Methods Of Modifying Metal-Oxide Nanoparticles

• US 20130253161A1
• Filed: 12/06/2011
• Published: 09/26/2013
• Est. Priority Date: 12/08/2010
• Status: Abandoned Application

• Current Assignee: Dow Corning Toray Company Limited (Dow, Inc.)
• Original Assignee: Dow Corning Toray Company Limited (Dow, Inc.)
• Inventors: Itoh, Maki, Suto, Michitaka, Amako, Masaaki
• Application Number:
  US13/991,851
• Publication Number:
  US 20130253161A1
• Time in Patent Office: Days
• US Class Current: 528/32
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2002/86 by NMR- or ESR-data
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C09C 1/00 Treatment of specific inorganic materials other than fibrous fillers tenebrescent materials C09K9/00; luminescent materials C09K11/00; Preparation of carbon black
• CPC Class Codes: C09C 1/3676 Treatment with macro-molecular organic compounds
• CPC Class Codes: C09C 1/3684 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 3/12 Treatment with organosilicon compounds C09C3/006 takes precedence
• CPC Class Codes: H01L 23/296 Organo-silicon compounds
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

Methods employing acidic and basic catalysts are disclosed, and generally entail hydrolysis and condensation reactions of silicon based components. The methods are useful for forming siloxane-modified metal-oxide nanoparticles, such as modified ZrO₂ nanoparticles. The siloxane-modified metal-oxide nanoparticles, and products including the siloxane-modified metal-oxide nanoparticles, can be used to form various products, such as lenses or encapsulants for making various devices, such as, but not limited to, light emitting diodes (LEDs).

Claims

1. A method of forming siloxane-modified metal-oxide nanoparticles, said method comprising the steps of:

I) providing (a) an alkoxysilane having at least one aryl group per molecule, (b) an organosiloxane having at least two alkenyl groups per molecule, (c) an acidic catalyst, (d) water, (e) a basic catalyst, (f) metal-oxide nanoparticles, and optionally, (g) a silane having at least one alkenyl group per molecule;

II) reacting the alkoxysilane (a) and the organosiloxane (b), in the presence of the acidic catalyst (c), the water (d), and optionally, the metal-oxide nanoparticles (f), to form an intermediate composition including monomers having hydroxyl groups;

III) reacting the monomers in the presence of the basic catalyst (e), and optionally, the metal-oxide nanoparticles (f), to form a silsesquioxane resin having residual hydroxyl groups; and

IV) optionally, reacting the silsesquioxane resin with the silane (g) to form the siloxane-modified metal-oxide nanoparticles having residual alkenyl groups;

wherein the metal-oxide nanoparticles (f) are present during at least one of steps II) and III).

2. The method as set forth in claim 1, wherein the metal-oxide nanoparticles:

i) are ZrO₂ nanoparticles or TiO₂ nanoparticles;

ii) have a mean particle diameter (D50) of from 1 to 100 nm;

or

iii) both i) and ii).

4. The method as set forth in claim 1, wherein the alkoxysilane is MePhSi(OMe)₃ or PhSi(OMe)₃, where Ph is a phenyl group and Me is a methyl group.

5. The method as set forth in claim 1, wherein the organosiloxane is (ViMe₂Si)₂O, where Vi is a vinyl group and Me is a methyl group.

6. The method as set forth in claim 1, wherein the silane is ViMe₂SiCl, where Vi is a vinyl group and Me is a methyl group.

7. The method as set forth in claim 1, further comprising the step of removing water from the intermediate composition after step II) for inducing step III).

8. The method as set forth in claim 1, wherein the intermediate composition includes methanol, and further comprising the step of removing at least a portion of the methanol from the intermediate composition prior to step III).

9. The method as set forth in claim 1, further comprising the step of applying heat for a period of time during at least one of steps II) and III).

