Expanded and expandable high glass transition temperature polymers

Abstract

A expandable or expanded composition comprises either: a) an immiscible blend of polymers having more than one glass transition temperature and one of the polymers has a glass transition temperature greater than 180 degrees Celsius; b) a miscible blend of polymers having a single glass transition temperature greater than 217 degrees Celsius; or, c) a single virgin polymer having a glass transition temperature of greater than 247 degrees Celsius.

Description

Claims

1. An expandable or expanded composition comprising either: a) an immiscible blend of polymers comprising one or more polyetherimides, having more than one glass transition temperature wherein the polyetherimide has a glass transition temperature greater than 217° Celsius; b) a miscible blend of polymers, comprising one or more polyetherimides, having a single glass transition temperature greater than 180° Celsius; or, c) a single polyetherimide having a glass transition temperature of greater than 247° Celsius.

2. The expandable or expanded composition according to claim 1 comprising an immiscible blend of polymers having more than one glass transition temperature and one of the polymers has a glass transition temperature greater than 180° Celsius.

3. The expandable or expanded composition according to claim 1 comprising a miscible blend of polymers having a single glass transition temperature greater than 217° Celsius.

4. The expandable or expanded composition according to claim 1 comprising a single virgin polymer having a glass transition temperature of greater than 247° C.elsius.

5. The expandable or expanded composition according to claim 1 comprising a blend of a first resin selected from the group consisting of: polysulfones, polyether sulfones, polyphenylene ether sulfones, and mixtures thereof, a second resin comprising a silicone copolymer and a third resin comprising a resorcinol based aryl polyester resin wherein greater than or equal to 50 mole % of the aryl polyester linkages are aryl ester linkages derived from resorcinol.

6. The expandable or expanded composition according to claim 5 wherein the silicone copolymer is selected from the group consisting of; polyimide siloxanes, polyetherimide siloxanes, polyetherimide sulfone siloxanes, polycarbonate siloxanes, polyestercarbonate siloxanes, polysulfone siloxanes, polyether sulfone siloxanes, polyphenylene ether sulfone siloxanes and mixtures thereof.

7. The expandable or expanded composition according to claim 6 wherein the silicone copolymer content is from 0.1 to 10.0 wt % of the polymer blend.

8. The expandable or expanded composition according to claim 6 wherein the silicone copolymer has from 20-50 wt % siloxane content.

9. The expandable or expanded composition according to claim 5 wherein the polysulfones, polyether sulfones, polyphenylene ether sulfones and mixtures thereof, have a hydrogen atom to carbon atom ratio of less than or equal to 0.85.

10. The expandable or expanded composition according to claim 5 further comprising one or more metal oxides at 0.1 to 20% by weight of the polymer blend.

11. The expandable or expanded composition according to claim 5 wherein the resorcinol based aryl polyester has the structure shown below:

12. The expandable or expanded composition according to claim 5 wherein the resorcinol based polyester resin is a copolymer containing carbonate linkages having the structure shown below:

13. The expandable or expanded composition according to claim 12 wherein R5 is derived from a bisphenol compound.

14. A expandable or expanded composition according to claim 1 wherein the immiscible blend of polymers comprises a mixture of: a) a first resin component selected from one or more of the group comprising: polyaryl ether ketones, polyaryl ketones, polyether ketones and polyether ether ketones; with, b) a second resin component comprising at least one polysulfone etherimide having greater than or equal to 50 mole % of the linkages containing at least one aryl sulfone group.

15. A expandable or expanded composition according to claim 14 wherein the polysulfone etherimide contains aryl sulfone and aryl ether linkages such that at least 50 mole % of the repeat units of the polysulfone etherimide contain at least one aryl ether linkage, at least one aryl sulfone linkage and at least two aryl imide linkages.

16. A expandable or expanded composition according to claim 14 wherein at least 50 mole % of the polysulfone etherimide linkages are derived from oxydiphthalic anhydride or a chemical equivalent thereof.

17. A expandable or expanded composition according to claim 14 wherein less than 30 mole % of polysulfone etherimide linkages are derived from a diamine or dianhydride containing an isoalkylidene group.

18. A expandable or expanded composition according to claim 14 wherein the substrate has a heat distortion temperature (HDT) of greater than or equal to 170° C., measured as per ASTM method D648 at 66 psi (0.46 Mpa) on a 3.2 mm sample.

19. A expandable or expanded composition according to claim 14 wherein the polysulfone etherimide is present from 30-70 wt % of the substrate.

20. A expandable or expanded composition according to claim 14 wherein the polysulfone etherimide is essentially free of benzylic protons.

21. A expandable or expanded composition according to claim 14 wherein the one or more polyaryl ether ketone, polyaryl ketone, polyether ketone, and polyether ether ketone have a crystalline melting point from 300° to 380° C.

22. A expandable or expanded composition according to claim 14 wherein the polysulfone etherimide has a glass transition temperature (Tg), from 250° to 350° C.

