POLYETHERIMIDES, METHODS OF MANUFACTURE, AND ARTICLES FORMED THEREFROM

• US 20130108851A1
• Filed: 10/28/2011
• Published: 05/02/2013
• Est. Priority Date: 10/28/2011
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Kuhlman, Matthew L., Haralur, Gurulingamurthy M.
• Granted Patent: US 8,907,042 B2
• Time in Patent Office: Days
• US Class Current: 428/220
• CPC Class Codes: C07C 63/04 Monocyclic monocarboxylic acids
• CPC Class Codes: C07C 63/22 Halides thereof
• CPC Class Codes: C07D 209/48 with oxygen atoms in positions 1 and 3, e.g. phthalimide
• CPC Class Codes: C08G 65/40 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
• 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: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/2942 Plural coatings
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers

Abstract

A polyetherimide 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 salt 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,
    • from more than 45 to less than 75 weight percent of a 3,3′-bis(halophthalimide) of the formula

• • less than 10 weight percent of a 3,4′-bis(halophthalimide) of the formula

and

• • from more than 45 to less than 75 weight percent of a (4,4′-bis(halophthalimide) of the formula

Claims

1. A polymer composition comprising a polyetherimide of the formula

2. The polymer composition of claim 1, wherein the polyetherimide is 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 salt 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,

from more than 45 to less than 75 weight percent of a 3,3′

-bis(halophthalimide) of the formula

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

a heat deflection temperature of at least 218°

C., determined by DMA on a film 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 weight percent of 3,4′

-bis(chlorophthalimide), each determined on a film sample,

at least 20% lower stiffness than the stiffness of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10 weight percent of 3,4′

-bis(chlorophthalimide), each determined by DMA over 30°

C. to 110°

C. and on a film sample, and

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

-bis(halophthalimide) and more than 55 weight percent of the 4,4′

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

4. The composition of claim 1, wherein the polyetherimide comprises less than 3000 parts per million of a halide, based on the total parts of the polyetherimide.

6. The composition of claim 1, wherein the bis(halophthalimide) composition comprises from 45 to less than 55 weight percent of the (3,3′

-bis(halophthalimide), less than 10 weight percent of the 3,4′

-bis(halophthalimide), and from 45 to 55 weight percent of the 4,4′

-bis(halophthalimide).

7. The composition of claim 1, wherein Z is a divalent radical of the formula

8. The composition of claim 7, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

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

10. The composition of claim 1, further comprising an additive selected from an antioxidant, a UV 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, an alkali metal salt of a dihydroxy aromatic compound of the formula

MO—

Z—

OM

wherein M is an alkali metal salt 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,

from more than 45 to less than 75 weight percent of a 3,3′

-bis(halophthalimide) of the formula

20. The method of claim 19, wherein the polyetherimide has

a heat deflection temperature of at least 218°

C., determined by DMA on a film 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 weight percent of 3,4′

-bis(halophthalimide), each determined DMA on a film sample,

at least 20% lower stiffness than the stiffness of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10 weight percent of 3,4′

-bis(halophthalimide), each determined by DMA over 30°

C. to 110°

C., on a film sample, and

a ratio of a low shear rate viscosity to a high 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 10 weight percent of 3,4′

-bis(halophthalimide) and more than 55 weight percent of the 4,4′

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

21. The method of claim 19, wherein

M is sodium,

Z is a divalent radical of the formula

22. The method of claim 21, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

27. An article comprising the composition of claim 1.

28. The article of claim 27, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

29. The article of claim 28, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

30. The article of claim 27, selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

31. The article of claim 27, 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.

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

34. The article of claim 31, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

35. The article of claim 31, selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

36. The article of claim 31, 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.

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

38. The method of claim 37, comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.

5. The composition of 4, wherein the polyetherimide comprises less than 5 weight percent of a cyclic byproduct, based on the total weight of the polyetherimide.

