Functionalized zirconium oxide particles

• US 7,037,583 B2
• Filed: 11/29/2000
• Issued: 05/02/2006
• Est. Priority Date: 05/19/1999
• Status: Expired due to Term

• Current Assignee: Southwest Research Institute, Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Southwest Research Institute, Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Dixon, Hong, Furman, Benjamin R., Wellinghoff, Stephen T., Norling, Barry K., Rawls, Henry R.
• Primary Examiner(s): LE, HOA T
• Application Number:
  US09/726,769
• Publication Number:
  US 20020013382A1
• Time in Patent Office: 1,980 Days
• Field of Search: 428/403, 428/407, 428/323, 428/328, 428/327
• US Class Current: 428/403
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/446 with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2004/02 obtained by optical microscopy
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/90 Other properties not specified above
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C09C 3/006 Combinations of treatments provided for in groups C09C3/04 - C09C3/12
• CPC Class Codes: Y10S 522/908 Dental utility
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

Metal oxide nanoparticles having at least some surface acid sites functionalized with an adhesion promoter and at least some surface acid sites functionalized with a coupling agent. The nanoparticles are useful in forming composites comprising photopolymerizable matrix monomers, and are primarily suitable for dental and medical restoration. In a preferred embodiment, the metal oxide comprises zirconium, and the coupling agent is a zirconate.

Claims

1. Functionalized zirconium oxide particles comprising:

surfaces comprising a total quantity of hydroxyl groups comprising a complexed fraction of hydroxyl groups comprising a reactive portion of hydroxyl groups and a less reactive portion of hydroxyl groups;

said reactive portion of hydroxyl groups being complexed with functionalities selected from the group consisting of functionalities with high steric hindrance, functionalities with low steric hindrance, and a combination thereof;

said less reactive portion of hydroxyl groups being complexed with said functionalities with low steric hindrance.

2. The functionalized zirconium oxide particles of claim 1 wherein said functionalities having a low steric hindrance comprise mobile adhesion promoters and said functionalities having a high steric hindrance comprise organofunctional coupling agents.

3. The functionalized zirconium oxide particles of claim 2 wherein said complexed fraction of hydroxyl groups is effective to produce a coagulation point of about 1 minute or more.

4. The functionalized zirconium oxide particles of claim 3 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

5. The functionalized zirconium oxide particles of claim 3 wherein a sufficient quantity of said reactive portion of hydroxyl groups is complexed with said organofunctional coupling agent that, upon addition to a resin and curing to form a filled composite, the cured filled composite has a fracture toughness substantially the same as the cured resin alone, upon curing.

6. The functionalized zirconium oxide particles of claim 3 wherein the organofunctional coupling agent comprises a polymerizable group selected from the group consisting of one or more vinyl groups, acryl groups, epoxy groups, and methacryl groups.

7. The functionalized zirconium oxide particles of claim 6 wherein the organofunctional coupling agent comprises a functionality selected from the group consisting of mono-, di-, and tri-functional silanes, isocyanates, zirconates, aluminozirconates, zirconyl methacrylate, titanates, and phosphonates.

8. The functionalized zirconium oxide particles of claim 3 wherein the organofunctional groups are hydrolyzable zirconates having the following general structure:

R¹—

O—

Zr—

(OR²)₃

wherein

R¹ is selected from the group consisting of hydrolyzable alkyl groups having 1 or more carbon atoms and hydrolyzable alkenyl groups having 2 or more carbon atoms; and

R² is selected from the group consisting of copolymerizable alkenyl substituents containing 2 or more carbon atoms.

9. The functionalized zirconium oxide particles of claim 8 wherein R¹ is selected from the group consisting of hydrolyzable alkyl groups having from about 1 to about 9 carbon atoms.

10. The functionalized metal oxide particles of claim 3 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates, neopentyl (diallyl) oxy triacryl zirconates, and aluminozirconates having the following general structure:

wherein R³ is selected from the group consisting of copolymerizable alkenyl groups and carboxyfunctional substituents containing 1 or more carbon atoms.