23. A expandable or expanded composition according to claim 14 wherein the polymer blend has at least two different glass transition temperatures, as measured by ASTM method D5418, wherein the first glass transition temperature is from 120°-200° C. and the second glass transition temperature is from 250°-350° C.

24. A expandable or expanded composition having improved flame retardance according to claim 1 comprising a blend of a first resin selected from the group consisting of: polyimides, polyetherimides, polyetherimide sulfones, and mixtures thereof, a second resin comprising a silicone copolymer and a third resin comprising a resorcinol based aryl polyester resin wherein greater than or equal to 50 mole % of the aryl polyester linkages are aryl ester linkages derived from resorcinol.

25. A expandable or expanded composition according to claim 24 wherein the silicone copolymer is one or more selected from the group consisting of: polyimide siloxanes, polyetherimide siloxanes, polyetherimide sulfone siloxanes, polycarbonate siloxanes, polyestercarbonate siloxanes, polysulfone siloxanes, polyether sulfone siloxanes, and polyphenylene ether sulfone siloxanes.

26. A expandable or expanded composition according to claim 24 wherein the silicone copolymer content is from 0.1 to 10.0 wt % of the polymer blend.

27. A expandable or expanded composition according to claim 24 wherein the silicone copolymer has from 20-50 wt % siloxane content.

28. A expandable or expanded composition according to claim 24 wherein the polyimides, polyetherimides, polyetherimide sulfones and mixtures thereof, have a hydrogen atom to carbon atom ratio of less than or equal to 0.75.

29. A expandable or expanded composition according to claim 24 further comprising one or more metal oxides at 0.1 to 20% by weight of the polymer blend.

30. A expandable or expanded composition according to claim 24 wherein the resorcinol based aryl polyester has the structure shown below:

31. A expandable or expanded composition according to claim 24 wherein the resorcinol based polyester resin is a copolymer containing carbonate linkages having the structure shown below:

32. A expandable or expanded composition according to claim 31 wherein R5 is derived from a bisphenol compound.

33. A expandable or expanded composition according to claim 24 wherein the polyimide, polyetherimide, or polyetherimide sulfone is made from aryl dianhydrides selected from the group consisting of: bisphenol A dianhydride, oxydiphthalic anhydride, pyromellitic dianhydride, diphthalic anhydride, sulfonyl dianhydride, sulfur dianhydride, benzophenone dianhydride and mixtures thereof; and,aryl diamines selected from the group consisting of: meta phenylene diamine, para phenylene diamine, diamino diphenyl sulfone, oxydianiline, bis amino phenoxy benzene, bis aminophenoxy biphenyl, bis aminophenyl phenyl sulfone, diamino diphenyl sulfide and mixtures thereof.

34. A expandable or expanded composition according to claim 1 comprising a copolyetherimide having a glass transition temperature of at least about 218° C., said copolyetherimide comprising structural units of the formulas (I) and (II):

35. A expandable or expanded composition according to claim 34 comprising a copolyetherimide having a Tg greater than 225° C.

36. A expandable or expanded composition according to claim 34 comprising a copolyetherimide comprising structural units of the formula (III).

37. A expandable or expanded composition according to claim 34 wherein R1 is derived from at least one diamine selected from the group consisting of meta-phenylenediamine; para-phenylenediamine; 2-methyl-4,6-diethyl-1,3-phenylenediamine; 5-methyl-4,6-diethyl-1,3-phenylenediamine; bis(4-aminophenyl)-2,2-propane; bis(2-chloro-4-amino-3,5-diethylphenyl)methane, 4,4′-diaminodiphenyl, 3,4′-diaminodiphenyl, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,4-toluenediamine; and mixtures thereof.

38. A expandable or expanded composition according to claim 34 wherein R2 is derived from at least one dihydroxy-substituted aromatic hydrocarbon of the formula (VI): HO---D---OHwherein D has the structure of formula (VII):

39. A expandable or expanded composition according to claim 34 wherein R2 structural units in each of formulas (I), (II) and (III) are the same.

40. A expandable or expanded composition according to claim 34 wherein at least a portion of R2 structural units in at least two of formulas (I), (II) and (III) are not the same.

