Method for preparing a composition comprising functionalised silico/germano-metal particles and composition obtained

Patent metadata

Field	Value
Publication number	US-10059598-B2
Application number	US-201414899817-A
Country	US
Kind code	B2
Filing date	Jun 20, 2014
Priority date	Jun 21, 2013
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

A method for preparing a composition includes silico/germano-metal particles functionalized by at least one organic group, which involves:—carrying out a hydrothermal treatment of a hydrogel precursor of the silico/germano-metal mineral particles, and—preparing a hydrogel including silico/germano-metal particles having at least one organic group by co-precipitation in an aqueous medium. A composition including functionalized silico/germano-metal mineral particles of which 1% to 75% of the silicon atoms and/or of the germanium atoms are covalently bonded to at least one organic group is also described.

First claim

The invention claimed is:

1. A method for preparing a composition comprising silico/germano-metallic mineral particles functionalised by at least one organic group, said particles comprising at least one silicon (Si) atom and/or at least one germanium (Ge) atom and at least one atom of a metal (M) chosen from the group formed of alkali metals, alkaline earth metals and transition metals, said method comprising:
carrying out a hydrothermal treatment under pressure of a hydrogel precursor of said silico/germano-metallic mineral particles,
preparing a hydrogel precursor comprising silico/germano-metallic particles having said at least one organic group by carrying out a coprecipitation reaction in an aqueous medium between:
at least one metal salt of said metal (M),
at least one source of silicon and/or of germanium, and
at least one compound chosen from water-soluble oxysilanes and oxygermanes of formula (I):

wherein:
T is chosen from silicon and germanium,
R1, R2 and R3 are identical or different and are chosen from a hydrogen and linear alkyl groups containing from 1 to 3 carbon atom(s), and
A is chosen from:
a methyl group, or
a hydrocarbon group of formula Q-[CH 2 ] n —, wherein
Q is selected from the group consisting of H 2 N—, a water-soluble cyclonic cationic group containing at least one heteroatom, a water-soluble aromatic cyclic cationic group containing at least one heteroatom, and a quaternary ammonium cation, and
n is an integer from 3 to 11.

2. The method according to claim 1 , wherein said hydrothermal treatment is carried out in the presence of at least one carboxylate salt of R8-COOM′, wherein:
M′ denotes a metal chosen from the group formed of Na and K, and
R8 is chosen from H and alkyl groups containing fewer than 5 carbon atoms.

3. The method according to claim 1 , wherein said hydrothermal treatment is carried out for a duration of from 1 second to 30 days.

4. The method according to claim 1 , wherein said hydrothermal treatment is carried out at a pressure of from 0.5 MPa to 20 MPa.

5. The method according to claim 1 , wherein said hydrothermal treatment of said hydrogel precursor is carried out at a temperature of from 150° C. to 300° C.

6. The method according to claim 1 , wherein said hydrogel precursor is of formula:
((Si y Ge 1−y ) x ((Si z Ge 1−z )-A) 1−x) 4 M 3 O 11 , n′H 2 O,

wherein:
Si denotes silicon,
Ge denotes germanium,
x is a real number of the interval [0.25; 1],
y is a real number of the interval [0 ; 1],
z is a real number of the interval [0 ; 1],
M denotes the metal atom, and
n′ relates to a number of molecule(s) of water associated with said hydrogel.

7. The method according to claim 1 , wherein the group A is of formula (II):

wherein:
R4, R5 and R6 are identical or different and are chosen from H and hydrocarbon groups containing at least one heteroatom.

8. The method according to claim 1 , wherein the group A is chosen from:
a methyl group, or
a hydrocarbon group of formula Q-[CH 2 ] n —, wherein:
Q is a group selected from the group consisting of H 2 N—, a water-soluble cyclic cationic group containing at least heteroatom, and a group of formula

 wherein:
R7 is chosen from linear and branched alkyls containing from 1 to 18 carbon atom(s),
X − is an anion wherein X is selected from the group consisting of chlorine, iodine and bromine, and

n is an integer from 3 to 11.

9. The method according to claim 8 , wherein there is carried out an at least partial exchange of the anion X − by at least one anionic species selected from the group consisting of a chloride anion, an iodide anion, a bromide anion, a fluorosulfonate anion, a bis(fluorosulfonyl)amide anion, a bis(trifluoromethanesulfonyl)amide anion, a trifluoromethanesulfonate anion, a hexafluorophosphate anion, a tetrafluoroborate anion, an acetate anion, a nitrate anion NO 3 − and a nitrite anion NO 2 − .

10. The method according to claim 2 , wherein said hydrothermal treatment is carried out for a duration of from 1 second to 30 days.

Assignees

• Centre Nat Rech Scient
• Univ Toulouse 3 Paul Sabatier

Inventors

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

Classifications

• C09C3/12

  Treatment with organosilicon compounds {(C09C3/006 takes precedence)} · CPC title

• C09C1/42

  Clays · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C09C1/28

  Compounds of silicon {(C09C1/0009, C09C1/0015, C09C1/0078 take precedence)} · CPC title

• C01P2002/78

  by stacking-plane distances or stacking sequences · CPC title