Biocidal particles of methylated polystyrene

• US 20040086480A1
• Filed: 10/31/2002
• Published: 05/06/2004
• Est. Priority Date: 10/31/2002
• Status: Active Grant

• Current Assignee: Auburn University
• Original Assignee: Auburn University
• Inventors: Chen, Yongjun, Worley, Shelby D.
• Granted Patent: US 7,687,072 B2
• Time in Patent Office: Days
• US Class Current: 424/78.22
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: C08F 112/08 Styrene
• CPC Class Codes: C08F 8/24 Haloalkylation
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups

Abstract

Methylated polystyrene having pendant N-halamine and N-halamine precursor groups. Biocidal particles have been prepared by reacting highly crosslinked methylated polystyrene beads as starting materials with various N-halamine precursor compounds. The resulting polymer beads are halogenated with chlorine or bromine. The porous beads will be useful in disinfection applications, as well as for sanitization and controlling noxious odor when mixed with absorbent materials in items such as disposable diapers, infant swimwear, incontinence pads, bandages, sanitary napkins, pantiliners, mattress covers, shoe inserts, sponges, animal litter, carpets, and fabrics.

Claims

1. A methylated polystyrene having pendant N-halamine precursor groups.

2. The methylated polystyrene of claim 1, wherein the N-halamine precursor groups comprise hydantoin groups.

3. The methylated polystyrene of claim 1, wherein the N-halamine precursor groups comprise imidazolidinone groups.

4. The methylated polystyrene of claim 1, wherein the N-halamine precursor groups comprise isocyanurate groups.

5. The methylated polystyrene of claim 1, wherein the N-halamine precursor groups comprise oxazolidinone groups.

6. The methylated polystyrene of claim 1, wherein the polystyrene is a crosslinked polystyrene.

7. The methylated polystyrene of claim 6, wherein the polystyrene is crosslinked with divinylbenzene

8. The methylated polystyrene of claim 6, wherein the polystyrene is from about 3 to about 10 percent crosslinked.

9. The methylated polystyrene of claim 6, wherein the polystyrene is from about 5 to about 8 percent crosslinked.

10. A biocidal methylated polystyrene having pendant N-halamine groups.

11. The biocidal methylated polystyrene of claim 10, wherein the N-halamine groups comprise hydantoin groups.

12. The biocidal methylated polystyrene of claim 10, wherein the N-halamine groups comprise imidazolidinone groups.

13. The biocidal methylated polystyrene of claim 10, wherein the N-halamine groups comprise oxazolidinone groups.

14. The biocidal methylated polystyrene of claim 10, wherein the N-halamine groups comprise isocyanurate groups.

15. The methylated polystyrene of claim 10, wherein the polystyrene is a crosslinked polystyrene.

16. The methylated polystyrene of claim 15, wherein the polystyrene is crosslinked with divinylbenzene.

17. The biocidal methylated polystyrene of claim 15, wherein the polystyrene is from about 3 to about 10 percent crosslinked.

18. The biocidal methylated polystyrene of claim 15, wherein the polystyrene is from about 5 to about 8 percent crosslinked.

19. A polymer having a repeating unit, said unit having the formula:

20. The polymer of claim 19, wherein R has the formula:

21. The polymer of claim 20, wherein R₁ and R₂ are methyl.

22. The polymer of claim 19, wherein R has the formula:

23. The polymer of claim 22, wherein R₁ and R₂ are methyl.

24. The polymer of claim 19, wherein R has the formula:

25. The polymer of claim 24, wherein R₁ and R₂ are methyl.

26. The polymer of claim 19, wherein R has the formula:

27. The polymer of claim 26, wherein R₁ and R₂ are methyl.

28. The polymer of claim 19, wherein R has the formula:

29. The polymer of claim 28, wherein R₁, R₂, R₃, and R₄ are methyl.

30. The polymer of claim 19, wherein R has the formula:

31. The polymer of claim 30, wherein R₁, R₂, R₃, and R₄ are methyl.

32. The polymer of claim 19, wherein R has the formula:

33. The polymer of claim 32, wherein R₁ is methyl or ethyl.

34. The polymer of claim 19, wherein R has the formula:

35. The polymer of claim 34, wherein R₁ is methyl or ethyl.

36. The polymer of claim 19, wherein R has the formula:

37. The polymer of claim 19, wherein R has the formula:

38. A method of making a methylated polystyrene having pendant N-halamine precursor groups, comprising:

reacting a functionalized methylated polystyrene with a N-halamine precursor and an alkali metal base to produce a methylated polystyrene having pendant N-halamine precursor groups.

39. The method of claim 38, wherein the functionalized methylated polystyrene comprises poly(chloromethyl)styrene.

40. The method of claim 38, wherein the N-halamine precursor comprises a hydantoin group, an imidazolidinone group, an oxazolidinone group, or an isocyanurate group.

41. The method of claim 38, wherein said reacting occurs for from about 12 to about 96 hours at a temperature of from about 70°

to about 120°

C.

