# US 9,518,071 B2 · Hydrosilylation method

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- Number: US 9,518,071 B2
- Document ID: US9518071B2
- Status: Granted
- Kind: B2
- Application number: 14/653,069
- Filed: 2013-12-20
- Published: 2015-11-12
- Granted: 2016-12-13
- Earliest claimed: 2012-12-21
- Assignees: Bluestar Silicones France SAS; Universite Claude Bernard Lyon 1
- Applicants: BLUESTAR SILICONES France SAS (50 Percent Part Interest); Universite Claude Bernard Lyon 1 (50 Percent Part Interest)
- Inventors: Chloe Thieuleux; Reine Sayah El Rayes; Marie-Line Zanota; Valerie Meille; Richard Vivier; Sebastien Marrot
- Web page: https://patentgrep.com/patent/US9518071B2

## CPC

- C07F 7/0838: {Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21)}
- B01J 19/24: Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02)
- B01J 21/08: Silica
- B01J 23/42: Platinum
- B01J 29/0325: {Noble metals}
- B01J 35/45: Nanoparticles
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0211: {using a colloidal suspension}
- B01J 37/033: {Using Hydrolysis}
- B01J 37/036: {to form a gel or a cogel}
- B01J 2219/24: Stationary reactors without moving elements inside
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A method (P) for hydrosilylating at least one compound (C), including at least one unsaturation in the presence of an organosilicon compound (O) including at least one hydrogen atom per molecule bonded directly to a silicon atom, and of a catalytic hydrosilylation system including a structured porous material (A) including pores and an inorganic structure consisting of silicon oxide walls, in which metal nanoparticles are contained.

## Claims

### Claim 1

A method (P) for hydrosilylating at least one compound (C) comprising at least one unsaturation in the presence of an organosilicon compound (O) comprising at least one hydrogen atom directly bound to a silicon atom and of a catalytic hydrosilylation system comprising a structured porous material (A) including pores and an inorganic backbone consisting of silicon oxide walls in which are contained metal nanoparticles.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the material (A) is in the form of a powder.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the material (A) as a powder is supported on a substrate.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the metal nanoparticles are platinum nanoparticles.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the material (A) has a double porosity with mesopores having a diameter from 2 to 50 nm and microporous channels, present in the walls of the material (A), having a diameter of less than 2 nm.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the material (A) has a BET specific surface area from 20 to 1,200 m2/g.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the metal nanoparticles have an average diameter from 1 to 10 nm.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the walls of the inorganic backbone of the material (A) have a thickness greater than or equal to 3 nm.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the inorganic backbone of the material (A) has a vermicular, cubic or hexagonal structure.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the compound (C) comprises one or several alkene functions and from 2 to 40 carbon atoms or one or several alkyn functions and from 2 to 40 carbon atoms.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the compound (C) is selected from the group consisting of:
C1-C4 alkyl acrylates and methacrylates;
acrylic acid or methacrylic acid;
acetylene;
alkenes;
non-conjugate dienes;
allyl alcohol;
allylamine;
allyl and glycidyl ether;
allyl and piperidine;
styrene;
1,2-epoxy-4-vinylcyclohexane;
chlorinated alkenes;
fluorinated alkenes;
with p having the value 1 or 2;
and mixtures thereof.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the compound (0) is selected from the group consisting of:
hydrogen silane compounds of formula (III):
wherein:
R represents independent of the others, a hydrogen atom; a halogen atom; an alkyl group optionally substituted with one or several aryl or cycloalkyl groups, with one or several halogen atoms and/or with one or several ketone functions; a cycloalkyl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms; or an aryl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms;
R′ represents, independently of the others, an alkyl group optionally substituted with one or several aryl or cycloalkyl groups with one or several halogen atoms and/or with one ketone function; a cycloalkyl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms; or an aryl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms;
R″ represents, independently of the others, a hydrogen atom; a halogen atom, preferably chlorine; an alkyl group optionally substituted with one or several aryl or cycloalkyl groups and/or with one or several halogen atoms; a cycloalkyl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms; or an aryl group optionally substituted with one or several alkyl groups and/or with one or several halogen atoms; and
m, n and o are integers of value 0, 1, 2 or 3, and m+n+o=3,
R, R′ and R″ being either identical or different;
the polyorganosiloxanes comprising:
(i) at least one siloxyl unit of formula (IV)
H
d
⁢
Z
e
3
⁢
SiO
4
-
(
d
+
e
)
2
(
IV
)
wherein:
d=1 or 2,
e=0, 1 or 2
d+e=1, 2 or 3,
the symbol(s) Z3, either identical or different, represent a monovalent hydrocarbon group notably having from 1 to carbon atoms optionally substituted with heteroatoms or radicals comprising heteroatoms,
(ii) optionally at least one siloxyl unit of formula (V)
Z
c
2
⁢
SiO
4
-
c
2
(
V
)
wherein:
c=0, 1, 2 or 3;
the symbol(s) Z2, either identical or different, represent a monovalent hydrocarbon group having from 1 to 30 carbon atoms optionally substituted with heteroatoms or with radicals comprising heteroatoms,
and mixtures thereof.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the molar ratio
R
=
number
⁢
⁢
of
⁢
⁢
unsaturations
⁢
⁢
of
⁢
⁢
the
⁢
⁢
C
⁢
⁢
compounds
number
⁢
⁢
of
⁢
⁢
SiH
⁢
⁢
groups
⁢
⁢
of
⁢
⁢
the
⁢
⁢
O
⁢
⁢
compounds
varies from 0.01 to 2.

### Claim 14 (depends on 1)

The method according to claim 1, wherein the amount of applied metal nanoparticles based on the total weight of the compounds (C) and (O) is from 1 to 50 ppm.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the molar ratio
R
=
number
⁢
⁢
of
⁢
⁢
unsaturations
⁢
⁢
of
⁢
⁢
the
⁢
⁢
C
⁢
⁢
compounds
number
⁢
⁢
of
⁢
⁢
SiH
⁢
⁢
groups
⁢
⁢
of
⁢
⁢
the
⁢
⁢
O
⁢
⁢
compounds
varies from 0.01 to 0.99.

### Claim 16 (depends on 1)

The method according to claim 1, comprising the following steps:
a) reacting the organosilicon compound (0) with a first compound (C), according to the method (P), R varying from 0.01 to 0.99; and
b) reacting the organosilicon compound obtained in step a) with a second compound (C) different from the one applied in step a), according to the method (P), the ratio R of this step b) concerning the application of a second compound (C) varying from 0.01 to 1,
steps a) and b) being carried out in the presence of the catalytic system.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the method is carried out continuously.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the method is carried out at a temperature from 20 to 100° C.

### Claim 19 (depends on 1)

A hydrosilylation catalytic system for reactions between an organosilicon compound (O) and a compound (C) comprising at least one unsaturation, comprising the material (A) according to claim 1.