JPS62149688A - Chloropropenyldialkoxysilane - Google Patents

Abstract

NEW MATERIAL:The compound of formula R<1>R<2>Si(OR)2 [R<1> and R<2> are 1-(chloromethyl)vinyl or 2-(chloromethyl)vinyl; R is 1-5C alkyl or alkoxyalkyl]. EXAMPLE:Bis[1-(chloromethyl)vinyl]dimethoxysilane. USE:A moisture-crosslinking agent, a silane coupling agent and sunthetic intermediate for other silane coupling agents. PREPARATION:The objective compound can be produced e.g. by reacting bis[1-(chloromethyl)vinyl]dichlorosilane, [1-(chloromethyl)vinyl][2-(chloromethyl) vinyl]dichlorosilane or bis[2-(chlormethyl)vinyl]dichlorosilane with an alcohol or an alcohol having alkoxy group in the molecule preferably in a reaction solvent such as benzene, etc., at 0-100 deg.C for 0.1-300hr.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to novel organosilicon compounds.

<Prior art> Alkoxysilane derivatives having a vinyl group, such as vinyltrimethoxysilane and vinyltriethoxysilane, are known, and examples of alkoxysilanes having a chlorine-substituted alkyl group on polyethylene include 3-chloroglobin. Trimethoxysilane, 3-di-0-loprobyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, etc. are known and can be used as silane coupling agents and intermediates for the synthesis of other silane coupling agents (Japanese Patent Application Laid-Open No. 1983-1999) -104890 Publication, JP-A-56-104891
Publication No.).

<Problems to be Solved by the Invention> However, when conventional vinyl alkoxy 77 run is used as a water crosslinking agent, the crosslinking property is low, and moreover, it only exhibits a water crosslinking effect, making it difficult to diversify the performance of silane coupling agents. However, there was a problem in that they did not necessarily show satisfactory performance. In addition, when conventional alkoxysilanes having a chlorine-substituted alkyl group in the molecule are used as silane coupling agents and intermediates in the synthesis of other silane coupling agents, their reactivity is low and they are functionally satisfactory. As a result of intensive research aimed at solving the above-mentioned drawbacks of the conventional technology, the present inventors have found that the present inventors have developed a method that has higher performance than when used as a water crosslinking agent. The present invention has discovered a novel rolopropenyldialkoxysilane which can exhibit the following properties and diversify its performance, and at the same time has high reactivity when used as a silane coupling agent and an intermediate for the synthesis of other silane coupling agents. reached.

That is, the present invention provides the following general formula R' R2S 1 (OR
).

In formula C, R1, R'' is a l-(chloromethyl)vinyl group or a 2-(chloromethyl)vinyl group, and R has 1 to 1 carbon atoms.
5 represents an alkyl group or an alkoxyalkyl group].

In the general formula, R represents an alkyl group or an alkoxyalkyl group having 1 to 5 carbon atoms, specifically a methyl group,
Ethyl group, n-propyl group, 1so-propyl group, n-
Butyl group, 5ec-butyl group, 1so-butyl group, te
1 to 5 carbon atoms such as rt-butyl group and n-pentyl group
Examples of preferable examples include diluted alkoxyalkyl groups having a total number of carbon atoms of 1 to 5, such as diluted alkyl groups, methoxyethyl groups, and ethoxyethyl groups.

Preferred specific examples of the compounds of the present invention include bis(1-
(chloromethyl)vinylcdimethoxysilane, ci-(
chloromethyl)vinyl)(2-(chloromethyl)vinylcdimethoxysilane, bis(2-(chloromethyl)vinylconmethoxysilane, bis(1-(chloromethyl)vinylcdiethoxysilane, [1-(chloromethyl) Vinyl] [2-(chloromethyl)vinylcdiethoxysilane, bis(2-(chloromethyl)vinylcdiethoxysilane, bis(1-(chloromethyl)vinyl) di(n-,
propoxy)silane, [l-(chloromethyl)vinyl)
(2-(chloromethyl)vinylkudi(n-propoxy) 7ran, bis[2-(chloromethyl)vinylkudi(n-propoxy)
-propoxy)silane, bis(1-(chloromethyl)vinylkdi(iso-propoxy)silane, [l-(chloromethyl)vinyl)(2-(chloromethyl)vinyl)cy(iso-7'roboxy)7ran, Bis[2-(chloromethyl)vinylkdi(iso-propoxy) 7rane, bis(1,-(chloromethyl)vinylkdi(n-butoxy)silane, (1-(chloromethyl)vinyl)(2-(chloromethyl) Vinylkoxy(n-butoxy)silane, bis(2-(chloromethyl)vinylkoxy(n-butoxy)silane, bis[:I-(chloromethyl)vinylkoxy(is
.