42. A method of making a biocidal methylated polystyrene having pendant N-halamine groups, comprising:

reacting a functionalized methylated polystyrene with a N-halamine precursor and an alkali metal base to produce a methylated polystyrene having pendant N-halamine precursor groups, and

halogenating the methylated polystyrene having pendant N-halamine precursor groups to produce the biocidal methylated polystyrene having pendant N-halamine groups.

43. The method of claim 42, wherein the functionalized methylated polystyrene comprises poly(chloromethyl)styrene.

44. The method of claim 42, wherein the N-halamine precursor comprises a hydantoin group, an imidazolidinone group, an oxazolidinone group, or an isocyanurate group.

45. The method of claim 42, wherein the alkali metal base comprises a carbonate.

46. The method of claim 42, wherein the alkali metal base comprises a hydroxide.

47. The method of claim 42, wherein the alkali metal base comprises a hydride.

48. The method of claim 42, wherein the alkali metal base comprises sodium or potassium base.

49. The method of claim 42, wherein said reacting occurs in anhydrous dimethylformamide.

50. The method of claim 42, wherein said reacting occurs in anhydrous dimethylsulfoxide.

51. The method of claim 42, wherein said reacting occurs for from about 12 to about 96 hours at a temperature of from about 70°

to about 120°

C.

52. A method for making a methylated polystyrene having pendant N-halamine precursor groups, comprising:

reacting a N-halamine precursor with an alkali metal base to produce an alkali metal salt of the N-halamine precursor; and

reacting the alkali metal salt of the N-halamine precursor with a functionalized methylated polystyrene to produce a methylated polystyrene having pendant N-halamine precursor groups.

53. The method of claim 52, wherein the functionalized methylated polystyrene comprises poly(chloromethyl)styrene.

54. The method of claim 52, wherein the N-halamine precursor comprises a hydantoin group, an imidazolidinone group, an oxazolidinone group, or an isocyanurate group.

55. The method of claim 52, wherein said reacting of the N-halamine precursor with the alkali metal base occurs for from about 15 minutes to about 2 hours at a temperature of from about 25°

to about 100°

C.

56. The method of claim 52, wherein said reacting of the alkali metal salt with the methylated polystyrene occurs for from about 4 to about 96 hours at a temperature of from about 70°

to about 120°

C.

57. A method for making a biocidal methylated polystyrene having pendant N-halamine groups, comprising:

reacting a N-halamine precursor with an alkali metal base to produce an alkali metal salt of the N-halamine precursor;

reacting the alkali metal salt of the N-halamine precursor with a functionalized methylated polystyrene to produce a methylated polystyrene having pendant N-halamine precursor groups; and

halogenating the methylated polystyrene having pendant N-halamine precursor groups to produce the biocidal methylated polystyrene having pendant N-halamine groups.

58. The method of claim 57, wherein the functionalized methylated polystyrene comprises poly(chloromethyl)styrene.

59. The method of claim 57, wherein the N-halamine precursor comprises a hydantoin group, an imidazolidinone group, an oxazolidinone group, or an isocyanurate group.

60. The method of claim 57, wherein the alkali metal base comprises a carbonate.

61. The method of claim 57, wherein the alkali metal base comprises a hydroxide.

62. The method of claim 57, wherein the alkali metal base comprises a hydride.

63. The method of claim 57, wherein the alkali metal base comprises sodium or potassium base.

64. The method of claim 57, wherein said reacting of the alkali metal salt with the methylated polystyrene occurs in anhydrous dimethylformamide.

65. The method of claim 57, wherein said reacting of the alkali metal salt with the methylated polystyrene occurs in anhydrous dimethylsulfoxide.

66. The method of claim 57, wherein said reacting of the N-halamine precursor with the alkali metal base occurs for from about 15 minutes to about 2 hours at a temperature of from about 25°

to about 100°

C.

67. The method of claim 57, wherein said reacting of the alkali metal salt with the methylated polystyrene occurs for from about 4 to about 96 hours at a temperature of from about 70°

to about 120°

C.

68. An absorbent article, comprising a methylated polystyrene having pendant N-halamine precursor groups.

69. The absorbent article of claim 68, further comprising an absorbent material.

70. The absorbent article of claim 69, wherein said absorbent material comprises cellulose.

71. The absorbent article of claim 69, wherein said absorbent material comprises a super absorbent polymer.

72. An absorbent article, comprising a biocidal methylated polystyrene having pendant N-halamine groups.

73. The absorbent article of claim 72, further comprising an absorbent material.

74. The absorbent article of claim 73, wherein said absorbent material comprises cellulose.

75. The absorbent article of claim 73, wherein said absorbent material comprises a superabsorbent polymer.

76. A polystyrene having a N-halamine precursor group bonded to at least some of the benzene rings of the polystyrene by a methylene group.

77. A polystyrene having a biocidal N-halamine group bonded to at least some of the benzene rings of the polystyrene by a methylene group.

78. A methylated polystyrene comprising a repeating unit, said unit having the formula: