Polyetherimides, methods of manufacture, and articles formed therefrom
View Patent ↗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
1. A polymer composition comprising a polyetherimide having the formula
wherein
n is greater than 1,
each R is the same or different, and is selected from an aromatic hydrocarbon group having 6 to 30 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent group of the formula
wherein Q 1 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is 1 to 5 and a halogenated derivative thereof,
each Z is the same or different, and is an aromatic C 6-24 monocyclic or polycylic polycyclic moiety optionally substituted with 1 to 6 C 1-18 alkyl groups, 1 to 8 halogen atoms, or a combination thereof , and
the divalent bonds between the —O—Z—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions, the divalent bonds of the —O—Z—O—group being made from 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
wherein each X is independently fluoro, chloro, bromo, or iodo and R is as defined above,
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and an alkali metal salt of a dihydroxy aromatic compound of the formula
MO—Z—OM
wherein M is an alkali metal and Z in the dihydroxy aromatic compound is the same as the Z in polyetherimide; and
wherein the polyetherimide has a glass transition temperature of greater than 180° C.
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
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
wherein
each R is selected from an aromatic hydrocarbon group having 6 to 30 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent group of the formula
wherein Q′ is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is 1to 5 and a halogenated derivative thereof, and
each X is independently fluoro, chloro, bromo, or iodo, and further wherein
the polyetherimide is of the formula
wherein n is greater than 1, each R is the same or different, each Z is the same or different, and are as defined above, and the divalent bonds between the —O—Z—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions,
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and the alkali metal salt of the formula
MO—Z—OM.
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
less than 100 parts per million of a bisphthalimide of the formula
less than 200 parts per million of a total of the 3,3′-bis(halophthalimide), the 4,3 ′-bis(halophthalimide), the 4,4′-bis(halophthalimide), and the halo(bisphthalimide).
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
wherein Q 1 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is an integer from 1 to 5 and a halogenated derivative thereof; and
Z is a divalent group of formula
wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y —wherein y is an integer from 1 to 5 and a halogenated derivative thereof.
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.
12. A polymer composition comprising a polyetherimide of the formula
wherein
n is greater than 1,
each R is the same or different, and wherein R is selected from an aromatic hydrocarbon group having 6 to 30 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent group of the formula
wherein Q 1 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y —wherein y is 1 to 5, and a halogenated derivative thereof,
each Z is the same or different and 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, and
the divalent bonds between the —O—Z—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions, the divalent bonds between —O—Z—O—group and the phenyl substituents being made from 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
wherein R is as defined above;
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and an alkali metal salt of a dihydroxy aromatic compound of the formula
MO—Z—OM
wherein M is an alkali metal and Z in the dihydroxy aromatic compound is the same as the Z in polyetherimide; and
wherein the polyetherimide has a glass transition temperature of greater than 180° C.
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
wherein Q is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is an integer from 1 to 5 and a halogenated derivative thereof, with
a bis(chlorophthalimide) composition comprising, based on the weight of the bis(chlorophthalimide) composition,
at least 15 wt.% of a 3,3′-bis(chlorophthalimide) of the formula
from more than 17 wt.% to less than 85 wt.% of a 4,3′-bis(chlorophthalimide) of the formula
from more than 0 to less than 27 wt.% of a 4,4′-bis(chlorophthalimide) of the formula
wherein
each R is a divalent group of the formula
and
Q 1 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y —wherein y is 1 to 5, and a halogenated derivative thereof, further wherein
the polyetherimide is of the formula
wherein n is greater than 1, each R is the same or different, each Z is the same or different, and are as defined above, and the divalent bonds between the —OZ—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions;
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and the alkali metal salt of the formula
MO—Z—OM.
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
less than 100 parts per million of a bisphthalimide of the formula
less than 200 parts per million of a total of the 3,3′-bis(chlorophthalimide), the 4,3′-bis(chlorophthalimide), the 4,4′-bis(chlorophthalimide), and the chloro(bisphthalimide).
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.
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.
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.
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.
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.
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.
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.