11. The functionalized zirconium oxide particles of claim 3 wherein said organofunctional coupling agents are methacryloxy aluminozirconates.

12. The functionalized zirconium oxide particles of claim 3 wherein one or more of said organofunctional coupling agents and said mobile adhesion promoter is bound to the oxide surface via an ester linkage to a phosphonate group.

13. The functionalized zirconium oxide particles of claim 12 wherein said phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.

14. The functionalized zirconium oxide particles of claim 3 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

15. The functionalized zirconium oxide particles of claim 3 wherein the mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

16. The functionalized zirconium oxide particles of claim 3 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates and neopentyl (diallyl) oxy triacryl zirconates.

17. The functionalized zirconium oxide particles of claim 3 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

18. The functionalized zirconium oxide particles of claim 2 wherein said complexed fraction of hydroxyl groups is effective to produce a coagulation point of about 1 hour or more.

19. The functionalized zirconium oxide particles of claim 18 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

20. The functionalized zirconium oxide particles of claim 18 wherein a sufficient quantity of said reactive portion of hydroxyl groups is complexed with said organofunctional coupling agent that, upon addition to a resin and curing to form a filled composite, the cured filled composite has a fracture toughness substantially the same as the cured resin alone, upon curing.

21. The functionalized zirconium oxide particles of claim 18 wherein the organofunctional coupling agent comprises a polymerizable group selected from the group consisting of one or more vinyl groups, acryl groups, epoxy groups, and methacryl groups.

22. The functionalized zirconium oxide particles of claim 21 wherein the organofunctional coupling agent comprises a functionality selected from the group consisting of mono-, di-, and tri-functional silanes, isocyanates, zirconates, aluminozirconates, zirconyl methacrylate, titanates, and phosphonates.

23. The functionalized zirconium oxide particles of claim 18 wherein the organofunctional groups are hydrolyzable zirconates having the following general structure:

R¹—

O—

Zr—

(OR²)₃

wherein

R¹ is selected from the group consisting of hydrolyzable alkyl groups having 1 or more carbon atoms and hydrolyzable alkenyl groups having 2 or more carbon atoms; and

R² is selected from the group consisting of copolymerizable alkenyl substituents containing 2 or more carbon atoms.

24. The functionalized zirconium oxide particles of claim 23 wherein R¹ is selected from the group consisting of hydrolyzable alkyl groups having from about 1 to about 9 carbon atoms.

25. The functionalized zirconium oxide particles of claim 18 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates, neopentyl (diallyl) oxy triacryl zirconates, and aluminozirconates having the following general structure:

wherein R³ is selected from the group consisting of copolymerizable alkenyl groups and carboxyfunctional substituents containing 1 or more carbon atoms.

26. The functionalized zirconium oxide particles of claim 18 wherein said organofunctional coupling agents are methacryloxy aluminozirconates.

27. The functionalized zirconium oxide particles of claim 18 wherein one or more of said organofunctional coupling agents and said less reactive functionalities is bound to the oxide surface via an ester linkage to a phosphonate group.

28. The functionalized zirconium oxide particles of claim 27 wherein said phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.

29. The functionalized zirconium oxide particles of claim 18 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

30. The zirconium oxide particles of claim 18 wherein the mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

31. The functionalized zirconium oxide particles of claim 18 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

32. The functionalized zirconium oxide particles of claim 2 wherein said organofunctional coupling agents are irreversibly complexed with said reactive portion of hydroxyl groups.

33. The functionalized zirconium oxide particles of claim 32 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates and neopentyl (diallyl) oxy triacryl zirconates.

34. The functionalized zirconium oxide particles of claim 32 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

35. The functionalized zirconium oxide particles of claim 32 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

36. The functionalized zirconium oxide particles of claim 2 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

37. The functionalized zirconium oxide particles of claim 36 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

38. The functionalized zirconium oxide particles of claim 2 wherein a sufficient quantity of said reactive portion of hydroxyl groups is complexed with an organofunctional coupling agent that, upon addition to a resin and curing to form a filled composite, the cured filled composite has a fracture toughness substantially the same as said resin alone, upon curing.

