Claims
- 1. A method of forming polymers of a metal 4,4',4",4"' tetraamino phthalocyanine which comprises reacting the metal 4,4',4",4"' tetraamino phthalocyanine in liquid phase at about 20.degree. C. to about 50.degree. C. with a tetracarboxylic dianhydride of the formula ##STR11## wherein R is an organic group selected from the group consisting of aromatic and alicyclic groups to produce an amic acid polymer having a ##STR12## recurring unit wherein M is the metal and R is the organic group of the dianhydride.
- 2. The method of claim 1 wherein M is a divalent metal having an atomic radius of approximately 1.35 .ANG..
- 3. The method of claim 1 wherein the dianhydride is an aromatic dianhydride.
- 4. The method of claim 3 wherein the dianhydride is 1,2,4,5-benzene tetracarboxylic dianhydride.
- 5. The method of claim 3 wherein the dianhydride is 3,3',4,4'-benzophenone tetracarboxylic dianhydride.
- 6. The method of claim 1 comprising the additional step of dehydrocyclizing the amic acid polymer by a process selected from thermal cyclization, azeotroping water of cyclization, refluxing in glacial acetic acid in the presence of fused sodium acetate to produce an imide polymer having the recurring unit ##STR13##
- 7. The method of claim 6 wherein the metal M is a divalent metal having an atomic radius about 1.35 .ANG..
- 8. The method of claim 6 wherein the dianhydride is aromatic.
- 9. The method of claim 8 wherein the dianhydride is 1,2,4,5-benzene tetracarboxylic dianhydride.
- 10. The method of claim 8 wherein the dianhydride is 3,3',4,4'-benzophenone tetracarboxylic dianhydride.
- 11. A method of forming polymers of a metal 4,4',4",4"'-tetraamino phthalocyanine which comprises reacting the metal 4,4',4",4"'-tetraamino phthalocyanine in liquid phase at a temperature of from about 20.degree. C. to about 50.degree. C. with a tetracarboxylic dianhydride of the formula ##STR14## wherein R is an organic group selected from the group consisting of aromatic and alicyclic groups, and a diamine of the formula H.sub.2 N--R'--NH.sub.2 wherein R' is a bivalent organic group selected from the group consisting of bivalent aliphatic groups, bivalent cycloaliphatic groups, and bivalent aromatic groups to yield an amic acid copolymer.
- 12. The method of claim 11 wherein the metal is a divalent metal having an atomic radius about 1.35 .ANG..
- 13. The method of claim 11 wherein the dianhydride is aromatic.
- 14. The method of claim 11 wherein the diamine is aromatic.
- 15. The method of claim 11 wherein both R and R' are aromatic.
- 16. The method of claim 1 comprising the additional step wherein the amic acid copolymer is dehydrocyclized by a process selected from thermal cyclization, azeotroping water of cyclization, refluxing in glacial acetic acid in the presence of fused sodium acetate to produce a polymer having the recurring unit ##STR15## wherein R is an organic group selected from the group consisting of aromatic and alicyclic groups which are derived from the dianhydride and R' is an organic group selected from the group consisting of aromatic, aliphatic and cycloaliphatic groups which are derived from the diamine.
- 17. The method of claim 16 wherein M is a divalent metal having an atomic radius about 1.35 .ANG..
- 18. The method of claim 16 wherein the dianhydride is aromatic.
- 19. The method of claim 16 wherein the diamine is aromatic.
- 20. The method of claim 16 wherein both the dianhydride and the diamine are aromatic.
- 21. Polymers having the following recurring unit wherein M is a metal and R is an organic group derived from a dianhydride and selected from the group consisting of aromatic groups and alicyclic groups ##STR16##
- 22. Polymers of claim 21 wherein M is divalent and has an atomic radius about 1.35 .ANG..
- 23. Polymers of claim 21 wherein R is an aromatic group derived from an aromatic dianhydride.
- 24. Polymers of claim 23 wherein the dianhydride is 1,2,3,4-benzene tetracarboxylic dianhydride.
- 25. Polymers of claim 23 wherein the dianhydride is 3,3',4,4'-benzophenone tetracarboxylic dianhydride.
- 26. Polymers having the following recurring unit wherein M is a metal and R is an organic group derived from a dianhydride and selected from the group consisting of aromatic groups and alicyclic groups ##STR17##
- 27. Polymers of claim 26 wherein M is a divalent metal having an atomic radius about 1.35 .ANG..
- 28. Polymers of claim 26 wherein the dianhydride is aromatic.
- 29. Polymers of claim 28 wherein the dianhydride is 1,2,3,4-benzene tetracarboxylic dianhdride.
- 30. Polymers of claim 28 wherein the dianhydride is 3,3',4,4'-benzophenone tetracarboxylic dianhydride.
- 31. Copolymers of a metal 4,4',4",4"'-tetraamino phthalocyanine, a tetracarboxylic dianhydride selected from the group consisting of aromatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides and a diamine selected from aromatic diamines, aliphatic diamines and cycloaliphatic diamines.
- 32. Polymers of claim 3 wherein the metal is a divalent metal having an atomic radius about 1.35 .ANG..
- 33. Polymers of claim 31 wherein the dianhydride is aromatic.
- 34. Polymers of claim 31 wherein the diamine is aromatic.
- 35. Polymers of claim 31 wherein both the dianhydride and the diamine are aromatic.
- 36. Polymers having the following recurring unit wherein M is a metal, R is an organic group selected from aromatic and alicyclic groups derived from a dianhydride and R' is an organic group selected from aromatic groups, cycloaliphatic groups and aliphatic groups derived from a diamine ##STR18##
- 37. Polymers of claim 36 wherein M is a divalent metal having an atomic radius about 1.35 .ANG..
- 38. Polymers of claim 36 wherein the dianhydride is aromatic.
- 39. Polymers of claim 36 wherein the diamine is aromatic.
- 40. Polymers of claim 36 wherein both the dianhydride and the diamine are aromatic.
ORIGIN OF THE INVENTION
The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of Section 305 of the National Aeronautics and Space Act of 1958, Public Law 85-568 (72 Stat. 435; 42 U.S.C. 2457).
US Referenced Citations (15)