Coupling of polyorganophosphazenes to carboxylic acid

• US 4,440,921 A
• Filed: 06/21/1982
• Issued: 04/03/1984
• Est. Priority Date: 06/21/1982
• Status: Expired due to Fees

• Current Assignee: Research Corporation
• Original Assignee: Research Corporation
• Inventors: Allcock, Harry R., Neenan, Thomas X., Kossa, Walter C.
• Primary Examiner(s): Lee, Lester L.
• Application Number:
  US06/390,350
• Time in Patent Office: 652 Days
• Field of Search: 528/167-169, 528/367, 528/368, 528/369, 528/399, 528/228, 528/229, 525/417, 525/540, 525/535, 525/538
• US Class Current: 528/168
• CPC Class Codes: C08G 73/00 Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00 polycarbodiimides prepared from isocyanates C08G18/025, C08G18/797
• CPC Class Codes: C08G 79/025 Polyphosphazenes

Abstract

A carboxylated phosphazene polymer, comprising a phosphazene polymer backbone covalently coupled to a carboxylate-containing compound through a divalent organic radical attached at one end to the carboxylate by an amide bond formed at a primary aliphatic amino group of the radical and at the other end to a phosphorous of the phosphazene backbone.

Claims

1. A carboxylated phosphazene polymer, comprising a phosphazene polymer backbone covalently coupled to a carboxylate-containing compound through a linking group attached at one end to said carboxylate-containing compound by an amide bond formed at a primary aliphatic amino group of said linking group and at the other end of said linking group to a phosphorous of said backbone.

2. The carboxylated phosphazene polymer of claim 1, wherein said linking group comprises a divalent organic radical of the formula --AL-- or --AM--, wherein A represents --O-- or --NH--, L represents a divalent C₂ -C₁₂ alkylene group or a divalent C₂ -C₁₂ alkylene group substituted by a halogen atom or --CN or said alkylene group having a divalent organic functional group of the formula --O--, --COO--, --CONR--, --RC═

CR--, --C═

C--, ##STR22## or --CO--, in the chain wherein each R independently represents hydrogen or a C₁ -C₄ alkyl group, m is an integer from 0 to 4, and each E independently represents a halogen atom, --NO₂, --CN, or --R, and M represents a divalent aryl radical of the formula ##STR23## wherein n is 1 or 2, or ##STR24## wherein L¹ is L or --CH₂ --, and A is directly bonded to a phosphorous atom of said backbone, while L or M is bonded to the nitrogen that forms said amide bond through an aliphatic carbon of group L or M.

3. The carboxylated phosphazene polymer of claim 2, wherein said linking group has the formula ##STR25## wherein A is O or NH;

m is an integer from 0 to 4; and

each R¹ independently represents an alkyl group containing 1 to 4 carbon atoms, a nitro group, a cyano group, or a halogen atom.

4. The carboxylated phosphazene polymer of claim 3, wherein said linking group has the formula ##STR26##

5. The carboxylated phosphazene polymer of claim 4, wherein A is O.

6. The carboxylated phosphazene polymer of claim 2, wherein organic groups of the formula --QJ are attached to phosphorous atoms of said backbone, wherein Q represent --NR¹ -- wherein R¹ represents hydrogen or methyl, --O--, or a covalent bond and J represents L¹ H, MH, or ##STR27##

7. The carboxylated phosphazene polymer of claim 6, wherein the ratio of linking groups to organic groups is from 1:

100 to 3;

1.

8. The carboxylated phosphazene polymer of claim 7, wherein said ratio is from 1:

10 to 1;

1.

9. The carboxylated phosphazene polymer of claim 7, wherein said ratio is about 1:

3.

10. The carboxylated phosphazene polymer of claim 6, wherein said linking group has the formula ##STR28##

11. The carboxylated phosphazene polymer of claim 10, wherein A is O.

12. The carboxylated phosphazene polymer of claim 11, wherein the ratio of linking groups to organic groups is from 1:

100 to 2;

1.

13. The carboxylated phosphazene polymer of claim 6, wherein said organic groups --QJ impart water solubility to said complex.

14. The carboxylated phosphazene polymer of claim 13, wherein --QJ represent --N(CH₃)₂ or ##STR29## wherein R² represents a side chain of a naturally occurring amino acid.

15. The carboxylated phosphazene polymer of claim 14, wherein R² represents hydrogen.

16. The carboxylated phosphazene polymer of claim 6, wherein said organic groups --QJ impart biodegradability to said complex.

17. The carboxylated phosphazene polymer of claim 16, wherein --QJ represents ##STR30## wherein R² represents a side chain of a naturally occurring amino acid.

18. The carboxylated phosphazene polymer of claim 6, wherein said organic group --QJ imparts biochemical stability to said complex.

19. The carboxylated phosphazene polymer of claim 18, wherein --QJ represents ##STR31## or a fluorinated C₂ -C₄ alkoxyl.

20. The carboxylated phosphazene polymer of claim 19, wherein --QJ represents --OCH₂ CF₃.

21. The carboxylated phosphazene polymer of claim 1, wherein said polymeric phosphazene backbone is a cyclic trimer.

22. The carboxylated phosphazene polymer of claim 1, wherein said polymeric phosphazene backbone is a linear chain containing from 3 to 30,000 ##STR32## repeating units.

23. The carboxylated phosphazene polymer of claim 22, wherein said backbone contains from 100 to 20,000 repeating units.

24. The carboxylated phosphazene polymer of claim 23, wherein said backbone contains about 15,000 repeating units.

32. The carboxylated phosphazene polymer of claim 11, wherein QJ represents ##STR39## or a flourinated C₂ -C₄ alkoxyl.

25. A phosphazene polymer, comprising a phosphazene polymer backbone covalently coupled to a radical of the formula ##STR33## wherein A is O or NH;

m is an integer from 0 to 4;

each R¹ independently represents an alkyl group containing 1 to 4 carbon atoms, a nitro group, a cyano group, or a halogen atom; and

Y is --CH₂ NH₂ or --CN,

wherein A is covalently attached to a phosphorous of said phosphazene polymer backbone.

26. The phosphazene polymer of claim 25, wherein said radical has the formula ##STR34##

27. A method of attaching a compound having a carboxylic acid functional group to a phosphazene polymer, comprising condensing under suitable condensation conditions said compound with a polyorganophosphazene having a primary aliphatic amino group in an organic radical of said polyorganophosphazene to give an amide bond.

28. The method of claim 27, wherein said radical has the formula --ALNH₂ or --AMNH₂, wherein A represents --O-- or --NH--, L represents a divalent C₂ -C₁₂ alkylene group or a divalent C₂ -C₁₂ alkylene group substituted by a halogen atom or --CN or said alkylene group having a divalent organic functional group of the formula --O--, --COO--, --CONR--, --RC═

CR--, --C═

C--, ##STR35## or --CO--, in the chain wherein each R independently represents hydrogen or a C₁ -C₄ alkyl group, m is an integer from 0 to 4, and each E independently represents a halogen atom, --NO₂, --CN, or --R, and M represents a divalent aryl radical of the formula ##STR36## wherein n is 1 or 2, or ##STR37## wherein L¹ is L or --CH₂ --, and A is directly bonded to a phosphorous atom of said backbone, while L or M is bonded to the nitrogen that forms said amide bond through an aliphatic carbon of group L or M.

29. The method of claim 27, wherein said radical has the formula ##STR38##

30. The method of claim 29, wherein m is zero.

31. The method of claim 29, wherein A is O.