Branched polyphosphonates

• US 20070032633A1
• Filed: 02/24/2004
• Published: 02/08/2007
• Est. Priority Date: 02/24/2003
• Status: Active Grant

• Current Assignee: FRX Polymers, Inc.
• Original Assignee: Triton Systems, Inc.
• Inventors: Freitag, Dieter, Rice, Norman, Lusignea, Richard, Vinciguerra, Michael
• Granted Patent: US 7,816,486 B2
• Time in Patent Office: Days
• US Class Current: 528/398
• CPC Class Codes: C08G 79/04 Phosphorus linked to oxygen or to oxygen and carbon
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 85/02 containing phosphorus

Abstract

Disclosed are branched polyphosphonates produced using a polycondensation process, that result in polyphosphonates having a T_g of at least 100° C., and which can be further processed to have improved hydrolytic stability compared to other polyphosphonates. The method and polyphosphonate compositions may be made from readily available starting materials providing lower cost fire retardant materials. Also disclosed are polymer compositions that comprise these branched polyphosphonates and at least one other polymer, wherein the resulting polymer compositions exhibit flame retardant properties.

Claims

1. A method of making moldable branched polyphosphonates comprising:

heating in a vessel a phosphonium catalyst with an amount of phosphonic acid diaryl ester and a bisphenol in a ratio to form a polyphosphonate, said heating performed at a reduced pressure.

2. The method of claim 1 wherein said vessel includes a branching agent.

3. The method of claim 1 wherein said bisphenol is forms branching agent in situ.

4. The method of claim 1 wherein at least a portion of said phosphonium catalyst is removed during said heating.

5. The method of claim 1 wherein the amount of phosphonic acid diaryl ester and a bisphenol is in a non-stoichiometric ratio.

6. The method of claim 1 wherein said bisphenol is bisphenol A, or a mixture of bisphenol A and a bisphenol of formula (XV) the amount of bisphenol A in the

7. The method of claim 1 wherein said heating is stopped when substantially all generated hydroxy aromatic compound is removed from the reaction vessel.

8. A method of making a hydrolytically stable polyphosphonate comprising:

heating a polyphosphonate and a removable phosphonium catalyst in a vessel to form a hydrolytically stable polyphosphonate at a reduced pressure.

9. The method of claim 8 wherein less than 0.5 g of hydrolytically stable polyphosphonate is soluble in 100 ml volume of methylene chloride at about 23°

C.

10. The method of claim 8 wherein said polyphosphonate has a polydispersity of greater than about 2.3.

11. The method of claim 8 wherein said polyphosphonate includes monomer derived units in its structure from bisphenol A.

12. The method of claim 8 wherein said polyphosphonate is formed using a phosphonium catalyst.

13. The method of claim 8. wherein said at least a portion of the phosphonium catalyst is removed by the heating.

14. A composition comprising:

a polyphosphonate including bisphenol A monomer derived units in its structure having a T_g of at least 100°

C., a relative viscosity of greater than 1.1 when measured on a 0.5 percent solution in methylene chloride, an M_w of at least 10,000 g/mol, and a polydispersity of 2.3 or greater.

15. A composition comprising:

a polyphosphonate characterized by having a T_g of at least 100°

C. made by heating an amount of phosphonic acid diaryl ester and bisphenol A to form a polyphosphonate with a removable polymerization catalyst in a vessel at a reduced pressure.

16. The composition of claim 15 wherein said phosphonic acid diaryl ester includes methyl-phosphonic acid diphenyl ester.

17. The composition of claim 15 further comprising bisphenols of formula (XV) to form a mixture of bisphenols and wherein an amount of bisphenol A in the mixture is less than 100%, and bisphenols of formula (XV) is:

18. A composition comprising:

a polyphosphonate including bisphenol A derived repeat units having a T_g of at least 100°

C., a relative viscosity of greater than 1.15 when measured on a 0.5 percent solution in methylene chloride, an M_w of at least 15,000 g/mol, a polydispersity of 2.3 or greater, and which is hydrolytically stable.

19. A composition comprising:

a hydrolytically stable polyphosphonate characterized by having a T_g of at least 100°

C. made by heating an amount of a polyphosphonate with a removable phosphonium catalyst in a vessel at a reduced.

20. The composition of claim 19 wherein less than 0.5 g of said hydrolytically stable polyphosphonate is soluble in 100 milliliters of methylene chloride at about 23°

C.

21. The composition of claim 19 forming less than 5% degradation product when heated in boiling water for 6 hours.

22. The composition of claim 19 wherein said hydrolytically stable polyphosphonate is transparent.

23. The composition of claim 19 wherein said phosphonic acid diaryl ester includes methyl-phosphonic acid diphenyl ester.

24. The composition of claim 19 wherein said polyphosphonate includes a repeat unit derived from bisphenol A.

25. A method for producing polyphosphonates, comprising:

heating a phosphonic acid diaryl ester, bisphenol A or bisphenol A and other bisphenols wherein the amount of bisphenol A in the mixture is less than 100%, and a tetraphenylphosphonium catalyst in a reaction vessel and removing phenol generated by the heating to form a moldable polyphosphonate;

said phosphonic acid diaryl ester being in a stiochiometric equivalent or excess amount of said bisphenol.

26. The method of claim 25 including wherein said vessel includes a branching agent.

27. The method of claim 25 wherein the number of moles of reactive groups of the phosphonic acid diaryl ester is within about +20% of the number of moles of reactive groups from said bisphenol.

