Polyetherimides, methods of manufacture, and articles formed therefrom

• US 9,127,128 B2
• Filed: 10/28/2011
• Issued: 09/08/2015
• Est. Priority Date: 10/28/2011
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Kuhlman, Matthew L., Haralur, Gurulingamurthy M.
• Primary Examiner(s): Listvoyb, Gregory
• Application Number:
  US13/283,965
• Publication Number:
  US 20130108852A1
• Time in Patent Office: 1,411 Days
• Field of Search: 528/126, 528/128, 528/170, 528/171
• US Class Current: 1/1
• 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 73/1046 Polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08G 73/1053 with oxygen only in the tetracarboxylic moiety
• CPC Class Codes: C08G 79/08 a linkage containing boron
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/00 Manufacture of articles or shaped materials containing macromolecular substances manufacture of semi-permeable membranes B01D67/00 - B01D71/00
• CPC Class Codes: C08K 3/01 characterized by their specific function
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09D 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09J 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/31681 Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Abstract

A polyetherimide composition comprising a polyetherimide manufactured by reaction of an alkali metal salt of a dihydroxy aromatic compound with a bis(halophthalimide) composition comprising, based on the weight of the bis(halophthalimide) composition,

• • at least 15 wt. % of a 3,3′-bis(halophthalimide) of the formula

• • from more than 17 wt. % to less than 85 wt. % of a 4,3′-bis(halophthalimide) of the formula

• • from more than 0 to less than 27 wt. % of a 4,4′-bis(halophthalimide) of the formula

Claims

1. A polymer composition comprising a polyetherimide having the formula

3. The composition of claim 1, wherein the polyetherimide has

a heat deflection temperature of at least 218°

C., determined in accordance with ASTM 648 on a molded sample,

a heat deflection temperature at least 10°

C. higher than a heat deflection temperature of the same polyetherimide manufactured using a bis(halophthalimide) composition comprising more than 10 wt.% of the 4,3′

-bis(halophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample,

at least 10% higher stiffness than a stiffness of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10 wt.% of the 4,3′

-bis(halophthalimide), each determined by dynamic mechanical analysis over 30°

C. to 210°

C. on a molded sample, and

a ratio of a high shear rate viscosity to a low shear rate viscosity that is at least 30% higher than the same ratio of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10wt.% of the 4,3′

-bis(halophthalimide), each determined by parallel plate rheometry.

4. The composition of claim 1, wherein

the bis(halophthalimide) composition comprises from more than 47 wt.% to less than 85 wt.% of the 4,3′

-bis(halophthalimide).

5. The composition of claim 4, wherein the polyetherimide comprises, based on parts of the polyetherimide,

less than 100 parts per million each of the 3,3′

-bis(halophthalimide), the 4,3′

-bis(halophthalimide), and the 4,4′

-bis(halophthalimide).,

less than 100 parts per million of a halo(bisphthalimide) of the formula

6. The composition of claim 4, wherein

the polyetherimide has a heat deflection temperature of at least 218°

C., determined in accordance with ASTM 648 on a molded sample,

the polyetherimide has a heat deflection temperature at least 10°

C. higher than the heat deflection temperature of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising less than 10 wt.% of the 4,3′

-bis(halophthalimide) and more than 27wt.% of the 4,4′

-bis(halophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample,

the polyetherimide has at least 10% higher stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising less than 10 wt.% of the 4,3′

-bis(halophthalimide) and more than 27 wt.% of the 4,4′

-bis(halophthalimide), each determined by dynamic mechanical analysis over 30°

C. to 210°

C., on a molded sample, and

the polyetherimide has a ratio of a high shear rate viscosity to a low shear rate viscosity that is at least 30% higher than the same ratio of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising less than 10 wt.% of the 4,3′

-bis (halophthalimide) and more than 27 wt.% of the 4,4′

-bis(halophthalimide), each determined by parallel plate rheometry.

7. The composition of claim 1, wherein the bis(halophthalimide) composition comprises

from 15 to less than 85 wt.% of the 3,3′

-bis(halophthalimide),

from more than 47 to less than 85wt.% of the 4,3′

-bis(halophthalimide), and

from more than 0 to less than 27 wt.% of the 4,4′

-bis(halophthalimide).

8. The composition of claim 1, wherein

R is a divalent radical of the formula

9. The composition of claim 1, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene diarylsulfone, or a combination thereof.

10. The composition of claim 1, further comprising an additive selected from impact modifiers, fillers, reinforcing agents, anti-oxidants, heat stabilizers, light stabilizers, ultraviolet light absorbers, plasticizers, lubricants, mold release agents, antistatic agents, colorants, blowing agents, flame retardants, anti-drip agents, and radiation stabilizers, and a combination thereof.

11. The composition of claim 1, further comprising an additive selected from an antioxidant, an ultraviolet light absorber, a mold release agent, and a combination thereof.

19. A method for the manufacture of the polyetherimide composition of claim 1, the method comprising reacting, in the presence of a catalytically active amount of a phase transfer catalyst, the alkali metal salt of the dihydroxy aromatic compound with the bis(halophthalimide) composition.

20. The method of claim 19, wherein a first portion of the alkali metal salt of the dihydroxy aromatic compound reacted with the bis(halophthalimide) composition to form a first polyetherimide having a first molecular weight;

and a second portion of the e alkali metal salt of the dihydroxy aromatic compound is added to first polyetherimide to form a second polyetherimide having a second molecular weight higher than the first molecular weight.

