Methods of manufacture of bis(ether anhydride)s and polyetherimides

1. A method for the manufacture of a bis(ether anhydride), the method comprising

contacting an N-substituted bis(ether phthalimide) with a base under conditions effective to ring open the N-substituted bis(ether phthalimide) to provide a ring-opened product wherein the ring-opened product comprises a bis(ether) diacid diamide salt of the formula

and

optionally a bis(ether) triacid amide salt of the formula

and

optionally a bis(ether) tetracid salt of the formula

wherein in the foregoing formulas,

R is a C 1-12 alkyl;

M is an alkaline metal; and

T is —O— or a group of the formula —O—Z—O—, wherein

Z is of the formula

wherein

R a and R b are each independently a halogen atom or a monovalent C 1-6 alkyl group;

p and q are each independently integers of 0 to 4;

c is 0 to 4; and X a is a bridging group connecting the ether-substituted aromatic groups, where the bridging group and the ether substituent of each C 6 arylene group are disposed ortho, meta, or para to each other on the C 6 arylene group; and

contacting the ring-opened product with an acid under conditions effective to provide a composition comprising the bis(ether anhydride).

2. The method of claim 1 , wherein contacting the N-substituted bis(ether phthalimide) with a base is conducted in the presence of water and optionally an organic co-solvent.

3. The method of claim 2 , wherein the organic co-solvent comprises an optionally substituted C 1-6 aliphatic alcohol.

4. The method of claim 1 , wherein the base is an alkali hydroxide, an alkali carbonate, an alkali bicarbonate, or a combination comprising at least one of the foregoing.

5. The method of claim 1 , wherein the molar ratio of the base relative to the N-substituted bis(ether phthalimide) is 1:1 to 100:1.

6. The method of claim 1 , wherein contacting the N-substituted bis(ether phthalimide) with a base is conducted in the presence of a phase transfer catalyst.

7. The method of claim 6 , wherein the phase transfer catalyst comprises a guanadinium salt, a quaternary ammonium salt, a quaternary phosphonium salt, a pyridinium salt, an imidazolium salt, a tertiary amine, a polyether, a glycol ether, or a combination comprising at least one of the foregoing.

8. The method of claim 6 , wherein the phase transfer catalyst is present in an amount of 0.1 to 8 mol %, based on the total moles of the N-substituted bis(ether phthalimide).

9. The method of claim 1 , wherein contacting an N-substituted bis(ether phthalimide) with a base is conducted at a temperature of 70 to 130° C.

10. The method of claim 1 , wherein the acid comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or a combination comprising at least one of the foregoing.

11. The method of claim 1 , wherein contacting the ring-opened product with an acid comprises:

contacting the ring-opened product with an inorganic acid under conditions effective to hydrolyze amide groups in the ring-opened product to provide a bis(ether phthalic acid);

removing the inorganic acid; and

heating the bis(ether phthalic acid) to provide a composition comprising the bis(ether anhydride).

12. The method of claim 11 , wherein the bis(ether phthalic acid) is formed at a temperature of 90 to 140° C.

13. The method of claim 11 , wherein heating the bis(ether phthalic acid) is carried out at a temperature of 140 to 220° C.

14. The method of claim 1 , wherein contacting the ring-opened product with the inorganic acid is conducted in the presence of a non-polar aromatic solvent comprising ortho-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, benzene, toluene, xylene, dichlorotoluene, 1,2,4-trichlorobenzene, chlorobenzene, bromobenzene, diphenyl sulfone, sulfolane, phenetole, anisole, or a combination comprising at least one of the foregoing.

15. The method of claim 1 , further comprising heating the composition comprising the bis(ether anhydride) to convert additional bis(ether phthalic acid) to the bis(ether anhydride).

16. The method of claim 1 , wherein the N-substituted bis(ether phthalimide) is of the formula

and the bis(ether anhydride) is of the formula

wherein in the foregoing formulas,

R is a C 1-5 alkyl; and

T is —O— or a group of the formula —O—Z—O—, wherein

Z is of the formula

wherein

R a and R b are each independently a halogen atom or a monovalent C 1-6 alkyl group;

p and q are each independently integers of 0 to 4;

c is 0 to 4; and X a is a bridging group connecting the ether-substituted aromatic groups, where the bridging group and the ether substituent of each C 6 arylene group are disposed ortho, meta, or para to each other on the C 6 arylene group.

17. The method of claim 16 , wherein Z is 2,2-(4-phenylene)isopropylidene.

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

manufacturing a bis(ether anhydride) in accordance with a method of claim 1 ; and

polymerizing the bis(ether anhydride) and a diamine to provide a polyetherimide composition.