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 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

and 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,

the polyetherimide being a catalyzed polymerization reaction product of the bis(halophthalimide) composition and a 1.6 to 2.0 mole % excess 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 as defined above,

in the presence of from 2 to 4 mole % of an endcapping agent selected from derivatives of sodium phenoxide, and

wherein the polyetherimide has:

a Tg above 220° C.;

20 wt. % to 35 wt. % solids;

an Mw of at least 42,000 Daltons;

a maximum chloride content of less than 900 ppm by weight;

a maximum of 700 ppm by weight OH endgroup polymer functionality; and

the low shear viscosity of the polyetherimide is at least 30% lower than a polyetherimide made from a bis(halophthalimide) composition comprising less than 10 wt. % of the 4,3′-bis(halophthalimide).

2. 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).

3. 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 85 wt. % of the 4,3′-bis(halophthalimide), and

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

4. 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.

5. 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.

6. 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.

7. 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.

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

and

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

wherein R is as defined above.

9. The composition of claim 8 , 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).

10. A method for the manufacture of a polyetherimide composition, the method comprising reacting:

from 1.6 to 2.0 mole % excess 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

and

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 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 X is independently fluoro, chloro, bromo, or iodo; and

adding from 2 to 4 mole % of a derivative of sodium phenoxide to the polyetherimide; to produce a polyetherimide of the formula

wherein n is greater than 1, each R is the same or different and is as defined above, each Z is the same or different, and is 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 polyetherimide has:

a Tg of greater than 220° C.;

20 to 35 wt. % solids;

an Mw of at least 42,000 Daltons;

a maximum chloride content of 900 ppm;

a maximum of 700 ppm OH endgroup polymer functionality; and

the low shear viscosity of the polyetherimide is at least 30% lower than a polyetherimide made from a bis(halophthalimide) composition comprising less than 10% of 4,3′-bis(halophthalimide.

11. The method of claim 10 , wherein the derivative of sodium phenoxide is sodium para cumyl phenol.

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 14 , selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

16. The article of claim 14 , wherein the article is a connector for electronic or electrical applications.

17. The article of claim 15 , the article comprising

(i) a polytetrafluoroethylene substrate having a first surface,

(ii) a metal substrate having a second surface, and

(iii) the polymer composition situated between the polytetrafluoroethylene substrate and the metal substrate.

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

19. The method of claim 18 , further comprising molding the composition to form an article having a thickness from 1 to 5 millimeters.