23. An article comprising the composition of claim 1.

24. The article of claim 23, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

25. The article of claim 24, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

26. The article of claim 23, selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

27. The article of claim 23, the article comprising

(i) a polytetrafluoroethylene substrate having a first surface,

(ii) a metal substrate having a second surface, and

(iii) the polymer composition of claim 1, situated between the polytetrafluoroethylene substrate and the metal substrate.

28. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 1 to form the article.

29. The method of claim 28, further comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

30. An article comprising the composition of claim 4.

31. The article of claim 30, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

32. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 4 to form the article.

33. The method of claim 32, comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

38. The article of claim 34, the article comprising

(i) a polytetrafluoroethylene substrate having a first surface,

(ii) a metal substrate having a second surface, and

(iii) the polymer composition of claim 1, situated between the polytetrafluoroethylene substrate and the metal substrate.

2. A polyetherimide composition manufactured by reaction of an alkali metal salt of a dihydroxy aromatic compound of the formula

MO—

Z—

OM

wherein M is an alkali metal and Z is an aromatic C_6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C_1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, with

a bis(halophthalimide) composition comprising, based on the weight of the bis(halophthalimide) composition,

at least 15 wt.% of a 3,3′

-bis(halophthalimide) of the formula

12. A polymer composition comprising a polyetherimide of the formula

14. The composition of claim 12, wherein the polyetherimide has a heat deflection temperature of at least 218°

C., in accordance with ASTM 648 on a molded sample,

the polyetherimide has a heat deflection temperature at least 10°

C. higher than a heat deflection temperature of the same polyetherimide manufactured using a bis(chlorophthalimide) composition comprising more than 10 wt.% of the 4,3′

-bis bis(chlorophthalimide), each determined in accordance with ASTM 648 at, 0.455megaPascals stress and at 3.2 millimeters thickness on a molded sample,

the polyetherimide has at least 10% higher stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising more than 10 wt.% of the 4,3′

-bis(chlorophthalimide), each determined by dynamic mechanical analysis over 30°

C. to 210°

C. on a molded sample, and

the polyetherimide has a ratio of a high shear rate viscosity to a low shear rate viscosity that is at least 30% higher than the same ratio of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising more than 10 wt.% of the 4,3′

-bis(chlorophthalimide), each determined by parallel plate rheometry.

15. The composition of claim 12, wherein

the bis(chlorophthalimide) composition comprises from more than 47 wt.% to less than 85 wt.% of the 4,3′

-bis(chlorophthalimide), and

the polyetherimide comprises, based on parts of the polyetherimide,

less than 100 parts per million each of the 3,3′

-bis(chlorophthalimide), the 4,3′

-bis(chlorophthalimide), and the 4,4′

-bis(chlorophthalimide),

less than 100 parts per million of a chloro(bisphthalimide) of the formula

16. The composition of claim 15, wherein

the polyetherimide has a heat deflection temperature of at least 218°

C., in accordance with ASTM 648 on a molded sample;

the polyetherimide has a heat deflection temperature at least 10°

C. higher than the heat deflection temperature of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising less than 10 wt.% of the 4,3′

- bis (chlorophthalimide) and more than 27 wt.% of the 4,4′

-bis(chlorophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2millimeters thickness on a molded sample;

the polyetherimide has at least 10% higher stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising less than 10 wt.% of the 4,3′

-bis(chlorophthalimide) and more than 27 wt.% of the 4,4′

-bis(chlorophthalimide), each determined by dynamic mechanical analysis over 30°

C. to 210°

C., on a molded sample; and

the polyetherimide has a ratio of a high shear rate viscosity to a low shear rate viscosity that is at least 30% higher than the same ratio of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising less than 10 wt.% of the 4,3′

-bis(chlorophthalimide)and more than 27 wt.% of the 4,4′

-bis(chlorophthalimide), each determined by parallel plate rheometry.

17. The composition of claim 12, wherein the bis(chlorophthalimide) composition comprises

from 15 to less than 85 wt.% of the 3,3′

-bis(chlorophthalimide),

from 47 to less than 85 wt.% of the 4,3-bis(chlorophthalimide), and

from more than 0 to less than 27 wt.% of the 4,4′

- bis(chlorophthalimide).

18. The composition of claim 12, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene diarylsulfone, or a combination thereof.

21. A method for the manufacture of the polyetherimide composition of claim 12, the method comprising reacting, in the presence of a catalytically active amount of a phase transfer catalyst, the alkali metal salt of a dihydroxy aromatic compound with the bis(chlorophthalimide) composition.

22. The method of claim 21, wherein a first portion of the alkali metal salt of the dihydroxy aromatic compound reacted with the bis(halophthalimide) composition to form a first polyetherimide having a first molecular weight;

and a second portion of the alkali metal salt of the dihydroxy aromatic compound is added to first polyetherimide to form a second polyetherimide having a second molecular weight higher than the first molecular weight.

34. An article comprising the composition of claim 12.

35. The article of claim 34, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

36. The article of claim 35, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

37. The article of claim 34, selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

39. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 12 to form the article.

40. The method of claim 39, comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

41. An article comprising the composition of claim 15.

42. The article of claim 41, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

43. The article of claim 42, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

44. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 15 to form the article.

45. The method of claim 44, comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

46. An article comprising the composition of claim 17.

47. The article of claim 46, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

48. The article of claim 47, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

49. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 17 to form the article.

50. The method of claim 49, comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

13. A polyetherimide composition manufactured by reaction of an alkali metal salt of a dihydroxy aromatic compound of the formula

MO—

Z—

OM

wherein M is an alkali metal and Z is a divalent radical of the formula