Hydrosilylation method

Patent metadata

Field	Value
Publication number	US-9518071-B2
Application number	US-201314653069-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Dec 21, 2012
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

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.

First claim

The invention claimed is:

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.

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

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

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

5. 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.

6. The method according to claim 1 , wherein the material (A) has a BET specific surface area from 20 to 1,200 m 2 /g.

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

8. 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.

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

10. 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.

11. The method according to claim 1 , wherein the compound (C) is selected from the group consisting of:
C 1 -C 4 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.

12. 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) Z 3 , 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) Z 2 , 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.

13. The method according to claim 1 , wherein the molar ratio

R
=

number
⁢

⁢
of
⁢

⁢
unsaturations
⁢

⁢
of
⁢

⁢
the
⁢

⁢
C
⁢

⁢

Assignees

• BLUESTAR SILICONES France SAS (50 Percent Part Interest)
• Univ Claude Bernard Lyon 1 (50 Percent Part Interest)
• Bluestar Silicones France
• Univ Claude Bernard Lyon

Inventors

• Thieuleux Chloe
• Sayah El Rayes Reine
• Zanota Marie-Line
• Meille Valerie
• Vivier Richard
• Marrot Sebastien

Classifications

• B01J37/033 Primary

  Using Hydrolysis · CPC title

• B01J21/08

  Silica · CPC title

• B01J23/42

  Platinum · CPC title

• B01J2219/24

  Stationary reactors without moving elements inside · CPC title

• B01J37/0211

  using a colloidal suspension · CPC title