-butoxy)silane, (1-(chloromethyl)vinyl)
(2-(chloromethyl)vinyl)(is.

-butoxy)silane, bis(2-(chloromethyl)vinyl-butoxy)silane, bis[l-(chloromethyl)vinyl-butoxy)silane, (1-(chloromethyl)vinyl)(2-( Chloromethyl) vinyl tert-butoxysilane, bis[
2-(Chloromethyl)vinylkudi(tert-butoxy)silane, bis[1-(chloromethyl)vinylkudi(n
-pentoxy)silane, (1-(chloromethyl)vinyl](2-(chloromethyl)vinylkdi(n-pentoxy)silane, bis(2-(chloromethyl)vinylkdi(n)
-pentoxy)silane, bis[l-(chloromethyl)vinyl]bis(methoxyethoxy)silane, C1-(chloromethyl)vinyl)(2-(chloromethyl)vinyl]bis(methoxyethoxy)silane, bis(2- (chloromethyl)vinyl]bis(methoxyethoxy)silane, bis(1-(chloromethyl)vinyl]bis(ethoxyethoxy)silane, (1-(chloromethyl)vinyl) [2-
(chloromethyl)vinyl]bis(ethoxyethoxy)silane, bis(2-(chloromethyl)vinyl)bis(ethoxyethoxy)silane, and the like.

The compounds of the present invention can be produced by any method.

As a method for producing the compound of the present invention, for example,
1-(chloromethyl)vinyl]dichlorosilane, (1-
(chloromethyl)vinyl](2-(chloromethyl)vinyl)cyclosilane, or bis(2-(chloromethyl)vinyl)
A method of reacting vinylfudichlorosilane with alcohol or an alcohol having a t,t flukoxy group in the molecule, (13) bis(1-(chloromethyl)vinylfudichlorosilane, (1-(chloromethyl)vinyl)(2-(
chloromethyl)vinyl]dichlorosilane or bis[2-
Examples include a method in which (chloromethyl)vinylfudichlorosilane is reacted with an alcohol or a metal salt of an alcohol containing an alkoxy group in the molecule, and a method in which a hydrosilylation reaction is performed between glopargyl chloride and dialkoxysilane.

The prison method will be explained in detail below.

(4) In the method, for the purpose of neutralizing the by-product hydrochloric acid,
Amines can also be introduced into the reaction system. In that case, stirring may become difficult due to the hydrochloride of the amine produced, so it is recommended to use benzene, xene, toluene, ether, tetrahydrofuran, hexane, petroleum ether, ligroin, etc. as the reaction solvent. desirable.

The reaction can be carried out by mixing and stirring raw materials and reactants in a solvent. Bis[l-(chloromethyl)vinyl fudichlorosilane, [:l-(chloromethyl)vinyl)(2
Any ratio (molar ratio) of -(rimole)vinylfudichlorosilane or bis(2-(chloromethyl)vinyldichlorosilane/) and alcohol or alcohol having an alkoxy group in the molecule or its metal salt. Although it is possible to carry out the reaction even when the reaction is carried out, it is preferable to carry out the reaction at a molar ratio of 1:2 or more in order to carry out the reaction completely.

The reaction temperature is -30 to 150°C, preferably O-1
It is 00℃.

The reaction time can be varied within the range of 0.1 to 300 hr depending on the amount of reaction solvent, reaction temperature, molar ratio of raw materials, etc.

The reaction can be carried out either under normal pressure or under increased pressure.

The compound of the present invention can be isolated from the reaction mixture thus obtained by a conventional method, for example, the target product can be isolated and purified by distillation under reduced pressure or column chromatography.

The thus obtained chloropropenyl dialkoxy 7-rane of the present invention is a novel compound, and is a colorless liquid substance with extremely good fluidity at around room temperature.

Since the compound of the present invention simultaneously has an allyl group substituted with a chlorine atom and an alkoxy group in the molecule, it can be applied both as a water crosslinking agent and as a silane coupling agent. In addition, the chlorine atom is activated by being in the allyl position and has high reactivity, so when used as a water crosslinking agent, it has high crosslinking properties, and because of its high reactivity, it can be used in the synthesis of other organosilicon compounds. It is effective as an intermediate for

<Examples> The compounds of the present invention will be specifically explained using the following examples. However, the following examples explain some examples of the present invention and do not limit the scope of the claims.

