Dendritic polymer coatings

• US 5,731,095 A
• Filed: 10/23/1996
• Issued: 03/24/1998
• Est. Priority Date: 10/23/1996
• Status: Expired due to Term

• Current Assignee: AVC Holdings Inc., Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Original Assignee: Oxazogen, Inc.
• Inventors: Milco, Larry A., Tomalia, Donald A.
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/735,883
• Time in Patent Office: 517 Days
• Field of Search: 528/288, 528/290, 528/299, 528/401, 525/437, 525/440, 525/540, 524/801, 524/802, 524/805, 524/839, 428/482
• US Class Current: 428/482
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: C09D 201/005 Dendritic macromolecules
• CPC Class Codes: Y10S 977/754 Dendrimer, i.e. serially branching or "tree-like" structure
• CPC Class Codes: Y10T 428/31794 Of cross-linked polyester

Abstract

A water-soluble or water-dispersible fluorine-containing dendritic polymer surfactant having at least one terminal fluorocarbon moiety and at least one terminal anionic moiety, and which is suitable for use in preparing protective coating compositions is disclosed. The water-soluble or water-dispersible fluorine-containing dendritic polymer surfactants are represented by the general formula: ##STR1## where D represents a dendritic polymer, R_F represents a fluorocarbon containing moiety, A^- represents an anionic containing moiety, C⁺ represents a cation, T represents a terminal group of the dendritic polymer which has not been functionalized with a fluorocarbon or anionic moiety, n and m are at least each at least one, and the sum of n+m+q is the total number of terminal groups on the dendritic polymer. Also disclosed is a coating composition capable of forming a highly crosslinked, non-stick, protective coating. The coating composition includes a water-soluble or water-dispersible fluorine-containing dendritic polymer surfactant having at least one terminal fluorocarbon moiety and at least one terminal anionic moiety, an oxazoline crosslinking agent, and a water-based solvent.

Claims

1. A water-soluble or water-dispersible fluorine-containing dendritic polymer surfactant having at least one pendant fluorocarbon moiety and at least one pendant anionic moiety.

2. The dendritic polymer surfactant of claim 1 represented by the formula ##STR9## where D represents a dendritic polymer, R_F represents a fluorocarbon-containing moiety, A^- represents an anionic-containing moiety, C⁺ represents a cation, T represents a terminal group of the dendritic polymer which has not been functionalized with a fluorocarbon or anionic moiety, n and m are each at least one, and the sum of n+m+q is the total number of terminal groups on the dendritic polymer.

3. The dendritic polymer surfactant of claim 2, wherein the dendritic polymer is a dendron or dendrimer.

4. The dendritic polymer surfactant of claim 2, wherein the dendritic polymer is a hyperbranched polyester.

5. The dendritic polymer surfactant of claim 2, wherein the fluorocarbon-containing moiety includes a linear or branched fluoroalkyl group having at least one terminal trifluoromethyl group and containing at least three fully fluorinated carbon atoms.

6. The dendritic polymer surfactant of claim 2, wherein the fluorocarbon-containing moiety includes a perfluoroalkyl group.

7. The dendritic polymer surfactant of claim 2, wherein the fluorocarbon-containing moiety is represented by the formula--COCH₂ N(C₂ H₅)SO₂ (C₇ F₁₄ CF₃).

8. The dendritic polymer surfactant of claim 2, wherein the anionic-containing moiety includes a carboxylate group.

9. The dendritic polymer surfactant of claim 2, wherein the T groups are hydroxy groups.

10. The dendritic polymer surfactant of claim 2, wherein the cation is ammonium.

11. The dendritic polymer surfactant of claim 2, wherein the cation is a low molecular weight protonated amine.

12. A non-stick coating composition comprising:

a water-soluble or water-dispersible fluorine-containing dendritic polymer surfactant having at least one pendant fluorocarbon moiety and at least one pendant anionic moiety;

a crosslinking compound containing a plurality of oxazoline or oxazine moieties represented by the formula ##STR10## where each R is a hydrogen atom, a hydroxy methyl group or an organic radical, and k is one or two; and

an aqueous solvent comprising primarily water and optionally containing a minor amount of an organic solvent.