11. A polymer composition comprising a polyetherimide of the formula

12. The polymer composition of claim 11, wherein the polyetherimide is 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 salt 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(chlorophthalimide) composition comprising, based on the weight of the bis(chlorophthalimide) composition,

from more than 45 to less than 75 weight percent of a 3,3′

-bis(chlorophthalimide) of the formula

13. The composition of claim 11, wherein the polyetherimide has

a heat deflection temperature of at least 218°

C., determined using DMA on a film sample,

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 weight percent of 3,4′

-bis(chlorophthalimide), each determined by DMA on a film sample,

at least 20% lower stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising more than 10 weight percent of 3,4′

-bis(chlorophthalimide), each determined by DMA over 30°

C. to 110°

C. on a film sample, and

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

-bis(chlorophthalimide) and more than 55 weight percent of the 4,4′

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

14. The composition of claim 11, wherein the polyetherimide comprises less than 3000 parts per million of chloride, based on the total parts of the polyetherimide.

15. The composition of claim 11, wherein the polyetherimide comprises less than 5 weight percent of a cyclic byproduct of the alkali metal salt and the bis(halophthalimide), based on the total weight of the polyetherimide.

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

from 45 to 55 weight percent of the (3,3′

-bis(chlorophthalimide),

less than 10 weight percent of the 4,3′

-bis(chlorophthalimide), and

from 45 to 55 weight percent of the 4,4′

-bis(chlorophthalimide).

17. The composition of claim 12, wherein Z is a divalent radical of the formula

18. The composition of claim 17, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

32. An article comprising the composition of claim 11.

39. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 11 to form an article.

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

23. A method for the manufacture of a polyetherimide composition, the method comprising reacting, in the presence of a catalytically active amount of a phase transfer catalyst, an alkali metal salt of a dihydroxy aromatic compound of the formula

MO—

Z—

OM

wherein M is an alkali metal salt 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(chlorophthalimide) composition comprising, based on the weight of the bis(chlorophthalimide) composition,

from more than 45 to less than 75 weight percent of a 3,3′

-bis(chlorophthalimide) of the formula

24. The method of claim 23, wherein the polyetherimide has

a heat deflection temperature of at least 218°

C., determined by DMA on a film sample

a heat deflection temperature at least 10°

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

-bis(chlorophthalimide), each determined by DMA on a film sample,

at least 30% lower stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising more than 10 weight percent of 3,4′

-bis(chlorophthalimide), each determined by DMA over 30°

C. to 110°

C., on a film sample, and

a ratio of low shear rate viscosity to high 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 weight percent of 3,4′

-bis(chlorophthalimide) and more than 55 weight percent of the 4,4′

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

25. The method of claim 23, wherein

M is sodium,

Z is a divalent radical of the formula

26. The method of claim 25, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

41. A method for the manufacture of a bis(halophthalimide) composition from a combination of a 4-halophthalic anhydride isomer of the formula

42. The method of claim 41, wherein

X is chlorine;

and

R is a divalent group of formula

43. The method of claim 41, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

44. A polyetherimide of the formula

45. The polyetherimide of claim 44, wherein R is a divalent group of formula

46. The composition of claim 44, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene, p-phenylene diarylsulfone, or a combination thereof.

47. The composition of claim 44, wherein the polyetherimide comprises less than 3000 parts per million of a halide, based on the total parts of the polyetherimide.

48. The composition of claim 44, wherein the polyetherimide comprises less than 5 weight percent of a cyclic byproduct, based on the total weight of the polyetherimide.

49. The composition of claim 44, wherein

more than 45 to less than 55 mole percent the divalent bonds of the —

O—

Z—

O-groups are in the 3,3′

position,

less than 10 mole percent of the —

O—

Z—

O—

groups are in the 3,4′

, and 4′

,3 positions, and

more than 45 to less than 55 mole percent of the —

O—

Z—

O—

groups are in the 4,4′

position.