Method of producing silica-based particles

Patent metadata

Field	Value
Publication number	US-10239759-B2
Application number	US-201514607394-A
Country	US
Kind code	B2
Filing date	Jan 28, 2015
Priority date	Jul 21, 2004
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

A method of producing silica-based particles includes, when a dispersion liquid of composite oxide particles is prepared by simultaneously adding an aqueous silicate solution and/or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound in an alkali aqueous solution or in an alkali aqueous solution with seed particles dispersed therein, if required, the aqueous silicate solution and/or the acidic silicic acid solution and the aqueous solution of alkali-soluble inorganic compound are added so that the molar ratio of MO x /SiO 2 are in a range from 0.01 to 2, herein MO x denoting an inorganic oxide other than silica and SiO 2 denoting silica to prepare the dispersion liquid of composite oxide particles with an average diameter (D p1 ) in a range from 3 to 300 nm.

First claim

The invention claimed is:

1. A method of producing hollow spherical silica-based particles, comprising:
(a) a step of preparing a first dispersion liquid of first composite oxide particles having an average diameter (D p1 ) of 3 to 300 nm by simultaneously adding a solution (M) containing element M and a solution (S) into an alkali aqueous solution so that a molar ratio (MO x /SiO 2 ) of the first dispersion liquid is 0.01 to 2,
wherein the solution (M) is an aqueous solution of an alkali soluble inorganic compound,
the element M is at least one of Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, and W,
the solution (S) is at least one of an aqueous silicate solution and an acidic silicic acid solution,
the MO x denotes a molar number of the element M contained in the solution (M) in terms of an oxide, and
the SiO 2 denotes a molar number of an element Si contained in the solution (S) in terms of an oxide (SiO 2 ),
(b-1) a step of preparing a second dispersion liquid by adding an electrolytic salt into the first dispersion liquid so that a molar ratio (M E /M S ) of the second dispersion liquid is 0.1 to 10,
(b-2) a step of preparing a third dispersion liquid of third composite oxide particles that are the first composite oxide particles forming shells around the first composite oxide particles by adding a solution (M) containing element M and a solution (S) into the second dispersion liquid so that a value of B/A (the A denotes the molar ratio (MOx/SiO 2 ) of the first dispersion liquid, the B denotes the molar ratio (MOx/SiO 2 ) of the third dispersion liquid) satisfies 0<(B/A)≤0.8,
wherein the electrolytic salt is a water-soluble compound selected from the group consisting of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, ammonium sulfate, magnesium chloride, and magnesium nitrate,
the M E denotes a number of mole of the electrolytic salt,
the M S denotes a number of mole of the element Si contained in the first dispersion liquid in terms of the oxide (SiO 2 ),
the solution (M) of the step (b-2) is an aqueous solution of an alkali soluble inorganic compound,
the element M is at least one of Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, and W,
the solution (S) of the step (b-2) is at least one of an aqueous silicate solution and an acidic silicic acid solution,
the MO x denotes a molar number of the element M contained in the solution (M) of the step (b-2) in terms of an oxide, and
the SiO 2 denotes a molar number of an element Si contained in the solution (S) of the step (b-2) in terms of an oxide (SiO 2 ),
(c-1) a step of adding an acid into the third dispersion liquid to dissolve elements constituting the third composite oxide particles other than silicon,
(c-2) a step of removing dissolved elements from a fourth dispersion liquid obtained by the step (c-1), and
(e) a step of aging a fifth dispersion liquid obtained by the step (c-2) at a room temperature to 300° C.,
wherein the third composite oxide particles have an average diameter (Dp 2 ) of up to 500 nm, and a relationship between the Dp 1 and the Dp 2 is 3≤Dp 1 <Dp 2 ≤500 nm.

2. The method of producing hollow spherical silica-based particles according to claim 1 , wherein a ratio (D p1 /D p2 ) of the average diameter (D p1 ) of the first composite oxide particles versus the average diameter (D p2 ) of the third composite oxide particles is 0.4 to 0.98.

3. The method of producing hollow spherical silica-based particles according to claim 1 , further comprising a step (d) performed between the step (c-2) and the step (e):
(d) a step of adding at least one of an organic silicon compound expressed by the following chemical formula (1) and a partially hydrolyzed product thereof into the fifth dispersion liquid obtained by the step (c-2) to form a silica-coating layer on fifth composite oxide particles included in the fifth dispersion liquid:
R n SiX (4-n)   (1)

wherein R denotes a not-substituted or substituted hydrocarbon group having 1 to 10 carbon atoms, an acrylic group, an epoxy group, a methacrylic group, amino group, mercapto group, or a CF 3 group; X denotes an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen or hydrogen; and n indicates an integral number of 0 to 3.

4. The method of producing hollow spherical silica-based particles according to claim 1 , further comprising a step (f):
(f) a step of adding at least one of an organic silicon compound expressed by the following chemical formula (1) and a partially hydrolyzed product thereof into a sixth dispersion liquid obtained by the step (e) to form a silica-coating layer on sixth composite oxide particles included in the sixth dispersion liquid:
R n SiX (4-n)   (1)

wherein R denotes a not-substituted or substituted hydrocarbon group having 1 to 10 carbon atoms, an acrylic group, an epoxy group, a methacrylic group, amino group, mercapto group, or a CF 3 group; X denotes an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen or hydrogen; and n indicates an integral number of 0 to 3.

5. The method of producing hollow spherical silica-based particles according to claim 4 , further comprising a step (g-2) after the step (f):
(g-2) a step of hydrothermal processing at 50 to 300° C. after cleaning an eighth dispersion liquid obtained by the step (f).

6. The method of producing hollow spherical silica-based particles according to claim 5 , further comprising a step (h-2) after the step (g-2):
(h-2) a step of adding at least one of an organic silicon compound expressed by the following chemical formula (1) and a partially hydrolyzed product thereof into a ninth dispersion liquid obtained by the step (g-2) to form a silica-coating layer on ninth composite oxide particles included in the ninth dispersion liquid:
R n SiX (4-n)   (1)

wherein R denotes a not-substituted or substituted hydrocarbon group having 1 to 10 carbon atoms, an acrylic group, an epoxy group, a methacrylic group, amino group, mercapto group, or a CF 3 group; X denotes an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen or hydrogen; and n indicates an integral number of 0 to 3.

7. The method of producing hollow spherical silica-based particles according to claim 1 , wherein pH of the alkali aqueous solution is 10 or more.

8. The method of producing hollow spherical silica-based particles according to claim 1 , further comprising a step (g-1) after the step (e):
(g-1) a step of hydrothermal processing at 50 to 300° C. after cleaning a sixth dispersion liquid obtained by the step (e).

9. The method of producing hollow spherical silica-based particles according to claim 8 , further comprising a step (h-1) after the step (g-1):
(h-1) a step of adding at least one of an organic silicon compound expressed by the following chemical formula (1) and a partially hydrolyzed product thereof into a seventh dispersion liquid obtained by the step (g-1) to form a silica-coating layer on seventh composite oxide particles included in the seventh dispersion liquid:
R n SiX (4-n)   (1)

wherein R denotes a not-substituted or substituted hydrocarbon group having 1 to 10 carbon atoms, an acrylic group, an epoxy group, a methacrylic group, amino group, mercapto group, or a CF 3 group; X denotes an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen or hydrogen; and n indicates an integral number of 0 to 3.

10. The method of producing hollow spherical silica-based particles according to claim 1 , further comprising:
a step of cleaning, drying, and calcining.

11. The method of producing hollow spherical silica-based particles according to claim 1 , wherein a content of an alkali metal oxide in a sixth

Assignees

• Jgc Catalysts & Chemicals Ltd

Inventors

• Muraguchi Ryo
• Kumazawa Mitsuaki
• Hirai Toshiharu

Classifications

• C08K7/26

  Silicon- containing compounds · CPC title

• C01B33/18 Primary

  Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof (preparation of aerogels by dehydrating gels C01B33/158; treatment to enhance the pigmenting or filling properties C09C) · CPC title

• C08K3/36

  Silica · CPC title

• C09D7/68

  Particle size between 100-1000 nm · CPC title

• Y10T428/31935

  Ester, halide or nitrile of addition polymer · CPC title