Method for preparing a hydrogel comprising silico-metallic mineral particles and hydrogel

Patent metadata

Field	Value
Publication number	US-9968924-B2
Application number	US-201214367702-A
Country	US
Kind code	B2
Filing date	Dec 19, 2012
Priority date	Dec 22, 2011
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A method for preparing a novel hydrogel including silico-metallic mineral particles of the formula (Si x (Si-A) 1−x ) 4 M 3 O 11 .n′H 2 O, in which: x is a real number in the range [0.75; 1], A denotes a group selected from methyl and hydrocarbon groups including at least one heteroatom, and M is a metal selected from the group consisting of magnesium, cobalt, zinc, copper, manganese, iron, nickel and chromium, wherein a coprecipitation reaction is carried out in an aqueous medium between: at least one metal salt of the metal M, sodium metasilicate, Na 2 OSiO 2 , and at least one water-soluble oxysilane of formula (I):

in which R1, R2 and R3 are selected from hydrogen and linear alkyl groups including 1 to 3 carbon atoms.

First claim

What is claimed is:

1. A method for preparing a hydrogel comprising silico-metallic mineral particles of the formula (Si x (Si-A) 1−x ) 4 M 3 O 11 ·n′H 2 O, in which:
x is a real number in the range of from 0.75 to 1, 1 being excluded from said range,
A denotes a methyl group or a hydrocarbon group with at least one heteroatom,
M is a metal selected from the group consisting of magnesium, cobalt, zinc, copper, manganese, iron, nickel and chromium, and
n′ refers to a number of water molecules associated with said hydrogel,
said method comprising carrying out a coprecipitation reaction, in an aqueous medium, between:
at least one metal salt of said metal M,
sodium metasilicate, Na 2 OSiO 2 , and
at least one water-soluble oxysilane of formula (I):

in which R1, R2and R3 are identical or different and are hydrogen or a linear alkyl group of 1 to 3 carbon atoms.

2. The method as claimed in claim 1 wherein the group A has formula (II):

in which R4, R5 and R6 are identical or different and are hydrogen and a hydrocarbon group with at least one heteroatom.

3. The method as claimed in claim 1 wherein, in formula (I), A is a methyl group or a hydrocarbon group with at least one heteroatom according to formula Y—[CH 2 ] n —, in which:
Y is a group comprising at least one nitrogen atom, and
n is an integer between 3 and 11.

4. The method as claimed in claim 3 wherein Y is selected from H 2 N— and

wherein:
R7 is a linear or a branched alkyl group with 1 to 18 carbon atoms, and
X − is an anion in which X is selected from the group consisting of chlorine, iodine and bromine.

5. The method as claimed in claim 4 wherein the anion X − is at least partially exchanged with at least one anionic species selected from the group consisting of a bistrifluoromethanesulfonamide anion, a trifluoromethanesulfonate anion, a hexafluorophosphate anion, a tetrafluoroborate anion, a tetrachloroaluminate anion, an acetate anion, a hydroxide anion, HO − , a nitrate anion, NO 3 − , and a nitrite anion, NO 2 − .

6. The method as claimed in claim 1 wherein said oxysilane has the formula:

wherein X − is an anion wherein X is selected from the group consisting of chlorine, iodine and bromine.

7. The method as claimed in claim 1 wherein carrying out said coprecipitation reaction comprises bringing together said metal salt, said sodium metasilicate and said oxysilane in such a way that the atomic ratio between the metal M and the silicon is substantially equal to 0.75.

8. The method as claimed in claim 1 wherein the molar ratio between said oxysilane and said sodium metasilicate is between 0.10 and 0.34.

9. The method as claimed in claim 1 wherein said metal salt is a metal chloride of the formula MCl 2 or a metal acetate of the formula M(CH 3 COO) 2 .

10. The method as claimed in claim 1 further comprising adding at least one of hydrochloric acid or acetic acid to the aqueous medium comprising said at least one metal salt, said sodium metasilicate and said at least one water soluble oxysilane, the total number of moles of chloride ions and acetate ions being equal to the number of moles of sodium, Na, in said coprecipitation reaction medium.

11. A hydrogel of the formula (Si x (Si-A) 1−x ) 4 M 3 O 11 ·n′H 2 O, in which:
x is a real number in the range of from 0.75 to 1, 1 being excluded from said range,
A denotes a methyl group or a hydrocarbon group with at least one heteroatom,
M is a metal selected from the group consisting of magnesium, cobalt, zinc, copper, manganese, iron, nickel and chromium, and
n′ refers to a number of water molecules associated with said hydrogel,

wherein A is a methyl group or a hydrocarbon group of formula Y—[CH 2 ] n —, in which:
n is an integer between 3 and 11, and
Y is a group of formula:

wherein
R7 is a linear or a branched alkyl group with 1 to 18 carbon atoms, and
X − is an anion in which X is selected from the group consisting of chlorine, iodine, and bromine.

Assignees

• Le Roux Christophe
• Martin Francois
• Micoud Pierre
• Dumas Angela
• Centre Nat Rech Scient
• Univ Toulouse 3 Paul Sabatier

Inventors

• Le Roux Christophe
• Martin Francois
• Micoud Pierre
• Dumas Angela

Classifications

• C01B33/158

  Purification; Drying; Dehydrating · CPC title

• C01B33/38

  Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type {(activation of naturally occurring clays B01J20/12; pillared layered base-exchange silicates B01J29/049)} · CPC title

• B01J31/0285

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0274 · CPC title

• B01J21/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J37/036 Primary

  to form a gel or a cogel · CPC title