Coated titanium dioxide particles
View Patent ↗A method for producing nanoscale titanium dioxide particles which are coated with an oxide, a hydroxide or an oxide hydroxide of Al, Ce, Zr and/or Si wherein the enzymatic precipitant system urease/urea is used. Said coated titanium dioxide particles can have an average size of less than 50 nm, the coating providing effective protection against photocatalytic reactions. The coated particles are suitable, in particular, as UV absorbers in a transparent organic matrix.
1. A process for preparing (hydr)oxide-coated nanoscale titanium dioxide particles, wherein the process comprises contacting the titanium dioxide particles in a suspension thereof with one or more compounds of at least one of Al, Ce, Zr and Si in the presence of urea and urease and under conditions which result in a precipitation of at least one of an oxide, hydroxide and oxide hydroxide of one or more of Al, Ce, Zr and Si on the surface of the titanium dioxide particles.
2. The process of claim 1 , wherein the conditions which result in a precipitation comprise a pH of at least 4.
3. The process of claim 2 , wherein the suspension comprises water.
4. The process of claim 3 , wherein the titanium dioxide particles have a number-average diameter of below 30 nm.
5. The process of claim 4 , wherein the precipitation results in from 5% to 10% by weight of a coating on the titanium dioxide particles.
6. The process of claim 3 , wherein the titanium dioxide particles have a number-average diameter of below 40 nm.
7. The process of claim 2 , wherein the titanium dioxide particles have a number-average diameter of below 50 nm.
8. The process of claim 7 , wherein the titanium dioxide particles comprise rutile.
9. The process of claim 7 , wherein the precipitation results in from 3% to 10% by weight of a coating on the titanium dioxide particles.
10. The process of claim 1 , wherein the titanium dioxide particles have a number-average diameter of below 100 nm.
11. The process of claim 1 , wherein the titanium dioxide particles comprise surface-modified particles.
12. The process of claim 11 , wherein the surface-modified particles comprise particles surface-modified with at least one of a diphosphate, a polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone and a methyl vinyl ether-maleic anhydride copolymer.
13. The process of claim 12 , wherein the surface-modified particles comprise from 0.1% to 10% by weight of at least one surface-modifying agent.
14. The process of claim 11 , wherein the surface-modified particles comprise particles which are surface-modified with polyvinyl alcohol.
15. The process of claim 1 , wherein the titanium dioxide particles comprise at least one of anatase and rutile.
16. The process of claim 15 , wherein the one or more compounds comprise aluminum sulfate.
17. The process of claim 1 , wherein the one or more compounds comprise at least one of a nitrate, sulfate, halide, hydrogen phosphate and phosphate of one or more or Al, Ce, Zr and Si.
18. The process of claim 17 , wherein the one or more compounds comprise at least one of aluminum sulfate, aluminum chloride and cerium chloride.
19. The process of claim 17 , wherein the one or more compounds comprise aluminum.
20. The process of claim 1 , wherein the process is carried out at a pH of from 4 to 9.
21. The process of claim 1 , wherein the process is carried out at room temperature.
22. The process of claim 1 , wherein the process is carried out at about 25° C.
23. The process of claim 1 , wherein from 20 to 100 parts by weight of urea are used per 1 part by weight of urease.
24. The process of claim 1 , wherein the precipitation results in from 0.1% to 10% by weight of a coating on the titanium dioxide particles.
25. The process of claim 24 , wherein the coating comprises at least one of aluminum oxide and aluminum hydroxide.
26. The process of claim 25 , wherein the coating consists essentially of boehmite.
27. The process of claim 24 , wherein the coating has a substantially uniform thickness.
28. The process of claim 1 , which further comprises a hydrothermal treatment of the coated titanium dioxide particles.
29. The process of claim 1 , which further comprises recovering the coated titanium dioxide particles from the suspension.
30. A process for preparing (hydr)oxide-coated titanium dioxide particles, wherein the process comprises contacting titanium dioxide particles which comprise at least one of anatase and rutile and have a number-average diameter of below 50 nm in an aqueous suspension thereof with at least one compound selected from nitrates, sulfates, halides, hydrogen phosphates and phosphates of one or more or Al, Ce, Zr and Si in the presence of urea and urease and under conditions which result in a precipitation of at least one of an oxide, hydroxide and oxide hydroxide of one or more of Al, Ce, Zr and Si on the surface of the titanium dioxide particles.
31. The process of claim 30 , wherein the conditions which result in a precipitation comprise a pH of at least 4.
32. The process of claim 30 , wherein the titanium dioxide particles have a number-average diameter of below 30 nm.
33. The process of claim 30 , wherein the titanium dioxide particles comprise surface-modified particles.
34. The process of claim 33 , wherein the surface-modified particles comprise particles surface-modified with at least one of a diphosphate, a polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone and a methyl vinyl ether-maleic anhydride copolymer.
35. The process of claim 33 , wherein the surface-modified particles comprise from 0.1% to 10% by weight of at least one surface-modifying agent.
36. The process of claim 30 , wherein the at least one compound comprises at least one of aluminum sulfate, aluminum chloride and cerium chloride.
37. The process of claim 36 , wherein the process is carried out at a pH of from 4 to 9.
38. The process of claim 37 , wherein the process is carried out at room temperature.
39. The process of claim 30 , wherein from 20 to 100 parts by weight of urea are used per 1 part by weight of urease.
40. The process of claim 30 , wherein the precipitation results in from 3% to 10% by weight of a coating on the titanium dioxide particles.
41. The process of claim 40 , wherein the coating comprises at least one of aluminum oxide and aluminum hydroxide.
42. The process of claim 40 , wherein the coating consists essentially of boehmite.
43. A process for preparing (hydr)oxide-coated titanium dioxide particles, wherein the process comprises contacting surface-modified titanium dioxide particles which comprise rutile and have a number-average diameter of below 30 nm in an aqueous suspension thereof with at least one compound selected from aluminum sulfate, aluminum chloride and cerium chloride in the presence of urea and urease and under conditions which result in a precipitation of at least one of an oxide, hydroxide and oxide hydroxide of at least one of Al and Ce on the surface of the titanium dioxide particles.
44. The process of claim 43 , wherein the process is carried out at a pH of from 4 to 9.
45. The process of claim 44 , wherein from 20 to 100 parts by weight of urea are used per 1 part by weight of urease.