POLYETHERIMIDES, METHODS OF MANUFACTURE, AND ARTICLES FORMED THEREFROM

• US 20130260125A1
• Filed: 03/28/2013
• Published: 10/03/2013
• Est. Priority Date: 03/30/2012
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Guggenheim, Thomas Link, Bernabe, Beatriz Penalver, Odle, Roy Ray, Ordonez, Juan Justino Rodriguez, Hemmer, Gregory L.
• Granted Patent: US 9,193,829 B2
• Time in Patent Office: Days
• US Class Current: 428/220
• CPC Class Codes: C08G 73/1003 Preparatory processes
• 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 73/1067 Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• CPC Class Codes: C08G 73/1071 Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08K 5/51 Phosphorus bound to oxygen
• 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: D01F 6/74 from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/2925 Helical or coiled

Abstract

Polyetherimide compositions of formula (1) are described wherein the polyetherimide compositions comprise a polyetherimide comprising a reacted combination of alkali metal salts comprising an alkali metal salt of a dihydroxy aromatic compound and an alkali metal salt of a monohydroxy aromatic compound with a bis(halophthalimide), wherein the alkali metal salt of the monohydroxy aromatic compound is included in an amount of more than 0 and less than 5 mole percent, based on the total moles of the alkali metal salts, and the polyetherimide has a weight average molecular weight greater than or equal to 43,000 Daltons. The polyetherimide exhibits lower levels of chlorine and chlorine end groups, lower levels of bis(halophthalimide) and bis(phthalimide), and low plate-out during manufacturing.

Claims

1. A polyetherimide composition comprising a polyetherimide comprising a reacted combination of alkali metal salts and a bis(halophthalimide):

(a) the combination of alkali metal salts comprising

an alkali metal salt of a dihydroxy aromatic compound having the formula

M¹O—

Z¹—

OM¹ and

an alkali metal salt of a monohydroxy aromatic compound having the formula

M²O—

Z²

wherein

M¹ and M² are each independently an alkali metal, and

Z¹ and Z² are each independently an aromatic C_6-24 monocyclic or polycyclic hydrocarbyl moiety optionally substituted with 1 to 6 C_1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and

the alkali metal salt of the monohydroxy aromatic compound is included in an amount of more than 0 and less than 5 mole percent, based on the total moles of the alkali metal salts;

with

(b) the bis(halophthalimide) of the formula

2. The polyetherimide composition of claim 1, wherein R is the aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups and has the formula:

3. The polyetherimide composition of claim 1, wherein the polyetherimide comprises from 0.5 to 4 weight percent of a monohydroxy aromatic compound substituent, based on the total weight of the polyetherimide.

4. The polyetherimide composition of claim 1, wherein a total content of residual bis(halophthalimide) and residual bis(phthalimide) is less than 0.05 weight percent, based on the total weight of the polyetherimide.

5. The polyetherimide composition of claim 1, wherein a total content of residual bis(halophthalimide) is less than 600 ppm, based on the total weight of the polyetherimide.

6. The polyetherimide composition of claim 1, wherein a content of chloride is less than 3000 ppm, based on the total weight of the polyetherimide.

7. The polyetherimide composition of claim 1, wherein the polyetherimide has a plate-out weight of less than 1.1 mg, when determined using 200 shots from a 100°

F. (37.8°

C.) mold having the dimensions of 5×

6×

0.16 inches (12.7×

15.2×

0.4 cm).

8. The polyetherimide composition of claim 1, wherein the polyetherimide has a plate-out weight of less than 1.1 mg, when determined using 200 shots from a 350°

F. (177°

C.) Dynatup having the dimensions 4 inches (101.6 mm) in diameter and 0.125 inches (3.175 mm) thick.

9. The polyetherimide composition of claim 1, wherein M¹ and M² are each sodium.

10. The polyetherimide composition of claim 1, wherein Z¹ and Z² are each independently a C_12-24 polycyclic hydrocarbyl moiety optionally substituted with 1 to 6 C_1-8 alkyl groups.

11. The polyetherimide composition of claim 1, wherein

Z¹ is a divalent group having the formula

12. The polyetherimide composition of claim 1, wherein Z² is selected from

13. The polyetherimide composition of claim 1, wherein the alkali metal salt is selected from lithium salts, sodium salts, potassium salts, cesium salts, and a combination thereof.

14. The polyetherimide composition of claim 1, wherein the alkali metal salt of the monohydroxy aromatic compound is the sodium salt of p-cumyl phenol.

15. The polyetherimide composition of claim 1, wherein Z¹ is 2,2-(4-phenylene)isopropylidene and R is selected from m-phenylene, p-phenylene, diarylsulfone, and a combination thereof.

16. The polyetherimide composition of claim 1, further comprising a filler.

17. The polyetherimide composition of claim 1, wherein a filler is absent or substantially absent.

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

19. The polyetherimide composition of claim 18, further comprising an additive selected from an antioxidant, a UV absorber, a mold release agent, and a combination thereof.

20. The polyetherimide composition of claim 19, wherein other additives are absent or substantially absent from the composition.

21. The polyetherimide composition of claim 1, wherein an additive is absent or substantially absent from the composition.

22. The polyetherimide composition of claim 1, wherein a molded sample of the polyetherimide has an unnotched Izod impact strength of greater than 25 ft-lbs/in, when determined according to ASTM D4812 at 23°

C., and the polyetherimide has a melt flow index of less than or equal to 22 g/10 min, when determined according to ASTM D1238, at 337°

C./6.6 kg.

40. An article comprising the polyetherimide of claim 1.

41. The article of claim 40, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, membrane, foam, composite, and fiber.

42. The article of claim 41, wherein the sheet is selected from a foam sheet, paper sheet, and fabric sheet.

43. The article of claim 40, wherein the article is a spring comprising the polyetherimide.

44. The article of claim 40, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

45. A method of forming an article, comprising shaping, extruding, molding, spinning, or thermoforming the composition of claim 1 to form the article.

46. The method of claim 45, wherein the method forms fibers, and the method further comprising weaving or entangling the fibers to form a fabric.

23. A polyetherimide composition comprising a polyetherimide comprising a reacted combination of alkali metal salts and a bis(chlorophthalimide)

(a) the combination of alkali metal salts comprising

an alkali metal salt of bisphenol A, and

an alkali metal salt of p-cumylphenol

wherein the alkali metal salt of the p-cumyl phenol is included in an amount of more than 0 and less than 5 mole percent, based on the total moles of the alkali metal salts;

with

(b) a bis(chlorophthalimide) having the formula

24. A method for the manufacture of a polyetherimide, the method comprising

(a) contacting a halophthalic anhydride having the formula

25. The method of claim 24, wherein the aromatic hydrocarbon moiety having from 1 to 6 aromatic groups has the formula:

26. The method of claim 24, further comprising forming the polyetherimide at a pressure greater than atmospheric pressure.

27. The method of claim 24, wherein the polyetherimide comprises from 0.5 to 4 weight percent of a monohydroxy aromatic compound substituent, based on the total weight of the polyetherimide.

28. The method of claim 24, wherein a total content of residual bis(halophthalimide) and residual bis(phthalimide) is less than 0.05 weight percent, based on the total weight of the polyetherimide.

29. The method of claim 24, wherein a total content of residual bis(halophthalimide) is less than 600 ppm, based on the total weight of the polyetherimide.

30. The method of claim 24, wherein a content of chloride is less than 3000 ppm, based on the total weight of the polyetherimide.

31. The method of claim 24, wherein

the polyetherimide has a plate-out weight of less than 1.1 mg, when determined using 200 shots from a 100°

F. (37.8°

C.) mold having the dimensions of 5×

6×

0.16 inches (12.7×

15.2×

0.4 cm);

a molded sample of the polyetherimide has an unnotched Izod impact strength of greater than 25 ft-lbs/in, when determined according to ASTM D4812 at 23°

C.; and

the polyetherimide has a melt flow index of less than or equal to 22 g/10 min, when determined according to ASTM D1238, at 337°

C./6.6 kg.

32. The method of claim 24, wherein the polyetherimide has a plate-out weight of less than 1.1 mg, when determined using 200 shots from a 350°

F. (177°

C.) Dynatup having the dimensions 4 inches (101.6 mm) in diameter and 0.125 inches (3.175 mm) thick.

33. The method of claim 24, wherein M¹ and M² are each sodium.

34. The method of claim 24, wherein Z¹ and Z² are each independently a C_12-24 polycyclic hydrocarbyl moiety optionally substituted with 1 to 6 C_1-8 alkyl groups.

35. The method of claim 24, wherein

Z¹ is a divalent group having the formula

36. The method of claim 24, wherein Z² is selected from

37. The method of claim 24, wherein the alkali metal salt is selected from lithium salts, sodium salts, potassium salts, and cesium salts.

38. The method of claim 24, wherein the alkali metal salt of the monohydroxy aromatic compound is the sodium salt of p-cumyl phenol.

39. The method of claim 24, wherein Z¹ is 2,2-(4-phenylene)isopropylidene and R is selected from m-phenylene, p-phenylene, diarylsulfone, and a combination thereof.