Porous metal oxide particles, production method thereof and application thereof

Patent metadata

Field	Value
Publication number	US-10045942-B2
Application number	US-201414892385-A
Country	US
Kind code	B2
Filing date	May 14, 2014
Priority date	May 22, 2013
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

Provided are porous metal oxide particles, in which 50% mean particle size by volume is equal to or larger than 50 nm and equal to or smaller than 300 nm, ratio of 90% mean particle size by volume to 50% mean particle size by volume (D90/D50) is equal to or lower than 2.0, the particles have mesopores having a pore size determined by BJH method of equal to or larger than 5 nm and equal to or smaller than 30 nm, and the structure of the pores is a three-dimensional cubic phase structure.

First claim

The invention claimed is:

1. Porous metal oxide particles,
the 50% mean particle size by volume thereof being equal to or larger than 50 nm and equal to or smaller than 90 nm,
the ratio of 90% mean particle size by volume to 50% mean particle size by volume (D90/D50) being equal to or lower than 2.0,
the particles having mesopores having a pore size determined by BJH method equal to or larger than 5 nm and equal to or smaller than 30 nm, and
the structure of the pores being a three-dimensional cubic phase structure.

2. The porous metal oxide particles according to claim 1 ,
wherein the 50% mean particle size by volume thereof is equal to or larger than 50 nm and equal to or smaller than 90 nm,
the ratio of 90% mean particle size by volume to 50% mean particle size by volume (D90/D50) is equal to or lower than 1.5,
the particles have mesopores having a pore size determined by BJH method equal to or larger than 5 nm and equal to or smaller than 30 nm, and
the structure of the pores is a three-dimensional cubic phase structure.

3. A method of producing the porous metal oxide particles according to claim 1 , comprising:
a step of obtaining a mixture comprising water and/or an organic solvent miscible or partially miscible with water, water-insoluble polymer particles having 50% mean particle size by volume equal to or larger than 5 nm and equal to or smaller than 30 nm, and a base catalyst;
a step of obtaining organic and inorganic composite particles by mixing a metal oxide precursor to said mixture and causing a sol-gel reaction of the metal oxide precursor; and
a step of removing said water-insoluble polymer particles from said organic and inorganic composite particles.

4. The method of producing the porous metal oxide particles according to claim 3 ,
wherein said water-insoluble polymer particles are particles composed of a terminal branched polyolefin based copolymer represented by the following general formula (1), and having number average molecular weight equal to or lower than 2.5×10 4 ,

(In the formula, A represents polyolefin chain, R 1 and R 2 represent hydrogen atom or alkyl group having 1 to 18 carbon atoms and at least one thereof is hydrogen atom, X 1 and X 2 , which may be the same or different groups, represent a group having straight or branched polyalkylene glycol group).

5. The method of producing the porous metal oxide particles according to claim 4 ,
wherein X 2 and X 2 of the terminal branched polyolefin based copolymer represented by said general formula (1) are the same or different groups, and are represented by general formula (2)
-E-X 3   (2)

(In the formula, E represents oxygen atom or sulfur atom, X 3 represents polyalkylene glycol group or group represented by general formula (3)
—R 3 -(G) m   (3)

(In the formula, R 3 represents m+1 valent hydrocarbon group, G, which is the same or different groups, represents a group represented by —OX 4 or —NX 5 X 6 (X 4 to X 6 represent a polyalkylene glycol group,), m represents a number of bonds of R 3 with G and is an integer of from 1 to 10,))
or are represented by general formula (4),

(In the formula, X 7 and X 8 , which are the same or different groups, represent a polyalkylene glycol group or group represented by the above-described general formula (3)).

6. The method of producing the porous metal oxide particles according to claim 4 ,
wherein said terminal branched polyolefin based copolymer is represented by the following general formula (1a) or general formula (1b),

(In the formula, R 4 and R 5 represent hydrogen atom or alkyl group having 1 to 18 carbon atoms and at least one thereof is hydrogen atom, R 6 and R 7 represent hydrogen atom or methyl group and at least one thereof is hydrogen atom, R 8 and R 9 represent hydrogen atom or methyl group and at least one thereof is hydrogen atom, l+m represents an integer equal to or larger than 2 and equal to or smaller than 450, n represents an integer equal to or larger than 20 and equal to or smaller than 300,)

(In the formula, R 4 and R 5 represent hydrogen atom or alkyl group having 1 to 18 carbon atoms and at least one thereof is hydrogen atom, R 6 and R 7 represent hydrogen atom or methyl group and at least one thereof is hydrogen atom, R 8 and R 9 represent hydrogen atom or methyl group and at least one thereof is hydrogen atom, R 10 and R 11 represent hydrogen atom or methyl group and at least one thereof is hydrogen atom, l+m+o represents an integer equal to or larger than 3 and equal to or smaller than 450, n represents an integer equal to or larger than 20 and equal to or smaller than 300,).

7. The method of producing the porous metal oxide particles according to claim 3 ,
wherein said step of obtaining a mixture comprises a step of mixing said water and/or said organic solvent capable of dissolving a part or all of water, water dispersion of said water-insoluble polymer particles and said base catalyst.

8. The method of producing the porous metal oxide particles according to claim 3 ,
wherein the metal oxide precursor is mixed in a condition of being preliminarily diluted with an organic solvent miscible or partially miscible with water in said step of obtaining the organic and inorganic composite particles.

9. A resin composition comprising the porous metal oxide particles according to claim 1 and a binder resin.

10. A film comprising the porous metal oxide particles according to claim 1 .

11. A paint comprising the porous metal oxide particles according to claim 1 .

12. A thermal insulation material comprising the porous metal oxide particles according to claim 1 .

13. A low dielectric constant material comprising the porous metal oxide particles according to claim 1 .

14. An ink comprising the porous metal oxide particles according to claim 1 .

15. A medicinal agent adapting a drug delivery system (DDS) comprising the porous metal oxide particles according to claim 1 , wherein a drug is contained within the mesopores.

16. A coating material comprising a component (A) and a component (B):
(A) the porous metal oxide particles according to claim 1 ; and
(B) a curable functional group-containing compound.

17. The coating material according to claim 16 ,
wherein the component (B) is an activated energy beam-curable functional group-containing compound or a thermosetting functional group-containing silicon compound.

18. The coating material according to claim 16 ,
wherein ratio of the component (A) to 100 parts by weight of the components (A) and (B) in total is equal to or higher than 1 part by weight and equal to or lower than 60 parts by weight.

19. A coating film obtained by curing the coating material according to claim 16 .

20. A film comprising the coating film according to claim 19 in a surface section thereof.

21. A lens comprising the coating film according to claim 19 in a surface section thereof.

22. An image display device comprising the coating film according to claim 19 on the surface thereof.

Assignees

• Mitsui Chemicals Inc

Inventors

• Nakayama Norio
• Wang Hongbo
• Makio Haruyuki

Classifications

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C01B33/12

  Silica; Hydrates thereof, e.g. lepidoic silicic acid · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title

• C08K7/26

  Silicon- containing compounds · CPC title

• C01P2006/17

  Pore diameter distribution · CPC title