Phosphate ester flame retardants from resorcinol-ketone reaction products

• US 20060063867A1
• Filed: 09/21/2005
• Published: 03/23/2006
• Est. Priority Date: 09/22/2004
• Status: Active Grant

• Current Assignee: INDSPEC Chemical Corporation (Occidental Petroleum Corporation)
• Original Assignee: INDSPEC Chemical Corporation (Occidental Petroleum Corporation)
• Inventors: Durairaj, Raj B., Jesionowski, Gary A.
• Granted Patent: US 7,365,113 B2
• Time in Patent Office: Days
• US Class Current: 524/115
• CPC Class Codes: C07F 9/65522 condensed with carbocyclic rings or carbocyclic ring systems
• CPC Class Codes: C08K 5/529 Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids

Abstract

Flavan-based and spirodichroman compound-based phosphate esters prepared by reacting flavans and spirodichroman compounds with phosphorus oxychloride, monophenyl dichlorophosphate, or diphenyl chlorophosphate compounds are described. The flavans and spirodichroman compounds can be synthesized by the reaction of resorcinol with aliphatic acetone. Such phosphate esters can be used as flame retardants.

Claims

1. ) A flame retardant comprising at least a phosphate ester compound having the formula:

2. ) The flame retardant of claim 1, wherein the phosphate ester group has the

3. ) The flame retardant of claim 2, wherein each of R⁵ and R⁶ is independently aryl.

4. ) The flame retardant of claim 3, wherein each of R⁵ and R⁶ is independently phenyl.

5. ) The flame retardant of claim 1, wherein the phosphate ester group is selected from the group consisting of radicals having the following formulae:

31. ) A process for preparing the flame retardant of claim 2, comprising the step of reacting a compound of the formula:

32. ) The process of claim 31, wherein the compound of formula (VII) is prepared by reacting a compound of the formula:

33. ) The process of claim 32, wherein the reaction occurs in an inert organic solvent.

34. ) The process of claim 32, wherein the catalyst is an organic base selected from the group consisting of amines, 1-alkylpiperidines, 1-alkylpyrrolidines, pyridine, imidazole, and combinations thereof.

35. ) The process of claim 32, wherein the catalyst is magnesium chloride, aluminum trichloride, titanium tetrachloride, and zinc dichloride.

36. ) The process of claim 31, wherein each of R⁵ and R⁶ is independently aryl.

37. ) The process of claim 36, wherein each of R⁵ and R⁶ is independently phenyl.

39. ) The process of claim 31, wherein the compound of formula (IX) is prepared by reacting a compound of the formula:

40. ) The process of claim 39, wherein the reaction occurs in an inert organic solvent.

41. ) The process of claim 39, wherein the catalyst is an organic base selected from the group consisting of amines, 1-alkylpiperidines, 1-alkylpyrrolidines, pyridine, imidazole, and combinations thereof.

42. ) The process of claim 39, wherein the catalyst is magnesium chloride, aluminum trichloride, titanium tetrachloride, and zinc dichloride.

43. ) The process of claim 36, wherein each of R⁵ and R⁶ is independently aryl.

44. ) The process of claim 43, wherein each of R⁵ and R⁶ is independently phenyl.

45. ) A flame retardant composition comprising a polymer and a flame retardant of claim 1 or 6.

46. ) The flame retardant composition of claim 45, wherein the polymer is selected from the group consisting of polycarbonates, poly(phenylene oxide), polyarylates, polymethacrylates, polyesters, acrylonitrile-butadiene-styrene terpolymer, high-impact polystyrene, and combinations or blends thereof.

47. ) The flame retardant composition of claim 45, further comprising at least an additive selected from the group consisting of extenders, fibers, fillers, coupling agents, cross-linking agents, plasticizers, impact modifiers, compatibilizers, anti-blocking agents, anti-fogging agents, anti-aging agents, antioxidants, UV stabilizers, antiozonants, acid scavengers, processing aids, surfactants, lubricants, plasticizing agents, parting agents and abherents, nucleating agents, anti-static agents, slip agents, chemical blowing agents, fluorescent whitening agents, flow agents, deodorants, release agents, colorants, and anti-microbials.

