis(3-aminophenoxy)biphenyl and said diamine compound.

9. The process of claim 8 wherein said dicarboxylic acid anhydride is phthalic anhydride.

10. A non-crystalline polyimide prepared by the process of claim 1.

11. A non-crystalline polyimide prepared by the process of claim 2.

12. A crystalline polyimide prepared by the process of claim 1.

13. A crystalline polyimide prepared by the process of claim 2.

14. A process for preparing a polyimide having a melt viscosity of not more than 40,000 poise at 380°

C. comprising carrying out condensation of 4,4'"'"'-bis(3-aminophenoxy)biphenyl of the formula;

##STR45## with pyromellitic dianhydride of the formula;

##STR46## in the presence of at least one diamine compound in an amount of from about 1 to 100% by mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl, said at least one diamine compound being selected from the group consisting of;

##STR47## wherein X₁ is a direct bond, O, CO, SO₂, SO, S, or CH₂ with the proviso that the diamine compound is not 4,4'"'"'diaminodiphenyl ether ##STR48## wherein X₂ is a direct bond, CO, SO₂, SO, S, ##STR49## wherein n is 1-4, and ##STR50## wherein X₂ is defined above.

15. The process of claim 14 wherein the condensation is carried out further in the presence of a tetracarboxylic acid dianhydride of the formula:

##STR51## wherein R₂ is a tetravalent group selected from the group consisting of an aliphatic group, an alicyclic group, a monocyclic aromatic group, a fused polycyclic aromatic group and a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member, with the proviso that the tetracarboxylic acid dianhydride is not pyromellitic dianhydride.

16. The process of claim 15 wherein said polyimide is non-crystalline and said diamine compound is present in an amount of from about 1 to about 100% by mole per mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl and said tetracarboxylic acid dianhydride is present in an amount of from about 1 to about 100% by mole per mole of said pyromellitic dianhydride.

17. The process of claim 15 wherein said polyimide is crystalline and wherein said diamine compound is present in an amount of from about 1 to about 30% by mole per mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl and said tetracarboxylic acid dianhydride is present in an amount of from about 1 to about 30% by mole per mole of said pyromellitic dianhydride.

18. The process of claim 15 wherein said tetracarboxylic acid dianhydride is a compound wherein R₂ is a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member.

19. The process of claim 15 wherein said tetracarboxylic acid dianhydride is 3,3'"'"',4,4'"'"'-biphenyltetracarboxylic anhydride.

20. The process of claim 14 further comprising a dicarboxylic acid anhydride.

21. The process of claim 20 wherein said dicarboxylic acid anhydride is present in an amount of from 0.001 to 1.0 mole per total moles of said 4,4-bis(3-aminophenoxy)biphenyl and said diamine compound.

22. The process of claim 21 wherein said dicarboxylic acid anhydride is phthalic anhydride.

23. A non-crystalline polyimide prepared by the process of claim 14.

24. A non-crystalline polyimide prepared by the process of claim 15.

25. A crystalline polyimide prepared by the process of claim 14.

26. A crystalline polyimide prepared by the process of claim 15.

27. A process of preparing a polyimide having a melt viscosity of not more than 40,000 poise at 380°

C. comprising carrying out condensation of 4,4'"'"'-bis(3-aminophenoxy)biphenyl of the formula;

##STR52## with pyromellitic dianhydride of the formula;

##STR53## in the presence of 4,4'"'"'-diaminodiphenyl ether in an amount of from about 2 to 30% by mole of said 4,4'"'"'-bis(3-aminophenoxy)biphenyl.

28. The process of claim 27 wherein the condensation is carried out further in the presence of a tetracarboxylic acid dianhydride of the formula:

##STR54## wherein R₂ is a tetravalent group selected from the group consisting of an aliphatic group, an alicyclic group, a monocyclic aromatic group, a fused polycyclic aromatic group and a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member with the proviso that the tetracarboxylic acid dianhydride is not pyromellitic dianhydride.