39. The functionalized zirconium oxide particles of claim 2 wherein the organofunctional coupling agent comprises a polymerizable group selected from the group consisting of one or more vinyl groups, acryl groups, epoxy groups, and methacryl groups.

40. The functionalized zirconium oxide particles of claim 39 wherein the organofunctional coupling agent comprises a functionality selected from the group consisting of mono-, di-, and tri-functional silanes, isocyanates, zirconates, aluminozirconates, zirconyl methacrylate, titanates, and phosphonates.

41. The functionalized zirconium oxide particles of claim 2 wherein the organofunctional groups are hydrolyzable zirconates having the following general structure:

R¹—

O—

Zr—

(OR²)₃

wherein

R¹ is selected from the group consisting of hydrolyzable alkyl groups having 1 or more carbon atoms and hydrolyzable alkenyl groups having 2 or more carbon atoms; and

R² is selected from the group consisting of copolymerizable alkenyl substituents containing 2 or more carbon atoms.

42. The functionalized zirconium oxide particles of claim 41 wherein R¹ is selected from the group consisting of hydrolyzable alkyl groups having from about 1 to about 9 carbon atoms.

43. The functionalized zirconium oxide particles of claim 42 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty adds, fatty alcohols, and ester linked fatty acids.

44. The functionalized zirconium oxide particles of claim 42 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

45. The functionalized zirconium oxide particles of claim 41 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates and neopentyl (diallyl) oxy triacryl zirconates.

46. The functionalized zirconium oxide particles of claim 45 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

47. The functionalized zirconium oxide particles of claim 45 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

48. The functionalized zirconium oxide particles of claim 41 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

49. The functionalized zirconium oxide particles of claim 41 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

50. The functionalized zirconium oxide particles of claim 2 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates, neopentyl (diallyl) oxy triacryl zirconates, and aluminozirconates having the following general structure:

wherein R³ is selected from the group consisting of copolymerizable alkenyl groups and carboxyfunctional substituents containing 1 or more carbon atoms.

51. The functionalized zirconium oxide particles of claim 50 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

52. The functionalized zirconium oxide particles of claim 2 wherein said organofunctional coupling agents are methacryloxy aluminozirconates.

53. The functionalized zirconium oxide particles of claim 2 wherein one or more of said organofunctional coupling agent and said mobile adhesion promoter is bound to the oxide surface via an ester linkage to a phosphonate group.

54. The functionalized zirconium oxide particles of claim 53 wherein said phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.

55. The functionalized zirconium oxide particles of claim 2 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

56. The functionalized zirconium oxide particles of claim 2 wherein the mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

57. The zirconium oxide particles of claim 2 having an average diameter of from about 10 to about 150 nanometers.

58. The functionalized zirconium oxide particles of claim 2 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates and neopentyl (diallyl) oxy triacryl zirconates.

59. The functionalized zirconium oxide particles of claim 58 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

60. The functionalized zirconium oxide particles of claim 59 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

61. The functionalized zirconium oxide particles of claim 2 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

62. The functionalized zirconium oxide particles of claim 1 wherein said complexed fraction of hydroxyl groups is effective to produce a coagulation point of about 1 minute or more.

63. The functionalized zirconium oxide particles of claim 62 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

64. The zirconium oxide particles of claim 62 having an average diameter of from about 10 to about 150 nanometers.

65. The functionalized zirconium oxide particles of claim 1 wherein said complexed fraction of hydroxyl groups is effective to produce a coagulation point of about 1 hour or more.

66. The functionalized zirconium oxide particles of claim 65 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

67. The zirconium oxide particles of claim 65 having an average diameter of from about 10 to about 150 nanometers.

68. The functionalized zirconium oxide particles of claim 1 wherein said complexed fraction of hydroxyl groups is about 50% or more of said total quantity of hydroxyl groups.