28. The method of claim 25, wherein the phosphonium catalyst is tetraphenylphosphonium phenolate.

29. The method of claim 25, wherein the branching agent includes 1,1,1-tris(4-hydroxyphenyl)ethane.

30. The method of claim 25, wherein the phosphonic acid diaryl esters or mixtures of them used for making polyphosphonates include those of formula (XIII):

31. The method of claim 25, wherein the phosphonic acid diaryl ester includes methyl-phosphonic acid diphenyl ester.

32. The method of claim 25 further including a phosphoric triaryl ester.

33. The method of claim 25 wherein said bisphenol is bisphenol A or a mixture of bisphenol A wherein the amount of bisphenol A in the mixture is less than 100% and a bisphenol of formula (XV):

34. The method of claim 25, wherein the other bisphenols include 2,2-bis(3-chloro-4-hydroxyphenyl)propane;

2,2-bis(3-bromo-4-hydroxyphenyl)propane;

2,2-bis(4-hydroxy-3-isopropylphenyl)propane;

1,1-bis(4-hydroxyphenyl)cyclohexane;

1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane;

4,4′

-dihydroxydiphenyl;

4,4′

-dihydroxydiphenylether;

4,4′

-dihydroxydiphenylsulfide;

4,4′

dihydroxydiphenylsulfone, 9,9-dihydroxy-diphenylfluorene;

1,1-bis(4-hydroxyphenyl)-3,3-dimethyl-5-methyl cyclohexane, or a combination of these.

49. A polymer composition according to claim 48, wherein said other polymer is a polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyamide, polystyrene, polyurethane, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, polyether, polyphenylene oxide, cellulose polymer, the polyphosphonate of claim 31, or a combination of these.

35. A method of making polyphosphonates comprising:

heating a polyphosphonate and a tetraphenylphosphonium catalyst in a vessel to form a hydrolytically stable polyphosphonate.

43. A polymer composition according to claim 42, wherein said other polymer is a polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyamide, polystyrene, polyurethane, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, polyether, polyphenylene oxide, cellulose polymer, the polyphosphonate of claim 35, or a combination of these.

36. A polyphosphonate comprising:

a phosphonic acid diaryl ester, a bisphenol A or bisphenol A and other bisphenols wherein the amount of bisphenol A in the mixture is less than 100%, and a tetraphenylphosphonium catalyst in a reaction vessel heated at reduced pressure to form a polyphosphonate and removing material generated by the heating;

said phosphonic acid diaryl ester being in a stiochiometric equivalent or excess amount of said bisphenol.

37. The polyphosphonate according to claim 36, wherein the polyphosphonate has a relative viscosity of at least 1.1 when measured on a 0.5 percent solution in methylene chloride at 23°

C., a polymer dispersity of 2.3 or greater, and a Tg of at least 100°

C.

38. The polyphosphonate according to claim 36, wherein the other bisphenols include 2,2-bis(3-chloro-4-hydroxyphenyl)propane;

2,2-bis(3-bromo-4-hydroxyphenyl)propane;

2,2-bis(4-hydroxy-3-isopropylphenyl)propane;

1,1-bis(4-hydroxyphenyl)cyclohexane;

1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane;

4,4′

-dihydroxydiphenyl;

4,4′

-dihydroxydiphenylether;

4,4′

-dihydroxydiphenylsulfide;

4,4′

dihydroxydiphenylsulfone, 9,9-dihydroxy-diphenylfluorene;

1,1-bis(4-hydroxyphenyl)-3,3-dimethyl-5-methyl cyclohexane, or a combination of these.

39. The polyphosphonate according to claim 36 wherein the phosphonic acid diaryl esters or mixtures of them used for making polyphosphonates include those of formula (XIII):

40. A composition comprising:

a polyphosphonate and a tetraphenylphosphonium catalyst in a reaction vessel heated at reduced pressure whereby a hydrolytically stable polyphosphonate is formed.

41. The composition of claim 40 wherein said polyphosphonate forms less than 5% degradation product when heated in boiling water for 6 hours.

42. A polymer composition, comprising:

at least one polyphosphonate formed from a phosphonic acid diaryl ester, a bisphenol, and a phosphonium catalyst in a reaction vessel heated at reduced pressure to form a polyphosphonate;

said phosphonic acid diaryl ester being in a stiochiometric equivalent or excess amount of said bisphenol; and

at least one other polymer.

44. The polymer composition of claim 42, wherein the polymer includes polycarbonate.

45. The polymer composition of claim 42, wherein the polymer includes polystyrene and polyphenylene oxide.

46. The polymer composition of claim 42, wherein said other polymer includes polycarbonate and poly(acrylonitrile butadiene styrene).

47. The polymer composition of claim 42, wherein the polymer composition exhibits a limiting oxygen index of at least 27.

48. A polymer composition, comprising:

at least one polyphosphonate formed from a polyphosphonate and a phosphonium catalyst in a reaction vessel heated at reduced pressure to form a hydrolytically stable polyphosphonate; and

at least one other polymer.

50. The polymer composition of claim 48, wherein the polymer includes polycarbonate.

51. The polymer composition of claim 48, wherein the polymer includes polystyrene and polyphenylene oxide.

52. The polymer composition of claim 48, wherein said other polymer includes polycarbonate and poly(acrylonitrile butadiene styrene).

53. The polymer composition of claim 48, wherein the polymer composition exhibits a limiting oxygen index of at least 27.