10. The method as set forth in claim 1, wherein at least one of steps II) and III) is conducted in the presence of a solvent different than the water (d).

11. The method as set forth in claim 1, wherein the siloxane-modified metal-oxide nanoparticles include a silsesquioxane resin of the general formula:

^ViM_a^PhMeD_b^PhT_c

where M is SiO_1/2, D is SiO_2/2, T is SiO_3/2, a is from 0.005 to 0.20, b is from 0.0 to 0.40, c is from 0.40 to 0.90, a+b+c=1, Vi is a vinyl group, Ph is a phenyl group, and Me is a methyl group.

3. (canceled)

12-13. -13. (canceled)

14. A method of forming siloxane-modified metal-oxide nanoparticles, said method comprising the steps of:

I) providing (a) an acidic catalyst, (b) metal-oxide nanoparticles, (c) water, (d) an alcohol, (e) a solvent different than the water (c) and alcohol (d), and (f) an alkoxysilane having at least one acryl group per molecule;

II) combining the acidic catalyst (a), the metal-oxide nanoparticles (b), and the water (c) to form a first precursor composition;

III) combining the alcohol (d), the solvent (e), and the alkoxysilane (f) to form a second precursor composition; and

IV) reacting the first and second precursor compositions to form the siloxane-modified metal-oxide nanoparticles.

15. The method as set forth in claim 14, wherein the metal-oxide nanoparticles:

i) are ZrO₂ nanoparticles or TiO₂ nanoparticles;

ii) have a mean particle diameter (D50) of from 1 to 100 nm;

or

iii) both i) and ii).

17. The method as set forth in claim 14, wherein the alkoxysilane is acryloxypropyltrimethoxysilane or methacryloxypropyltrimethoxysilane.

18. The method as set forth in claim 14, wherein the alcohol is methanol and the solvent is toluene.

16. (canceled)

19-20. -20. (canceled)

21. A method of forming siloxane-modified metal-oxide nanoparticles, said method comprising the steps of:

I) providing (a) a sol comprising i) metal-oxide nanoparticles, ii) an acidic component, and iii) water, (b) an alcohol, (c) an alkoxysilane, and (d) a basic catalyst;

II) removing at least a portion of the water iii) from the sol (a) to obtain a particle composition;

III) mixing the alcohol (b) and the particle composition to form a transitional composition; and

IV) reacting the alkoxysilane (c) and the transitional composition to form monomers having hydroxyl groups; and

V) reacting the monomers in the presence of the basic catalyst (d) to form the siloxane-modified metal-oxide nanoparticles.

22. The method as set forth in claim 21, wherein the metal-oxide nanoparticles:

i) are ZrO₂ nanoparticles or TiO₂ nanoparticles;

ii) have a mean particle diameter (D50) of from 1 to 100 nm;

or

iii) both i) and ii).

24. The method as set forth in claim 21, wherein the alkoxysilane is MePhSi(OMe)₃ or PhSi(OMe)₃, where Ph is a phenyl group and Me is a methyl group.

25. The method as set forth in claim 21, wherein after step I), the precursor composition consists essentially of the metal-oxide nanoparticles and the acidic component.

23. (canceled)

26-27. -27. (canceled)

28. A method of forming siloxane-modified metal-oxide nanoparticles, said method comprising the steps of:

I) providing (a) linear- and/or cyclic-siloxane oligomers having residual hydroxyl groups, (b) metal-oxide nanoparticles, and (c) a basic catalyst; and

II) reacting the oligomers (a) in the presence of the metal-oxide nanoparticles (b) and the basic catalyst (c) to form the siloxane-modified metal-oxide nanoparticles.

29. The method as set forth in claim 28, wherein the metal-oxide nanoparticles:

i) are ZrO₂ nanoparticles or TiO₂ nanoparticles;

ii) have a mean particle diameter (D50) of from 1 to 100 nm;

or

iii) both i) and ii).

30-32. -32. (canceled)