Methods of manufacture for polyetherimide

1. A method of making polyetherimide comprising:

reacting a diamine having four bonds between the amine groups, a diamine having greater than or equal to five bonds between the amine groups, 4-halophthalic anhydride and 3-halophthalic anhydride at an imidization reaction temperature and pressure in the presence of a solvent and a polymer additive to produce a mixture comprising 3,3′-bis(halophthalimide)s, 3,4′-bis(halophthalimide)s, 4,4′-bis(halophthalimide)s, solvent and the polymer additive wherein the molar ratio of 3-halophthalic anhydride to 4-halophthalic anhydride is 98:02 to 50:50 and the molar ratio of the diamine having four bonds to the diamine having greater than or equal to five bonds between the amine groups is 98:02 to 02:98; and

reacting the mixture with an alkali metal salt of a dihydroxy aromatic compound to produce a polyetherimide having a cyclics content less than or equal to 5 weight percent, based on the total weight of the polyetherimide, a glass transition temperature greater than or equal to 216° C., and a weight average molecular weight greater than or equal to 25,000 Daltons; wherein the polymer additive dissolves in the solvent at the imidization reaction temperature and pressure;

wherein the polymer additive is present in an amount of 5 to 7.5 wt %, based on the weight of the polyetherimide produced.

2. The method of claim 1 , wherein the diamine having four bonds between the amine groups comprises an aromatic diamine having amine groups located on the aromatic ring in a meta relationship and the diamine having greater than or equal to five bonds between the amine groups comprises an aromatic diamine having amine groups located on the aromatic ring in a para relationship.

3. The method of claim 1 wherein the diamine having four bonds between the amine groups comprises m-phenylenediamine, and the diamine having greater than or equal to five bonds between the amine groups comprises one or more of p-phenylenediamine and 4,4′-diaminodiphenyl sulfone.

4. The method of claim 1 , wherein the molar ratio of diamine having 4 bonds between amine groups relative to diamine having greater than or equal to 5 bonds between the amine groups is 98:2 to 60:40.

5. The method of claim 1 , wherein the molar ratio of diamine having 4 bonds between amine groups relative to diamine having greater than or equal to 5 bonds between the amine groups is 90:10 to 10:90.

6. The method of claim 2 , wherein the molar ratio of diamine having amine groups in a meta relationship relative to diamine having amine groups in a para relationship is 98:2 to 60:40.

7. The method of claim 2 , wherein the molar ratio of diamine having amine groups in a meta relationship relative to diamine having amine groups in a para relationship is 90:10 to 10:90.

8. The method of claim 3 , wherein the molar ratio of m-phenylenediamine relative to the one or more of p-phenylenediamine and 4,4′-diaminodiphenyl sulfone is 98:2 to 60:40.

9. The method of claim 3 , wherein the molar ratio of m-phenylenediamine relative to the one or more of p-phenylenediamine and 4,4′-diaminodiphenyl sulfone is 90:10 to 10:90.

10. The method of claim 1 , wherein the solvent comprises ortho-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, anisole, veratrole, diphenyl ether, diphenyl sulfone, sulfolane, dimethyl sulfone, dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, hexamethyl phosphoramide, dimethyl imidazole, or a combination thereof.

11. The method of claim 1 , wherein the polymer additive comprises a polyetherimide, a polyamideimide, a polyethersulfone, a polyaryl ether ketone, a liquid crystal polymer, a polyimide or a combination thereof.

12. The method of claim 1 , wherein the imidization reaction temperature is greater than or equal to 110° C., and the imidization reaction pressure is greater than 0 to 7 atmospheres.

13. The method of claim 1 , wherein the mixture has a solids content of 20 to 55 wt %.

14. The method of claim 1 , wherein the polyetherimide has a cyclics content of 0.1 to 5 wt %.

15. The method of claim 1 , wherein the alkali metal salt of a dihydroxy aromatic compound is an alkali metal salt of bisphenol A.

16. The method of claim 1 , wherein the polyetherimide has a viscosity that is at least 25% lower than the viscosity of a polyetherimide produced using a molar ratio of 3-halophthalic anhydride to 4-halophthalic anhydride of 05:95, when viscosity is determined using Parallel Plate Rheometry at 380° C.

17. A method of making polyetherimide comprising:

reacting an aromatic diamine having amine groups located on the aromatic ring in a meta relationship, an aromatic diamine having amine groups located on the aromatic ring in a para relationship, 4-halophthalic anhydride and 3-halophthalic anhydride at an imidization reaction temperature and pressure in the presence of a solvent and a polymer additive to produce a mixture comprising 3,3′-bis(halophthalimide), 3,4′-bis(halophthalimide), 4,4′-bis(halophthalimide), solvent and the polymer additive wherein the molar ratio of 3-halophthalic anhydride to 4-halophthalic anhydride is 98:02 to 50:50 and the molar ratio of the diamine having amine groups in a meta relationship to the diamine having amine groups in a para relationship is 98:02 to 02:98; and

reacting the mixture with alkali metal salt of a dihydroxy aromatic compound to produce a polyetherimide having a cyclics content less than or equal to 5 weight percent based on the total weight of the polyetherimide, a glass transition temperature greater than or equal to 216° C., and a weight average molecular weight greater than or equal to 25,000 Daltons; wherein the polymer additive dissolves in the solvent at the imidization reaction temperature and pressure and wherein the polymer additive comprises a polyetherimide, a polyamideimide, a polyethersulfone, a polyaryl ether ketone, a liquid crystal polymer, a polyimide or a combination thereof;

wherein the polymer additive is present in an amount of to 7.5 wt %, based on the weight of the polyetherimide produced.

18. A method of making a polyetherimide comprising:

reacting 4-halophthalic anhydride and 3-halophthalic anhydride with m-phenylenediamine, and one or more of p-phenylenediamine and 4,4′-diaminodiphenyl sulfone, at an imidization reaction temperature and pressure in the presence of a solvent and a polymer additive to produce a mixture comprising:

3,3′-bis(halophthalimide) having formula (I)

wherein R is m-phenylene;

3,3′-bis(halophthalimide) having formula (I)

wherein R is p-phenylene, p-diphenylsulfone or a combination thereof;

3,4′-bis(halophthalimide) having formula (II)

wherein R is m-phenylene;

3,4′-bis(halophthalimide) having formula (II)

wherein R is p-phenylene, p-diphenylsulfone or a combination thereof;

4,4′-bis(halophthalimide) having formula (III)

wherein R is m-phenylene;

4,4′-bis(halophthalimide) having formula (III)

wherein R is p-phenylene, p-diphenylsulfone or a combination thereof, solvent, and polymer additive; and wherein the molar ratio of 3-halophthalic anhydride to 4-halophthalic anhydride is 98:02 to 50:50 and the molar ratio of the m-phenylenediamine to the one or more of p-phenylenediamine and 4,4′-diaminodiphenyl sulfone is 98:02 to 02:98; and

reacting the mixture with an alkali metal salt of a dihydroxy aromatic compound to produce a polyetherimide having a cyclics content less than or equal to 5 weight percent, based on the total weight of the polyetherimide, a glass transition temperature greater than or equal to 216° C., and a weight average molecular weight greater than or equal to 25,000 Daltons; wherein the polymer additive dissolves in the solvent at the imidization reaction temperature and pressure and wherein the polymer additive comprises a polyetherimide, a polyamideimide, a polyethersulfone, a polyaryl ether ketone, a liquid crystal polymer, a polyimide or a combination thereof;

wherein the polymer additive is present in an amount of to 7.5 wt %, based on the weight of the polyetherimide produced.