48. ) The flame retardant composition of claim 45, wherein the flame retardant composition is substantially free of an additive.

49. ) An article comprising a flame retardant composition of claim 45.

50. ) The article of claim 49, wherein the article is selected from the group consisting of plastic products, textiles, wood and paper products, adhesives and sealants, and rubber products, aerospace parts, automotive parts, wires, cables, construction materials, materials for interiors and furnishings, appliances, electronic components, computers, and business machines.

51. ) The article of claim 49, wherein the polymer is selected from the group consisting of polycarbonates, poly(phenylene oxide), polyarylates, polymethacrylates, polyesters, acrylonitrile-butadiene-styrene terpolymer, high-impact polystyrene, and combinations or blends thereof.

52. ) The article of claim 49, wherein the flame retardant composition further comprises at least an additive selected from the group consisting of extenders, fibers, fillers, coupling agents, cross-linking agents, plasticizers, impact modifiers, compatibilizers, anti-blocking agents, anti-fogging agents, anti-aging agents, antioxidants, UV stabilizers, antiozonants, acid scavengers, processing aids, surfactants, lubricants, plasticizing agents, parting agents and abherents, nucleating agents, anti-static agents, slip agents, chemical blowing agents, fluorescent whitening agents, flow agents, deodorants, release agents, colorants, and anti-microbials.

53. ) The article of claim 49, wherein the flame retardant composition is substantially free of an additive.

6. ) A flame retardant comprising at least a phosphate ester compound having the formula:

7. ) The flame retardant of claim 6, wherein the phosphate ester group has the formula:

8. ) The flame retardant of claim 7, wherein each of R⁵ and R⁶ is independently aryl.

9. ) The flame retardant of claim 8, wherein each of R⁵ and R⁶ is independently phenyl.

10. ) The flame retardant of claim 6, wherein the phosphate ester group is selected from the group consisting of radicals having the following formulae:

11. ) A process for preparing a flame retardant comprising at least a phosphate ester compound having the formula:

12. ) The process of claim 11, wherein the reaction occurs in an inert organic solvent.

13. ) The process of claim 12, wherein the inert organic solvent is selected from the group consisting of heptane, toluene, benzene, xylene, methylene chloride, chloroform, acetonitrile, ethers, and ketones.

14. ) The process of claim 11, wherein the catalyst is magnesium chloride, aluminum trichloride, titanium tetrachloride, and zinc dichloride.

15. ) The process of claim 14, wherein the inert organic solvent is toluene.

16. ) The process of claim 15, wherein the reaction temperature is greater than 100°

C.

17. ) The process of claim 11, wherein the acid acceptor is an organic base.

18. ) The process of claim 17, wherein the organic base is triethylamine.

19. ) The process of claim 18, wherein the inert organic solvent is methylene chloride.

20. ) The process of claim 19, wherein the reaction temperature is lower than 35°

C.

21. ) A process for preparing a flame retardant comprising at least a phosphate ester compound having the formula:

22. ) The process of claim 21, wherein the reaction occurs in an inert organic solvent.

23. ) The process of claim 22, wherein the inert organic solvent is selected from the group consisting of heptane, toluene, benzene, xylene, methylene chloride, chloroform, acetonitrile, ethers, and ketones.

24. ) The process of claim 21, wherein the catalyst is magnesium chloride, aluminum trichloride, titanium tetrachloride, and zinc dichloride.

25. ) The process of claim 24, wherein the inert organic solvent is toluene.

26. ) The process of claim 25, wherein the reaction temperature is greater than 100°

C.

27. ) The process of claim 21, wherein the acid acceptor is an organic base.

28. ) The process of claim 27, wherein the organic base is triethylamine.

29. ) The process of claim 28, wherein the inert organic solvent is methylene chloride.

30. ) The process of claim 29, wherein the reaction temperature is lower than 35°

C.

38. ) A process for preparing the flame retardant of 7, comprising the step of reacting a compound of the formula: