Platinum catalyzed hydrosilylation reactions utilizing cyclodiene additives

Patent metadata

Field	Value
Publication number	US-2016102178-A1
Application number	US-201514969559-A
Country	US
Kind code	A1
Filing date	Dec 15, 2015
Priority date	Jun 13, 2014
Publication date	Apr 14, 2016
Grant date	—

Abstract

A process and composition for the hydrosilylation of an unsaturated compound comprising reacting (a) a silyl hydride with (b) an unsaturated compound in the presence of (c) a platinum compound and (d) a cyclodiene, with the proviso that when the unsaturated compound is a terminal alkyne, the silyl hydride is other than a halosilane. The process and composition optionally comprise an inhibitor (e). The process and composition may be employed to form a variety of hydrosilylation products.

First claim

What is claimed is:

1 . A process for producing a crosslinked product comprising reacting (a) a silyl hydride with (b) an alkenyl silicone in the presence of (c) a platinum compound, (d) a cyclodiene, and (e) optionally a cure inhibitor.

2 . The process of claim 1 , wherein the cyclodiene is of the formula:

wherein R 1 -R 8 , R 3′ , R 4′ , R 7′ , and R 8′ are independently hydrogen; an substituted or unsubstituted alkyl or aryl group optionally containing at least one heteroatom; an alkoxy; and a halogen radical; optionally R 1 -R 2 and/or R 5 -R 6 taken together may form a saturated or unsaturated ring structure.

3 . The process of claim 1 , wherein the diene comprises 1,5-cyclooctadiene; 1,5-dimethyl-1,5-cyclooctadiene; 1,6-dimethyl-1,5-cyclooctadiene, or a combination of two or more thereof.

4 . The process of claim 1 , wherein the ratio of total moles of cyclodiene additive to moles of platinum is less than 2:1.

5 . The process of claim 1 , wherein the ratio of total moles of cyclodiene additive to moles of platinum is from about 0.1:1 to about 2:1.

6 . The process of claim 1 , wherein the platinum compound is a Pt(0) compound, and the ratio of total moles of cyclodiene additive to moles of platinum is from about 0.1:1 to about 100:1.

7 . The process of claim 1 , wherein the platinum compound is chosen from Karstedt's catalyst, Ashby's catalyst, or a combination thereof.

8 . The process of claim 1 , wherein the silylhydride is chosen from a compound of the formula R 9 m SiH p X 4-(m+p) and/or M a M H b D c D H d T e T H f Q g , where each R 9 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group, X is alkoxy, acyloxy, halogen, or silazane, m is 1-3, p is 1-3 the subscripts a, b, c, d, e, f, and g are such that the molar mass of the silylhydride is between 100 and 100,000 Dalton; M represents a monofunctional group of formula R 10 3 SiO 1/2 , a D represents a difunctional group of formula R 11 2 SiO 2/2 , a T represents a trifunctional group of formula R 12 SiO 3/2 , Q represents a tetrafunctional group of formula SiO 4/2 , M H represents HR 13 2 SiO 1/2 , T H represents HSiO 3/2 , and D H represents R 14 HSiO 2/2 ; each occurrence of R 10-14 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C6-C14 aryl or substituted aryl, wherein R10-14 optionally contains at least one heteroatom.

9 . The process of claim 1 , wherein the alkenyl silicone comprises at least two unsaturated groups and has a viscosity of at least 50 cps at 25° C.

10 . The process of claim 1 , wherein the alkenyl silicone is of the formula:
M vi a T b D c M d Q e
wherein M vi a =R 31 2 R 32 SiO 1/2 ; T b =R 33 SiO 3/2 where R 33 is chosen from R 31 or R 32 ; D c =R 31 R 33 SiO 2/2 where R 33 is chosen from R 31 or R 32 ; M d =R 31 3 SiO 1/2 ; and Q e =SiO 4/2 ; R 31 is independently selected from a monovalent hydrocarbon radical having one to forty carbon, optionally containing at least one heteroatom; and R 32 is selected from a terminal olefinic monovalent hydrocarbon radical having two to forty carbon atoms, optionally containing at least one heteroatom, and the alkenyl silicone is such as to provide at least two unsaturated groups reactive to hydrosilylation per chain; a≧0, b≧0, d≧0, e≧0; and the sum a+b+c+d+e is in the range 50-20,000.

11 . The process of claim 1 , wherein the inhibitor (e) is chosen from ethylenically unsaturated amides, aromatically unsaturated amides, acetylenic compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon mono-esters of unsaturated acids, conjugated ene-ynes, hydroperoxides, ketones, sulfoxides, amine, phosphines, phosphites, nitrites, diaziridines, or a combination of two or more thereof.

12 . The process of claim 1 , wherein the concentration of platinum is from about 100 parts per billion (ppb) to about 100 ppm.

13 . The process of claim 1 , wherein component (e) is present in an amount of from about 0 to about 10 weight percent.

14 . The process of claim 1 , wherein components (a)-(e) are provided in a single composition.

15 . The process of claim 1 , wherein the reaction is completed in about 10 seconds or less.

16 . The process of claim 1 , wherein the process is conducted by heating at a temperature above room temperature.

17 . The process of claim 1 , wherein a composition of components (a)-(e) has a working life of at least 2 hours when the concentration of inhibitor (c) is about 0.25 weight percent or less.

18 . A composition comprising (a) a silyl hydride, (b) an alkenyl silicone compound, (c) a platinum compound, (d) a cyclodiene, and (e) optionally an inhibitor, where the cyclodiene (d) is a compound of the formula:

wherein R 1 -R 8 , R 3′ , R 4′ , R 7′ , and R 8′ are independently hydrogen; an substituted or unsubstituted alkyl or aryl group optionally containing at least one heteroatom; an alkoxy; and a halogen radical; optionally R 1 -R 2 and/or R 5 -R 6 taken together may form a saturated or unsaturated ring structure.

19 . The composition of claim 18 , wherein the diene comprises 1,5-cyclooctadiene; 1,5-dimethyl-1,5-cyclooctadiene; 1,6-dimethyl-1,5-cyclooctadiene, or a combination of two or more thereof.

20 . The composition of claim 18 , wherein the ratio of total moles of cyclodiene additive to moles of platinum is less than 2:1.

21 . The composition of claim 18 , wherein the ratio of total moles of cyclodiene additive to moles of platinum is from about 0.1:1 to about 2:1.

22 . The composition of claim 18 , wherein the platinum compound is a Pt(0) compound, and the ratio of total moles of cyclodiene additive to moles of platinum is from about 0.1:1 to about 100:1.

23 . The composition of claim 18 , wherein the platinum compound is chosen from Karstedt's catalyst, Ashby's catalyst, or a combination thereof.

24 . The composition of claim 18 , wherein the silylhydride is chosen from a compound of the formula R 9 m SiH p X 4-(m+p) and/or M a M H b D c D H d T e T H f Q g , where each R 9 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group, X is alkoxy, acyloxy, halogen, or silazane, m is 1-3, p is 1-3 the subscripts a, b, c, d, e, f, and g are such that the molar mass of the silylhydride is between 100 and 100,000 Dalton; M represents a monofunctional group of formula R 10 3 SiO 1/2 , a D represents a difunctional group of formula R 11 2 SiO 2/2 , a T represents a trifunctional group of formula R 12 SiO 3/2 , Q represents a tetrafunctional group of formula SiO 4/2 , M H represents HR 13 2 SiO 1/2 , T H represents HSiO 3/2 , and D H represents R 14 HSiO 2/2 ; each occurrence of R 10-14 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C6-C14 aryl or substituted aryl, wherein R10-14 optionally contains at least one heteroatom.

25 . The composition of claim 18 , wherein the alkenyl silicone comprises at least two unsaturated groups and has a viscosity of at least 50 cps at 25° C.

26 . The composition of claim 18 , wherein the alkenyl silicone is chosen from an compound of the formula:
M vi a T b D

Assignees

• Momentive Performance Mat Inc

Inventors

• Roy Aroop K
• Boyer Julie L

Classifications

• C09D143/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C07F7/14

  Preparation thereof from {optionally substituted} halogenated silanes and hydrocarbons {hydrosilylation reactions} · CPC title

• C07F7/12

  Organo silicon halides · CPC title

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title