69. The functionalized zirconium oxide particles of claim 1 wherein said complexed fraction of hydroxyl groups is substantially all of said total quantity of hydroxyl groups.

70. The functionalized zirconium oxide particles of claim 1 wherein the functionality with low steric hindrance is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

71. The zirconium oxide particles of claim 1 having an average diameter of from about 10 to about 150 nanometers.

72. Functionalized zirconium oxide particles comprising a surface comprising a total quantity of hydroxyl groups comprising a complexed fraction of hydroxyl groups and an uncomplexed fraction of hydroxyl groups, said complexed fraction of hydroxyl groups being effective to produce a coagulation point of about one minute or more after removal of a solvent from a mixture of said zirconium oxide particles and a matrix resin.

73. The functionalized zirconium oxide particles of claim 72 wherein said complexed fraction of hydroxyl groups is effective to produce a coagulation point of about one hour or more after removal of a solvent.

74. The functionalized zirconium oxide particles of claim 73 wherein said complexed fraction of hydroxyl groups comprises a less reactive portion of hydroxyl groups complexed with a mobile adhesion promoter and a more reactive portion of hydroxyl groups complexed with an organofunctional coupling agent.

75. The functionalized zirconium oxide particles of claim 74 wherein the organofunctional coupling agent also comprises an adhesion promoter.

76. The functionalized zirconium oxide particles of claim 74 wherein a sufficient quantity of said reactive portion of hydroxyl groups is complexed with said organofunctional coupling agent that, upon addition to a resin and curing to form a filled composite, the cured filled composite has a fracture toughness substantially the same as the cured resin alone, upon curing.

77. The functionalized zirconium oxide particles of claim 74 wherein the organofunctional coupling agent comprises a polymerizable group selected from the group consisting of one or more vinyl groups, acryl groups, epoxy groups, and methacryl groups.

78. The functionalized zirconium oxide particles of claim 77 wherein the organofunctional coupling agent comprises a functionality selected from the group consisting of mono-, di-, and tri-functional silanes, isocyanates, zirconates, aluminozirconates, zirconyl methacrylate, titanates, and phosphonates.

79. The functionalized zirconium oxide particles of claim 74 wherein the organofunctional groups are hydrolyzable zirconates having the following general structure:

R¹—

O—

Zr—

(OR²)₃

wherein

R¹ is selected from the group consisting of hydrolyzable alkyl groups having 1 or more carbon atoms and hydrolyzable alkenyl groups having 2 or more carbon atoms; and

R² is selected from the group consisting of copolymerizable alkenyl substituents containing 2 or more carbon atoms.

80. The functionalized zirconium oxide particles of claim 79 wherein R¹ is selected from the group consisting of hydrolyzable alkyl groups having from about 1 to about 9 carbon atoms.

81. The functionalized zirconium oxide particles of claim 80 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

82. The functionalized zirconium oxide particles of claim 80 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

83. The functionalized zirconium oxide particles of claim 79 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates and neopentyl (diallyl) oxy triacryl zirconates.

84. The functionalized zirconium oxide particles of claim 83 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

85. The functionalized zirconium oxide particles of claim 83 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

86. The functionalized zirconium oxide particles of claim 79 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

87. The functionalized zirconium oxide particles of claim 79 wherein said mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

88. The functionalized zirconium oxide particles of claim 74 wherein the organofunctional coupling agents comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates, neopentyl (diallyl) oxy triacryl zirconates, and aluminozirconates having the following general structure:

wherein R³ is selected from the group consisting of copolymerizable alkenyl groups and carboxyfunctional substituents containing 1 or more carbon atoms.

89. The functionalized zirconium oxide particles of claim 74 wherein said organofunctional coupling agents are methacryloxy aluminozirconates.

90. The functionalized zirconium oxide particles of claim 74 wherein one or more of said organofunctional coupling agents and said less reactive functionalities is bound to the oxide surface via an ester linkage to a phosphonate group.

91. The functionalized zirconium oxide particles of claim 90 wherein the phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.