41. A expandable or expanded composition according to claim 34 wherein R2 is derived from at least one dihydroxy-substituted aromatic hydrocarbon selected from the group consisting of 4,4′-(cyclopentylidene)diphenol; 4,4′-(3,3,5-trimethylcyclopentylidene)diphenol; 4,4′-(cyclohexylidene)diphenol; 4,4′-(3,3-dimethylcyclohexylidene)diphenol; 4,4′-(3,3,5-trimethylcyclohexylidene)diphenol; 4,4′-(methylcyclohexylidene)diphenol; 4,4′-bis(3,5-dimethyl)diphenol, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane; 4,4-bis(4-hydroxyphenyl)heptane; 2,4′-dihydroxydiphenylmethane; bis(2-hydroxyphenyl)methane; bis(4-hydroxyphenyl)methane; bis(4-hydroxy-5-nitrophenyl)methane; bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 1,2-bis(4-hydroxyphenyl)ethane; 1,1-bis(4-hydroxy-2-chlorophenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(3-phenyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3-isopropylphenyl)propane; 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 3,5,3′,5′-tetrachloro-4,4′-dihydroxyphenyl)propane; bis(4-hydroxyphenyl)cyclohexylmethane; 2,2-bis(4-hydroxyphenyl)-1-phenylpropane; 2,4′-dihydroxyphenyl sulfone; dihydroxy naphthalene, 2,6-dihydroxy naphthalene; hydroquinone; resorcinol; C1-3 alkyl-substituted resorcinols; 2,2-bis-(4-hydroxyphenyl)butane; 2,2-bis-(4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(4-hydroxyphenyl)cyclohexane; bis-(4-hydroxyphenyl); bis-(4-hydroxyphenyl)sulphide; 2-(3-methyl-4-hydroxyphenyl-2-(4-hydroxyphenyl)propane; 2-(3,5-dimethyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane; 2-(3-methyl-4-hydroxyphenyl)-2-(3,5-dimethyl-4-hydroxyphenyl)propane; bis-(3,5-dimethylphenyl-4-hydroxyphenyl)methane; 1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)ethane; 2,2-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)propane; 2,4-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)-2-methylbutane; 3,3-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)pentane; 1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)cyclopentane; 1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)cyclohexane; bis-(3,5-dimethylphenyl-4-hydroxyphenyl)sulphide, 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol, and 2,2,2′,2′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diol.

42. A expandable or expanded composition according to claim 34 wherein R2 is derived from at least one dihydroxy-substituted aromatic hydrocarbon selected from the group consisting of those of the formula (IX):

43. A expandable or expanded composition according to claim 42 wherein R2 is derived from bisphenol A.

44. A expandable or expanded composition according to claim 34 further comprising structural units derived from at least one chain termination agent.

45. A expandable or expanded composition according to claim 44 wherein the chain termination agent is at least one unsubstituted or substituted member selected from the group consisting of alkyl halides, alkyl chlorides, aryl halides, aryl chlorides, and chlorides of formulas (XVII) and (XVIII):

46. A expandable or expanded composition according to claim 45 wherein the chain termination agent is at least one member selected from the group consisting of monochlorobenzophenone, monochlorodiphenylsulfone; a monochlorophthalimide; 4-chloro-N-methylphthalimide, 4-chloro-N-butylphthalimide, 4-chloro-N-octadecylphthalimide, 3-chloro-N-methylphthalimide, 3-chloro-N-butylphthalimide, 3-chloro-N-octadecylphthalimide, 4-chloro-N-phenylphthalimide, 3-chloro-N-phenylphthalimide; a mono-substituted bis-phthalimide; a monochlorobisphthalimidobenzene; 1-[N-(4-chlorophthalimido)]-3-(N-phthalimido)benzene; 1-[N-(3-chlorophthalimido)]-3-(N-phthalimido)benzene; monochlorobisphthalimidodiphenyl sulfone, monochlorobisphthalimidodiphenyl ketone, a monochlorobisphthalimidophenyl ether; 4-[N-(4-chlorophthalimido)]phenyl-4′-(N-phthalimido)phenyl ether; 4-[N-(3-chlorophthalimido)phenyl]-4′-(N-phthalimido)phenyl ether, and the corresponding isomers of the latter two compounds derived from 3,4′-diaminodiphenyl ether.

47. A expandable or expanded composition according to claim 34 wherein the weight ratio of units of formula I to those of formula II is in the range of between about 99:1 and about 25:75.

48. A expandable or expanded composition according to claim 34 wherein the expandable or expanded composition has a heat distortion temperature at 0.455 MPa of at least 205° C.

49. A expandable or expanded composition according to claim 34 wherein the expandable or expanded composition has a heat distortion temperature at 0.455 MPa of at least 210° C.

50. A expandable or expanded composition according to claim 34 wherein the expandable or expanded composition has a temperature of transition between the brittle and ductile states of at most 30° C. as measured by ASTM method D3763.

51. The expandable or expanded composition according to claim 1 further comprising a reinforcing filler.

52. The expandable or expanded composition according to claim 1 further comprising an electrically conductive additive.

53. The expandable or expanded composition according to claim 1 wherein the expandable or expanded composition comprises multiple layers.

54. The expanded composition according to claim 1 wherein the expanded composition has a bulk density of 3 to 25 kilograms per cubic meter.

55. The expanded material according to claim 54 wherein the expanded material is flexible.

56. The expanded material according to claim 55 wherein the expanded material is rigid.

57. The expandable or expanded material of claim 1 further comprising one or more fillers.

58. An article comprising the expanded material of claim 1 laminated to one or more films or sheets.

59. The article according to claim 58 wherein the film or sheet comprises either: a) an immiscible blend of polymers having more than one glass transition temperature and one of the polymers has a glass transition temperature greater than 180 degrees Celsius; b) a miscible blend of polymers having a single glass transition temperature greater than 217 degrees Celsius; or, c) a single virgin polymer having a glass transition temperature of greater than 247 degrees Celsius.

60. An article comprising two or more portions of the expanded material of claim 1 adhered together.