METHODS OF MANUFACTURE OF POLYETHERIMIDES

1 . A method for the manufacture of a polyetherimide composition, the method comprising

contacting a substituted phthalic anhydride and an organic diamine in the presence of diphenyl sulfone or sulfolane or a combination comprising at least one of the foregoing solvents at a temperature of greater than 130° C.,

wherein the substituted phthalic anhydride has a formula

and

the organic diamine has a formula

H 2 N—R—NH 2

to provide a bis(phthalimide) composition comprising diphenyl sulfone or sulfolane or a combination comprising at least one of the foregoing solvent and a bis(phthalimide) of the formula

and

polymerizing the bis(phthalimide) and an alkali metal salt of a dihydroxy aromatic compound of the formula

MO—Z—OM

in the presence of diphenyl sulfone or sulfolane or a combination comprising at least one of the foregoing solvents to form a polyetherimide of the formula

wherein in the foregoing formulae

X is fluoro, chloro, bromo, iodo, nitro, or a combination comprising at least one of the foregoing;

R is an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, —(C 6 H 10 ) z — wherein z is an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups, and a divalent group of the formula

 wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing;

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 comprising at least one of the foregoing; and

n is an integer greater than 1.

2 . The method of claim 1 , wherein the stoichiometric ratio of the substituted phthalic anhydride to the organic diamine is 1.95:1 to 2.05:1, and the stoichiometric ratio of the bis(phthalimide) to the alkali metal salt of the dihydroxy aromatic compound is 0.9:1 to 1.1:1.

3 . The method of claim 1 , wherein

weight





of





bis



(

phthalimide

)

weight





of





bis



(

phthalimide

)

+

weight





of





diphenyl





sulphone





or





sulfolane



(

100

)

is 1 to 30%.

4 . The method of claim 1 , further comprising

determining the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine during the imidization of the substituted phthalic anhydride and the organic diamine; and

optionally adjusting the stoichiometric molar ratio by adding additional substituted phthalic anhydride or organic diamine.

5 . The method of claim 1 , further comprising heating the diphenyl sulfone to a temperature of greater than 130° C., and combining the substituted phthalic anhydride and the organic diamine with the heated diphenyl sulfone.

6 . The method of claim 1 , further comprising adding a monofunctional reactant to the substituted phthalic anhydride, the organic diamine, the diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing.

7 . The method of claim 1 , wherein the contacting is conducted at a temperature of 130° C. to 250° C.

8 . The method of claim 1 , wherein the contacting is conducted in the absence of an imidization catalyst.

9 . The method of claim 1 , wherein the polymerization is conducted in the absence of a polymerization catalyst.

10 . The method of claim 1 , wherein the polymerization is conducted in the presence of a polymerization catalyst.

11 . The method of claim 1 , wherein

X is chloro, fluoro, bromo, or nitro, and

R is a divalent radical of the formula —(C 6 H 10 ) z — wherein z is an integer from 1 to 4,

or a combination comprising at least one of the foregoing, wherein Q 1 is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing.

12 . The method of claim 1 , wherein X is chloro and R is m-phenylene, p-phenylene, an arylene ether, a diarylsulfone, a group of the formula

wherein Q 1 — is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing, preferably wherein R is m-phenylene, p-phenylene, para, para-diphenyl ether, 4,4-diphenylsulfone, or a combination comprising at least one of the foregoing.

13 . The method of claim 1 , wherein the dihydroxy aromatic compound comprises bisphenol A, hydroquinone, biphenol, resorcinol, or a combination comprising at least one of the foregoing.

14 . The method of claim 1 , wherein the dihydroxy aromatic compound is in a powder form or in a slurry form.

15 . The method of claim 1 , wherein the dihydroxy aromatic compound is dispersed in a solvent comprising ortho-dichlorobenzene, xylenes, toluene, diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing.

16 . The method of claim 1 , wherein the dihydroxy aromatic compound is dispersed in ortho-dichlorobenzene.

17 . The method of claim 1 , wherein the bis(phthalimide) composition and the polyetherimide composition are manufactured in the same vessel.

18 . A method for the manufacture of a polyetherimide composition, the method comprising

contacting a substituted phthalic anhydride and an organic diamine in the presence of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents at a temperature of 130° C. to 250° C.,

wherein the substituted phthalic anhydride has a formula

and

the organic diamine has a formula

H 2 N—R—NH 2

to provide a bis(phthalimide) composition comprising diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents and a bis(phthalimide) of the formula

and

polymerizing the bis(phthalimide) and a sodium salt of a potassium salt of bisphenol A in the presence of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents to form a polyetherimide of the formula

wherein in the foregoing formulae

X is chloro;

R is m-phenylene, p-phenylene, p,p-diphenylether, or 4,4′-diphenylsulfone;

Z is

and

n is an integer greater than 1.

19 . A polyetherimide composition manufactured by a method of claim 1 .

20 . A polyetherimide composition wherein the polyetherimide has a structure of the formula

wherein

R is an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, —(C 6 H 10 ) z — wherein z is an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups, and a divalent group of the formula

wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing; 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 comprising at least one of the foregoing; and

n is an integer greater than 1;

preferably wherein

R is m-phenylene, p-phenylene, p,p-diphenylether, or 4,4′-diphenylsulfone;

Z is

and

n is an integer from 10 to 50; and

wherein

the composition comprises one or more of

greater than 0.1 parts per million of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing, or

greater than 1 part per million of sodium or potassium, or a yellowness index of less than 300.