Example 1 2 equipped with a stirrer, dropping funnel, reflux condenser, and thermometer
Bis(1-(chloromethyl)vinyldichlorosilane/, [l-(chloromethyl)vinyl:](2-(chloromethyl)vinylfudichlorosilane), bis(2-(chloromethyl)vinyl) in a 50 gt glass reactor. Vinyl dichlorosilane/mixture (ratio 8/49/43) 14.12 F
(56,5 dishes O1), prepare benzene 200gZ,
Add methanol 3 while stirring while keeping the reaction temperature below 15°C.
．． 981 (124 mmol) and triethylamine 1
A mixture of 3.14 f (130 mmol) was added dropwise over 40 minutes. After completing the dropwise addition, return the temperature of the reaction solution to room temperature,
Stirring was continued for an additional 1.5 hours. After the reaction, the by-produced triethylamine hydrochloride was filtered, and the reaction solution was distilled under reduced pressure to obtain a product 12 with a boiling point of 86-96°C and 70.9nHf.
．． 63F was obtained.

When the obtained distillation product was analyzed by gas chromatography, it was found to consist of three components (each of them will be referred to as product-1-1, product-1-2, and product-1-3 in descending order of boiling point). ) The production ratio was 8151/41.

Table 1 shows the results of infrared absorption spectra, nuclear magnetic resonance spectra, and mass spectra after each was further isolated and purified by chromatography. The elemental analysis result of the mixture consisting of three components is the measured value C: 39.72
iH: 5.84 iCl: 29.39 (calculated value C: 39.84; H: 5.85; C1: 2
9.40). The structure of the compound obtained from the above data is that product-1-1 is bis[l-(chloromethyl)vinylcdimethoxysilane, and product-1-2 is [
l-(chloromethyl)vinyl)(2-(chloromethyl)
With vinyl dimethoxysilane, product-1-3 is bis[
It was confirmed to be 2-(chloromethyl)vinyldimethoxysilane (yield 93%).

Table 1 (Note) *CI method (chemical
ion method) was used.

Example 2 Under the same reaction conditions as in Example 1, bis(1-(chloromethyl)vinylfudichlorosilane, (1-(chloromethyl)vinyl)(2-(chloromethyl)vinylfudichlorosilane), bis[2-(chloromethyl)vinylfudichlorosilane, methyl) vinyl fudichlorosilane mixture (ratio 18153/29) 9.09 f and n
-Butyl alcohol 7A21 is reacted with a boiling point of 124-
Product 9.43f was obtained at 133° C./1.4 mHp.

When analyzed by gas chromatography, the obtained distillation product consists of three components (each of them will be referred to as Product-2-11, Product-2-2, and Product-2-3 in order of decreasing boiling point). ) The production ratio was 27/44/29.

Each was isolated and purified in the same manner as in Example 1, and the results of infrared absorption spectra, nuclear magnetic resonance spectra, and mass spectrum measurements are shown in Table 2.

The structure of the compound obtained from the above data is vinylfudi(n-butoxy)silane, product-2-2 is [l-(chloromethyl)vinyl][2-(chloromethyl)vinylfudi(n-butoxy)silane] , product-2-3 is bisC2
-(Chloromethyl)vinylfudi(n-butoxy)silane was confirmed (yield: 80%).

Table 2 (Note) *CI method (chemical
ion method) Tare/-T-air was used.

Example 3 Under the same reaction conditions as in Example 1, bis(1-(chloromethyl)vinyl]dichloro/U'', (1-(chloromethyl)vinyl)[2-(chloromethyl)vinylfudichlorosilane, bisC2 -C chloromethyl) vinyl dichlorosilane mixture (ratio 18153/29) 9.099
and methyl cellosolve 7.31F to reach a boiling point of 136
7.34y of product was obtained at -145°C/1.4 mHf.

When analyzed by gas chromatography, the obtained distillation product consists of three components (each of them will be referred to as Product-3-11, Product-3-2, and Product-3-3 in descending order of boiling point). ) The production ratio was 21152/27.

Table 3 shows the measurement results of infrared absorption spectra, nuclear magnetic resonance spectra, and pawnshop spectra after each product was purified into single I8!9 in the same manner as in Example 1. .

The structure of the formulation obtained from the above data is Product-3
-1 is bis[l-(chloromethyl)vinyl]bis(methoxyethoxy)silane, product-3-2 is (1-(chloromethyl)vinyl](2-(chloromethyl)vinyl)bis(methoxyethoxy) The silane product-3-3 was confirmed to be bis[2-(chloromethyl)vinyl]bis(methoxyethoxy)silane (yield 61%).

Table 3 (Note) *C■ Method (chemical method)
Ammonia was used in the ion method).

<Effects of the Invention> The compound of the present invention is a novel compound that has high crosslinking properties when used as a water crosslinking agent, and also exhibits various performances in addition to the water crosslinking action. It exhibits high reactivity when used as an intermediate in the synthesis of organic silicon compounds. The compounds of the present invention can also be used as raw materials for new modified silicone oils.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] The following general formula R^1R^2Si(OR)_2 [in the formula R^1
, R^2 is a 1-(chloromethyl)vinyl group or a 2-(chloromethyl)vinyl group, and R is an alkyl group or an alkoxyalkyl group having 1 to 5 carbon atoms].