Method for the preparation poly(etherimide)s

1. A method for the synthesis of an activated bisimide, comprising

reacting 4-halotetrahydrophthalic anhydride with a primary amine having the formula A-NH 2 to yield an N-substituted-4-halotetrahydrophthalimide wherein A is a group which activates the tetrahydrophthalimide ring system to aromatization;

aromatizing activated 4-halotetrahydrophthalimide in the presence of a catalyst to yield an activated 4-halophthalimide; and

treating activated 4-halophthalimide (V) with a disodium salt of a dihydroxy compound having the structure HO—S—OH, to yield the activated bisimide (VI):

wherein S comprises a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a substituted straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, a substituted cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms or a substituted arylene group having from 6 to about 20 carbon atoms.

2. The method of claim 1 , wherein S is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of arylene groups having from about 6 to 20 carbons.

3. The method of claim 1 , wherein the dihydroxy compound is a bis(phenol) having the formula (XIII):

wherein T is selected from the group consisting of a single bond linking the two aryl groups, a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms; an arylene group having from 6 to about 20 carbon atoms, sulfide, carbonyl, sulfoxide, ether and mixtures thereof.

4. The method of claim 3 , wherein T is selected from the group consisting of 2,2-bis[4-hydroxyphenyl]propane; 4,4′-bis(4-hydroxyphenyl)diphenyl ether; 4,4′-bis(4-phenoxy)diphenyl sulfide; 4,4′-bis(4-hydroxyphenyl)benzophenone; 4,4′-bis(4-hydroxyphenyl)diphenyl sulfone; 2,2-bis[4-(3-hydroxyphenyl) phenyl]propane; 4,4′-bis(3-hydroxyphenyl)diphenyl ether; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfide; 4,4′-bis(3-hydroxyphenyl)benzophenone; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfone; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl-2,2-propane; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl ether; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfide; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfone dianhydride, and mixtures thereof.

5. The method of claim 3 , wherein the dihydroxy compound is bisphenol A.

6. The method of claim 1 , wherein A is selected from the group consisting of pyridine, chloropyridine, nitropyridine, pyrimidine, pyrazine, thiazole, methylthiazole, benzothiazole, 1,3,4-thiadiazole, and benzotriflouride.

7. The method of claim 1 , wherein A is 2-pyridyl.

8. The method of claim 1 , wherein the catalyst is copper based.

9. The method of claim 8 , wherein the catalyst further comprises activated carbon.

10. A method for the synthesis of poly(etherimide)s, comprising

reacting 4-halotetrahydrophthalic anhydride with a primary amine having the formula A-NH 2 to yield an N-substituted-4-halotetrahydrophthalimide wherein A is a group which activates the tetrahydrophthalimide ring system to aromatization;

aromatizing N-substituted-4-halotetrahydrophthalimide in the presence of a catalyst to yield an N-substituted-4-halophthalimide; and

treating N-substituted-4-halophthalimide with a disodium salt of a dihydroxy compound having the structure HO—S—OH, to yield the activated bisimide (VI);

wherein S comprises a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a substituted straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, a substituted cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms or a substituted arylene group having from 6 to about 20 carbon atoms; and

reacting activated bisimide (XII) with a diamine to form a poly(etherimide) and the primary amine.

11. The method of claim 10 , wherein S is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of arylene groups having from about 6 to 20 carbons.

12. The method of claim 11 , wherein the dihydroxy compound is a bis(phenol) having the formula (XIII):

wherein T is selected from the group consisting of a single bond linking the two aryl groups, a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms; an arylene group having from 6 to about 20 carbon atoms, sulfide, carbonyl, sulfoxide, ether and mixtures thereof.