92. The functionalized zirconium oxide particles of claim 74 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

93. The zirconium oxide particles of claim 74 wherein the mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

94. The functionalized zirconium oxide particles of claim 72 wherein said complexed fraction of hydroxyl groups comprises a less reactive portion of hydroxyl groups complexed with a mobile adhesion promoter and a more reactive portion of hydroxyl groups complexed with an organofunctional coupling agent.

95. The functionalized zirconium oxide particles of claim 94 wherein the organofunctional coupling agent also comprises an adhesion promoter.

96. The functionalized zirconium oxide particles of claim 94 wherein a sufficient quantity of said reactive portion of hydroxyl groups is complexed with said organofunctional coupling agent that, upon addition to a resin and curing to form a filled composite, the cured filled composite has a fracture toughness substantially the same as the cured resin alone, upon curing.

97. The functionalized zirconium oxide particles of claim 94 wherein the organofunctional coupling agent comprises a polymerizable group selected from the group consisting of one or more vinyl groups, acryl groups, epoxy groups, and methacryl groups.

98. The functionalized zirconium oxide particles of claim 97 wherein the organofunctional coupling agent comprises a functionality selected from the group consisting of mono-, di-, and tri-functional silanes, isocyanates, zirconates, aluminozirconates, zirconyl methacrylate, titanates, and phosphonates.

99. The functionalized zirconium oxide particles of claim 94 wherein the organofunctional groups are hydrolyzable zirconates having the following general structure:

R¹—

O—

Zr—

(OR²)₃

wherein

R¹ is selected from the group consisting of hydrolyzable alkyl groups having 1 or more carbon atoms and hydrolyzable alkenyl groups having 2 or more carbon atoms; and

R² is selected from the group consisting of copolymerizable alkenyl substituents containing 2 or more carbon atoms.

100. The functionalized zirconium oxide particles of claim 99 wherein R¹ is selected from the group consisting of hydrolyzable alkyl groups having from about 1 to about 9 carbon atoms.

101. The functionalized zirconium oxide particles of claim 94 wherein the organofunctional coupling agent comprise moieties selected from the group consisting of neopentyl (diallyl) oxy trimethacryl zirconates, neopentyl (diallyl) oxy triacryl zirconates, and aluminozirconates having the following general structure:

wherein R³ is selected from the group consisting of copolymerizable alkenyl groups and carboxyfunctional substituents containing 1 or more carbon atoms.

102. The functionalized zirconium metal oxide particles of claim 94 wherein said organofunctional coupling agents are methacryloxy aluminozirconates.

103. The functionalized zirconium oxide particles of claim 94 wherein one or more of said organofunctional coupling agents and said less reactive functionalities is bound to the oxide surface via an ester linkage to a phosphonate group.

104. The functionalized zirconium oxide particles of claim 103 wherein the phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.

105. The functionalized zirconium oxide particles of claim 94 wherein the mobile adhesion promoter is selected from the group consisting of silanes, phosphonates, phosphates, chelating agents, fatty acids, fatty alcohols, and ester linked fatty acids.

106. The zirconium oxide particles of claim 94 wherein the mobile adhesion promoter comprises dimethyl ethoxy vinyl silane.

107. Functionalized zirconium oxide particles comprising:

surfaces comprising a total quantity of hydroxyl groups comprising a complexed fraction of hydroxyl groups comprising a reactive portion of hydroxyl groups and a less reactive portion of hydroxyl groups;

said reactive portion of hydroxyl groups being complexed with functionalities selected from the group consisting of functionalities with high steric hindrance, functionalities with low steric hindrance, and a combination thereof;

said less reactive portion of hydroxyl groups being complexed with said functionalities with low steric hindrance;

wherein one or more of said functionalities with high steric hindrance and said functionalities with low steric hindrance is bound to the oxide surface via an ester linkage to a phosphonate group.

108. The functionalized zirconium oxide particles of claim 107 wherein said phosphonate group comprises a silyl ester which may or may not comprise a polymerizable group.