Mechanically strong and transparent or translucent composites made using zirconium oxide nanoparticles

• US 6,194,481 B1
• Filed: 05/19/1999
• Issued: 02/27/2001
• 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): Berman, Susan W.
• Application Number:
  US09/314,350
• Time in Patent Office: 650 Days
• Field of Search: 522/81, 522/83, 522/77, 522/79, 522/71, 522/908, 522/103, 522/182, 523/115, 523/116, 524/413, 524/398
• US Class Current: 522/77
• 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

Zirconium oxide nanoparticles having at least some surface acid sites functionalized with a silanating agent and at least some surface acid sites finctionalized with zirconate or a zircoaluminate. The nanoparticles are useful in composites comprising photopolymerizable alkene matrix monomers, and are primarily suitable for dental and medical restoration.

Claims

1. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising monomers comprising a photopolymerizable unsaturated carbon-carbon bond;

particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization;

wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate.

2. The composition of claim 1 wherein

said zirconate has the following general structure:

3. The composition of claim 1 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates and neopentyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.

4. A dental restoration comprising the composition of claim 1.

5. A resin for optical applications requiring a high refractive index comprising the, composition of claim 1.

6. An adhesive composition comprising the composition of claim 1.

7. A bone restoration comprising the composition of claim 1.

8. The composition of claim 1 wherein said silanating agent is a dialkyl alkoxy alkenyl silane wherein said alkyl groups and said alkoxy group have from about 1 to about 3 carbon atoms.

9. The composition of claim 1 wherein said silanating agent is dimethyl ethoxy vinyl silane.

10. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising monomers selected from the group consisting of bisacrylate monomers, bis-methacrylate monomers, and combinations thereof;

particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization;

wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate.

11. The composition of claim 10 wherein said silanating agent is a dialkyl alkoxy alkenyl silane wherein said alkyl groups and said alkoxy group have from about 1 to about 3 carbon atoms.

12. The composition of claim 10 wherein said silanating agent is dimethyl ethoxy vinyl silane.

13. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising photopolymerizable monomers selected from the group consisting of bisacrylate monomers, bis-methacrylate monomers, and combinations thereof;

particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization;

wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate;

wherein said zirconate has the following general structure;

14. The composition of claim 13 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates and neopentyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.

15. The composition of claim 13 wherein said silanating agent is a dialkyl alkoxy alkenyl silane wherein said alkyl groups and said alkoxy group have from about 1 to about 3 carbon atoms.

16. The composition of claim 13 wherein said silanating agent is dimethyl ethoxy vinyl silane.

17. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising photopolymerizable monomers selected from the group consisting of glycerol monomethacrylate, glycerol dimethacrylate, hydroxyethylmethacrylate, 2,2-bis[p-(2′

-hydroxy-3′

-methacryloxypropoxy)phenylene]propane, ethoxylated 2,2-bis[p-(2′

-hydroxy-3′

-methacryloxypropoxy)phenylene]propane, and combinations thereof;

particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization;

wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate.

18. The composition of claim 17 wherein

said zirconate has the following general structure:

19. The composition of claim 17 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates, neopeetyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.

20. The composition of claim 17 wherein said silanating agent is a dialkyl alkoxy alkenyl silane wherein said alkyl groups and said alkoxy group have from about 1 to about 3 carbon atoms.

21. The composition of claim 17 wherein said silanating agent is dimethyl ethoxy vinyl silane.

22. A method of making photopolymerizable, transparent or translucent X-ray opaque compositions comprising admixing a matrix comprising monomers comprising a photopolymerizable unsaturated carbon-carbon bond with X-ray opaque zirconium oxide particles having a diameter in nanometers which is small enough to provide sufficient transparency and large enough to provide effective fracture toughness after photopolymerization, wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymnerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate.

23. The method of claim 22 wherein

said zirconate has the following general structure:

24. The method of claim 22 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates, neopentyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.

25. A method of making photopolymerizable, transparent or translucent X-ray opaque compositions comprising admixing a matrix comprising photopolymerizable monomers selected from the group consisting of bisacrylate monomers, bis-methacrylate monomers, and combinations thereof with particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization, wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate,

wherein said zirconate has the following general structure:

26. The method of claim 25 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates, neopentyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.

27. A method of making photopolymerizable, transparent or translucent X-ray opaque compositions comprising

providing a matrix comprising photopolymerizable monomers selected from the group consisting of glycerol monomethacrylate, glycerol dimethacrylate, hydroxyethylmethacrylate, 2,2-bis[p-(2′

-hydroxy-3′

-methacryloxypropoxy)phenylene]propane, ethoxylated 2,2-bis[p-(2′

-hydroxy-3′

-methacryloxypropoxy)phenylene]propane, and combinations thereof; and

mixing said matrix with particles comprising zirconium oxide, said particles having a diameter in nanometers which is small enough to provide sufficient transparency but large enough to provide effective fracture toughness after photopolymerization, wherein said particles comprise a surface comprising hydroxyl groups, a first portion of said hydroxyl groups being bonded to a silicon atom of a silanating agent effective to increase hydrophobicity of said surface in an amount sufficent to allow said particles to be homogeneously dispersed in a hydrophobic resin, a second portion of said hydroxyl groups being bonded to a functionality selected from the group consisting of a zirconium atom of a photopolymerizable, hydrolyzable zirconate, and a zirconium atom or an aluminum atom of a photopolymerizable zircoaluminate.

28. The composition of claim 27 wherein

said zirconate has the following general structure:

29. The method of claim 27 wherein

said zirconate is selected from the group consisting of neopentyl(diallyl)oxy trimethacryl zirconates, neopentyl(diallyl)oxytriacryl zirconates;

and

said zircoaluminate is a methacryloxy-functional zircoaluminate.