13. The method of claim 12 , wherein the T is selected from the group consisting of 2,2-bis[4-hydroxyphenyl]propane; 4,4′-bis(4-hydroxyphenyl)diphenyl ether; 4,4′-bis(4-phenoxy)diphenyl sulfide; 4,4′-bis(4-hydroxyphenyl)benzophenone; 4,4′-bis(4-hydroxyphenyl)diphenyl sulfone; 2,2-bis[4-(3-hydroxyphenyl)phenyl]propane; 4,4′-bis(3-hydroxyphenyl)diphenyl ether; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfide; 4,4′-bis(3-hydroxyphenyl)benzophenone; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfone; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl-2,2-propane; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl ether; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfide; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfone dianhydride, and mixtures thereof.

14. The method of claim 10 , wherein A is selected from the group consisting of pyridine, chloropyridine, nitropyridine, pyrimidine, pyrazine, thiazole, methylthiazole, benzothiazole, 1,3,4-thiadiazole, and benzotriflouride.

15. The method of claim 10 , wherein A is 2-pyridyl.

16. The method of claim 10 , wherein the diamine has the structure H 2 N-Z-NH 2 , wherein Z is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of an arylene group having from 6 to about 20 carbon atoms, and diarylene radicals of the following general formula (XV):

wherein Q includes, but is not limited to, the formula (XVI):

wherein y is an integer from about 1 to about 5, methylene, ethylene, propylene, isopropylene, n-butylene, 1,3-phenylene, naphthylene, and mixtures thereof.

17. The method of claim 10 , wherein the catalyst is copper based.

18. The method of claim 17 , wherein the catalyst further comprises activated carbon.

19. The method of claim 10 further comprising recycling the primary amine.

20. A method for the synthesis of poly(etherimide)s, comprising

reacting 4-halotetrahydrophthalic anhydride with a primary amine having the formula A-NH 2 to yield an N-substituted-4-halotetrahydrophthalimide wherein A is a group which activates the tetrahydrophthalimide ring system to aromatization;

aromatizing the N-substituted-4-halotetrahydrophthalimide in the presence of a catalyst to yield an N-substituted-4-halophthalimide; and

treating N-substituted-4-halophthalimide with a disodium salt of a dihydroxy compound having the structure HO—S—OH, to yield the activated bisimide (VI); and

converting the activated bisimide (VI) to dianhydride (VIII)

wherein S comprises a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a substituted straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, a substituted cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms or a substituted arylene group having from 6 to about 20 carbon atoms

and reacting dianhydride (VIII) with a diamine to yield a poly(etherimide).

21. The method of claim 20 , wherein S is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of arylene groups having from about 6 to 20 carbons.

22. The method of claim 20 , wherein the dihydroxy compound is a bis(phenol) having the formula (XIII):

wherein T is selected from the group consisting of a single bond linking the two aryl groups, a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms; an arylene group having from 6 to about 20 carbon atoms, sulfide, carbonyl, sulfoxide, ether and mixtures thereof.

23. The method of claim 22 , wherein T is selected from the group consisting of 2,2-bis[4-hydroxyphenyl]propane; 4,4′-bis(4-hydroxyphenyl)diphenyl ether; 4,4′-bis(4-phenoxy)diphenyl sulfide; 4,4′-bis(4-hydroxyphenyl)benzophenone; 4,4′-bis(4-hydroxyphenyl)diphenyl sulfone; 2,2-bis[4-(3-hydroxyphenyl)phenyl]propane; 4,4′-bis(3-hydroxyphenyl)diphenyl ether; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfide; 4,4′-bis(3-hydroxyphenyl)benzophenone; 4,4′-bis(3-hydroxyphenyl)diphenyl sulfone; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl-2,2-propane; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl ether; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfide; 4-(3-hydroxyphenyl)-4′-(4-hydroxyphenyl)benzophenone, and 4-(hydroxyphenyl)-4′-(4-hydroxyphenyl)diphenyl sulfone dianhydride, and mixtures thereof.

24. The method of claim 20 , wherein A is selected from the group consisting of pyridine, chloropyridine, nitropyridine, pyrimidine, pyrazine, thiazole, methylthiazole, benzothiazole, 1,3,4-thiadiazole, and benzotriflouride.

