Polyetherimides, methods of manufacture, and articles formed therefrom

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 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 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

more than 10 wt. % of a 4,3′-bis(halophthalimide) of the formula

 and

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 polyetherimide comprises, based on parts of the polyetherimide,

less than 100 parts per million each of the 3,3′-bis(halophthalimide), 4,3′-bis(halophthalimide), and 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

 and

less than 2000 parts per million of halide ion; and

less than 4.7 wt.% of a cyclic adduct of the dihydroxy aromatic compound and the bis(halophthalimide) composition, wherein R is as defined above.

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, 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

more than 10 wt. % of a 4,3′-bis(halophthalimide) of the formula

 and

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 20 carbon atoms, a cycloalkylene group having 3 to 20 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 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, 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, and each X is independently fluoro, chloro, bromo, or iodo,

wherein the polyetherimide comprises, based on parts of the polyetherimide,

less than 100 parts per million each of the 3,3′-bis(halophthalimide), 4,3′-bis(halophthalimide), and 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

 and

less than 2000 parts per million of halide ion; and

less than 4.7 wt.% of a cyclic adduct of the dihydroxy aromatic compound and the bis(halophthalimide) composition, wherein R is as defined above.

3. The composition of claim 1 , wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of the 4,3′-bis(chlorophthalimide) and less than 15 wt. % of the 4,4′-bis(chlorophthalimide), and

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 less than 10 wt. % of the 4,3′-bis(chlorophthalimide) and more than 15 wt. % of the 4,4′-bis(chlorophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample.

4. The composition of claim 1 , wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of the 4,3′-bis(chlorophthalimide), and less than 15 wt. % of 4,4′-bis(chlorophthalimide), and

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 15 wt. % of the 4,4′-bis(chlorophthalimide), each determined by dynamic mechanical analysis over 30° C. to 210° C., on a molded sample.

5. The composition of claim 1 , wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of a 4,3′-bis(chlorophthalimide), and less than 15 wt. % of 4,4′-bis(chlorophthalimide), 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 a bis(chlorophthalimide) composition comprising less than 10 wt. % of one or both of the 4,3′-bis(chlorophthalimide) and more than 15 wt. % of the 4,4′-bis(chlorophthalimide), each determined by parallel plate rheometry.

6. The composition of claim 1 , wherein

R 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; 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.

7. The composition of claim 6 , wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene diarylsulfone, or a combination thereof.

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

from 15 to less than 53 wt. % of the 3,3′-bis(halophthalimide),

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

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

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 absorbers, plasticizers, lubricants, mold release agents, antistatic agents, colorants, blowing agents, flame retardants, anti-drip agents, and radiation stabilizers, and a combination thereof.

10. 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 a dihydroxy aromatic compound with the bis(halophthalimide) composition.

11. The method of claim 10 , 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.

12. An article comprising the composition of claim 1 .

13. The article of claim 12 , selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

14. The article of claim 13 , wherein the article is a molded part having a thickness from 1 to 5 millimeters.

15. The article of claim 12 , selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

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

17. A polyetherimide of the formula

wherein

based on the total weight percent of the —O—Z—O— groups in the polyetherimide,

from more than more than 0 to less than 15 mole percent of the —O—Z—O— groups are in the 3,3′ position,

more than 17 less than 85 mole percent of the —O—Z—O— groups are in the 3,4′, and 4′,3 positions, and

from more than 0 to less than 27 mole percent of the —O—Z—O— groups are 4,4′ position;

n is greater than 1;

each R is independently 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 20 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; and

each Z is independently 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,

wherein the polyetherimide comprises, based on parts of the polyetherimide,

less than 100 parts per million each of the 3,3′-bis(halophthalimide), 4,3′-bis(halophthalimide), and 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

 and

less than 2000 parts per million of halide ion; and

less than 4.7 wt.% of a cyclic adduct of the dihydroxy aromatic compound and the bis(chlorophthalimide), wherein R is as defined above.

18. The polyetherimide of claim 17 , comprising from more than 47 wt. % to less than 85 wt. % of the —O—Z—O— groups in the 3,4′, and 4′,3 positions.

19. The polyetherimide of claim 17 , comprising

from 15 to less than 85 mol % of the of the —O—Z—O— groups in the 3,3′ position,

from more than 47 to less than 85 mol % of the O—Z—O— groups in the 4,3′ and 3,4′ positions, and

from more than 0 to less than 27 mol % of the O—Z—O— groups in the 4,4′ position.