13. The coating composition of claim 12, wherein the dendritic polymer surfactant is represented by the formula ##STR11## where D represents a dendritic polymer, R_F represents a fluorocarbon containing moiety, A^- represents an anionic-containing moiety, C⁺ represents a cation, T represents a terminal group of the dendritic polymer which has not been functionalized with a fluorocarbon or anionic moiety, n and m are each at least one, and the sum of n+m+q is the total number of terminal groups on the dendritic polymer.

14. The coating composition of claim 13, wherein the T groups are hydroxy groups.

15. The coating composition of claim 13, wherein the dendritic polymer is a hyperbranched polyester.

16. The coating composition of claim 13, wherein the fluorocarbon moiety is a linear or branched fluoroalkyl group having at least one terminal trifluoromethyl group and containing at least three fully fluorinated carbon atoms.

17. The coating composition of claim 16, wherein the anionic-containing moiety includes a carboxylate group.

18. The coating composition of claim 13, wherein the oxazoline crosslinking agents include polymeric compounds containing pendant oxazoline moieties.

19. The coating composition of claim 18, wherein the oxazoline crosslinking agent is an acrylate polymer having pendant oxazoline moieties.

20. The coating composition of claim 13, wherein the dendritic polymer surfactant and oxazoline crosslinking agent comprise from about 0.01 to about 60% of the composition by weight.

21. The coating composition of claim 20, wherein the amounts of fluorine-containing dendritic polymers and oxazoline crosslinking agents are selected so that the mole ratio of oxazoline moieties to anionic moieties is from about 0.8:

1 to about 1.2;

1.

22. The coating composition of claim 13, wherein the pH is from about 7 to about 8.

23. The coating composition of claim 13, wherein the fluorocarbon-containing moiety includes a perfluoroalkyl group.

24. The coating composition of claim 13, wherein the fluorocarbon-containing moiety is represented by the formula--COCH₂ N(C₂ H₅)SO₂ (C₇ F₁₄ CF₃).

25. The coating composition of claim 13, wherein the anionic-containing moiety includes a carboxylate group.

26. The coating composition of claim 13, wherein the cation is ammonium.

27. The coating composition of claim 13, wherein the cation is a low molecular weight protonated amine.

28. A highly crosslinked protective coating comprising a reaction product of a dendritic polymer surfactant having at least one pendant fluorocarbon moiety and at least one pendant anionic moiety and an oxazoline crosslinking agent.

29. The coating of claim 28, wherein the dendritic polymer surfactant is represented by the formula ##STR12## where D represents a dendritic polymer, R_F represents a fluorocarbon containing moiety, A^- represents an anionic-containing moiety, C⁺ represents a cation, T represents a terminal group of the dendritic polymer which has not been functionalized with a fluorocarbon or anionic moiety, n and m are each at least one, and the sum of n+m+q is the total number of terminal groups on the dendritic polymer.

30. The coating of claim 29, wherein the T groups are hydroxy groups.

31. The coating of claim 29, wherein the dendritic polymer is a hyperbranched polyester.

32. The coating of claim 29, wherein the fluorocarbon moiety is a linear or branched fluoroalkyl group having at least one terminal trifuoromethyl group and containing at least three fully fluorinated carbon atoms.

33. The coating of claim 31, wherein the anionic-containing moiety includes a carboxylate group.

34. The coating of claim 29, wherein the oxazoline crosslinking agents include polymeric compounds containing pendant oxazoline moieties.

35. The coating of claim 34, wherein the oxazoline crosslinking agent is an acrylate polymer having pendant oxazoline moieties.

36. The coating of claim 35, wherein the amounts of fluorine-containing dendritic polymers and oxazoline crosslinking agents are selected so that the mole ratio of oxazoline moieties to anionic moieties is from about 0.8:

1 to about 1.2;

1.

37. The coating of claim 29, wherein the fluorocarbon-containing moiety includes a perfluoroalkyl group.

38. The coating of claim 29, wherein the fluorocarbon-containing moiety is represented by the formula--COCH₂ N(C₂ H₅)SO₂ (C₇ F₁₄ CF₃).

39. The coating of claim 29, wherein the anionic-containing moiety includes a carboxylate group.

40. The coating of claim 29, wherein the cation is ammonium.

41. The coating of claim 29, wherein the cation is a low molecular weight protonated amine.