25. The method of claim 20 , wherein A is 2-pyridyl.

26. The method of claim 20 , wherein the diamine has the structure H 2 N-Z-NH 2 , wherein Z is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of an arylene group having from 6 to about 20 carbon atoms, and diarylene radicals of the following general formula (XV):

wherein Q includes, but is not limited to, the formula (XVI):

wherein y is an integer from about 1 to about 5, methylene, ethylene, propylene, isopropylene, n-butylene, 1,3-phenylene, naphthylene, and mixtures thereof.

27. The method of claim 20 , wherein the activated bisimide (VI) is converted to dianhydride (VIII) by reacting the activated bisimide with phthalic anhydride.

28. The method of claim 20 , wherein the activated bisimide (VI) is converted to dianhydride (VIII) by hydrolysis ring closure.

29. The method of claim 20 , wherein the catalyst is copper based.

30. The method of claim 29 , wherein the catalyst further comprises activated carbon.

31. A method for the synthesis of poly(etherimide)s, comprising

reacting 4-halotetrahydrophthalic anhydride with a primary amine having the formula A-NH 2 to yield an N-substituted-4-halotetrahydrophthalimide wherein A is a group which activates the tetrahydrophthalimide ring system to aromatization;

aromatizing N-substituted-4-halotetrahydrophthalimide in the presence of a catalyst to yield an N-substituted-4-halophthalimide in the presence of a catalyst;

treating N-substituted-4-halophthalimide (V) with a diamine having the structure H 2 N-Z-NH 2 , wherein Z is selected from the group consisting of a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms, halogenated derivatives of an arylene group having from 6 to about 20 carbon atoms, and diarylene radicals of the following general formula (XV):

wherein O includes, but is not limited to, the formula (XVI):

wherein y is an integer from about 1 to about 5 methylene, ethylene, propylene, isopropylene, n-butylene, 1,3-phenylene, naphthylene, and mixtures thereof

to produce the dihalobisimide (IX); and

reacting dihalobisimide (IX) with the disodium salt of a dihydroxy compound having the structure HO—S—OH wherein S comprises a straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a substituted straight or branched chain alkylene group having from about 2 to about 20 carbon atoms, a cycloalkylene group having from about 3 to about 20 carbon atoms, a substituted cycloalkylene group having from about 3 to about 20 carbon atoms, an arylene group having from 6 to about 20 carbon atoms or a substituted arylene group having from 6 to about 20 carbon atoms, to yield poly(etherimide).

32. The method of claim 31 , wherein the catalyst is copper based.

33. The method of claim 32 , wherein the catalyst further comprises activated carbon.

34. The method of claim 31 , wherein A is selected from the group consisting of pyridine, chloropyridine, nitropyridine, pyrimidine, pyrazine, thiazole, methylthiazole, benzothiazole, 1,3,4-thiadiazole, and benzotriflouride.

35. The method of claim 34 , wherein A is 2-pyridyl.

36. The method of claim 31 , wherein the dihydroxy compound is bisphenol A.

37. A method for the synthesis of an activated 4-halophthalimide, comprising

reacting 4-halotetrahydrophthalic anhydride with a primary amine having the formula A-NH 2 to yield an N-substituted-4-halotetrahydrophthalimide wherein A is a group which activates the tetrahydrophthalimide ring system to aromatization; and

aromatizing activated 4-halotetrahydrophthalimide in the presence of a catalyst to yield an activated 4-halophthalimide.

38. The method of claim 37 , wherein the catalyst is copper based.

39. The method of claim 38 , wherein the catalyst further comprises activated carbon.

40. The method of claim 37 , wherein A is selected from the group consisting of pyridine, chloropyridine, nitropyridine, pyrimidine, pyrazine, thiazole, methylthiazole, benzothiazole, 1,3,4-thiadiazole, and benzotriflouride.

41. The method of claim 40 , wherein A is 2-pyridyl.