29. The process of claim 28 wherein said polyimide is non-crystalline and said tetracarboxylic acid dianhydride is present in an amount of from about 2 to about 30% by mole per mole of said pyromellitic dianhydride.

30. The process of claim 28 wherein said polyimide is transformed from non-crystalline to crystalline and wherein said tetracarboxylic acid dianhydride is present in an amount of from about 2 to about 30% by mole per mole of said pyromellitic dianhydride.

31. The process of claim 28 wherein said tetracarboxylic acid dianhydride is a compound wherein R₂ is a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member.

32. The process of claim 28 wherein said tetracarboxylic acid dianhydride is 3,3'"'"',4,4'"'"'-biphenyltetracarboxylic anhydride.

33. The process of claim 27 further comprising a dicarboxylic acid anhydride.

34. The process of claim 33 wherein said dicarboxylic acid anhydride is present in an amount of from 0.001 to 1.0 mole per total moles of said 4,4-bis(3-aminophenoxy)biphenyl and said diamine compound.

35. The process of claim 34 wherein said dicarboxylic acid anhydride is phthalic anhydride.

36. A non-crystalline polyimide prepared by the process of claim 27.

37. A non-crystalline polyimide prepared by the process of claim 28.

38. A crystalline polyimide prepared by the process of claim 27.

39. A crystalline polyimide prepared by the process of claim 28.

40. A polyimide having a melt viscosity of not more than 40,000 poise at 380°

C. and having two or more of recurring structural units represented by the formula (V);

##STR55## wherein Q₁ and Q₂ are each groups selected from the group consisting of an aliphatic group, a alicyclic group, a monocyclic aromatic group, a fused polycyclic aromatic group and a polycyclic aromatic group combined with a member selected from the group consisting of a direct bond and a bridge member, Q₁ is a divalent group and Q₂ is a tetravalent group;

said recurring structural units of the formula (V) comprising about 50% by mole or more of recurring structural units having the formula (VI);

##STR56## and from about 0.5 to about 50% by mole of at least one recurring structural unit of the formula;

##STR57## wherein Q₂ is a defined above and R₁ is derived from at least one diamine compound selected from (a) aminobenzylamine, phenylenediamine, diaminocyclohexane and ethylene diamine;

(b) 4,4'"'"'-diaminobiphenyl, 3,4'"'"'-diaminobiphenyl, 3,3'"'"'-diaminobiphenyl, 4,4'"'"'-diaminobenzophenone, 3,3'"'"'-diaminobenzophenone, 3,4'"'"'-diaminobenzophenone, bis(3-aminophenyl)ether, (3-aminophenyl)(4-aminophenyl)ether, bis(3-aminophenyl)sulfide, (3-aminophenyl)(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfoxide, (3-aminophenyl)(4-aminophenyl)sulfoxide, bis(4-aminophenyl)sulfoxide, bis(3-aminophenyl)sulfone, (3-aminophenyl)(4-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, 3,3'"'"'-diaminodiphenylmethane, 3,4'"'"'-diaminodiphenylmethane, 4,4'"'"'-diaminodiphenylmethane and diaminonaphthalene;

(c) 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, and 1,3-bis(4-aminophenoxy)benzene;

(d) bis-[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl ether;

(e) 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'"'"'-bis[3-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'"'"'bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4'"'"'-bis[4-(4-amino-α

,α

-dimethylbenzyl)phenoxy]benzophenone, 4,4'"'"'-bis[4-(4-amino-α

,α

-dimethylbenzyl)phenoxy]diphenyl sulfone and bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone.

41. The polyimide of claim 40 wherein said polyimide is non-crystalline.

42. The polyimide of claim 40 wherein said polyimide is crystalline and comprises at least about 85% by mole of the recurring structural unit of the formula (VI) and from about 0.5 to about 15% by mole of at least one recurring structural unit of the formula:

##STR58##