Poly(N-substituted iminocarbonate)

• US 5,194,570 A
• Filed: 11/05/1990
• Issued: 03/16/1993
• Est. Priority Date: 11/05/1990
• Status: Expired due to Fees

• Current Assignee: Rutgers University
• Original Assignee: Rutgers University
• Inventors: Liz, Chun, Kohn, Joachim B.
• Primary Examiner(s): Anderson, Harold D.
• Application Number:
  US07/609,204
• Time in Patent Office: 862 Days
• Field of Search: 528/211, 528/86, 528/219
• US Class Current: 528/211
• CPC Class Codes: C08G 71/04 Polyurethanes

Abstract

Poly(N-phenyl urethanes) and methods of preparing same by heating poly(N-phenyl iminocarbonates) to a temperature above 250° C. so that the backbone of the polyiminocarbonate rearranges to form the poly(N-phenyl urethane). Poly(N-substituted iminocarbonates and methods of preparing same by suspending a dialkaline diphenol in an aprotic solvent at a basic pH and adding to the suspension an N-substituted iminophosgene. Methods for making heat-stable articles by forming an article from a poly(N-phenyl iminocarbonate) while heating the article to a temperature above about 250° C. so that the poly(N-phenyl iminocarbonate) rearranges to form a poly(N-phenyl urethane).

Claims

1. A poly(N-substituted iminocarbonate), wherein the imide nitrogens are substantially free of hydrogen.

2. A poly(N-substituted iminocarbonate), wherein said N-substituent is selected from the group consisting of lower alkyl groups of 1 to 17 carbon atoms, aryl groups, arylalkyl groups and aromatic functional groups containing heteroatoms.

3. The poly(N-substituted iminocarbonate) of claim 2, wherein said N-substituent is a methyl or ethyl group.

4. The poly(N-substituted iminocarbonate) of claim 2, wherein said N-substituent is a functional group having a benzene ring directly bonded to the nitrogen atom.

5. The poly(N-substituted iminocarbonate) of claim 4, wherein said N-substituent is an unsubstituted phenyl group.

6. The poly(N-substituted iminocarbonate) of claim 2, comprised of one or more recurring structural units represented by the formula:

##STR10## wherein R₁ is selected from the group consisting of aryl and arylalkyl functional groups and aromatic functional groups containing one or more heteroatoms, and R₄ is selected from the group consisting of alkyl, aryl and arylalkyl functional groups and functional groups containing one or more heteroatoms.

7. The poly(N-substituted iminocarbonate) of claim 6, wherein R₁ is represented by the formula:

##STR11## with R₃ being selected from the group consisting of;

##STR12## and Z₁ and Z₂ are independently selected from the group consisting of hydrogen, halogen, alkyl, carboxyl, nitro, thioether sulfoxide and sulfonyl.

8. The poly(N-substituted iminocarbonate) of claim 7, wherein Z₁ and Z₂ are hydrogen.

9. A polymerization process for making a poly(N-substituted iminocarbonate) comprising the steps of suspending a dialkaline salt of a diphenol in an aprotic polar solvent at a basic pH, adding to the suspension an N-substituted iminophosgene, reacting said iminophosgene with said diphenol to produce a poly(N-substituted iminocarbonate), and recovering said poly(N-substituted iminocarbonate).

10. The process of claim 9, wherein said N-substituted iminophosgene is selected from the group consisting of N-alkyl, N-aryl, N-arylalkyl and N-heterofunctional substituted iminophosgenes.

11. The process of claim 10, wherein said N-aryl iminophosgene is N-phenyl iminophosgene.

12. The process of claim 10, wherein said N-alkyl iminophosgene is N-methyl iminophosgene.

13. The process of claim 9, wherein said solvent is selected from the group consisting of dimethyl formamide (DMF), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), and mixtures thereof.

14. The process of claim 13, wherein said solvent consists essentially of DMF.

15. The process of claim 13, wherein said solvent consists, essentially of NMP.

16. The process of claim 13, Wherein said solvent consists essentially of DMSO.

17. The process of claim 9, comprising suspending said dialkaline salt and adding said iminophosgene at a temperature between about room temperature and about 60°

C.

18. The process of claim 9, comprising suspending said dialkaline salt and adding said iminophosgene under an insert atmosphere.

19. The process of claim 9, wherein said diphenol has the formula:

##STR13## wherein R₃ is selected from the group consisting of alkyl, aryl and arylalkyl functional groups and functional groups containing one or more heteroatoms and Z₁ and Z₂ are independently selected from the group consisting of hydrogen, halogen, alkyl, carboxyl, nitro, thioether, sulfoxide and sulfonyl.

20. The process of claim 19, wherein R₃ is selected from the group consisting of:

##STR14##

21. The process of claim 19, wherein Z₁ and Z₂ are both hydrogen.