JPS63135394A - Norbornyldimethylmethacryloxysilane - Google Patents

Abstract

NEW MATERIAL:Norbornyldimethylmethacryloxysilane. USE:An intermediate for reactive polymers, having controlled hydrolyzability and readily synthesized without functional groups other than the methacryloxysilyl group. PREPARATION:For example, methacrylic acid is blended with a solvent, e.g. benzene, and a hydrogen chloride acceptor, e.g. triethylamine, is added. The resultant solution is then reacted while stirring dripping a solution of norbornyldimethylchlorosilane is an organic solvent thereto and controlling temperature preferably at about 40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel compound, norbornyldimethylmethacryloxysilane.

[Technical background of the invention and its problems] Various silane compounds are known in which a carbon functional group is bonded to a silicon atom via a silicon functional bond. Among them, trimethylmethacryloxysilane is a silane compound in which a methacryloxy group is bonded to a silicon atom (Andreev, D, N1.et,
al, ;Zhurnal 0bshc-hei Kbi
mii, Vol. 30, p. 2782 (1960)). However, this compound is highly hydrolyzable and has poor stability.

In order to control hydrolyzability, 5i-
As other substituents bonded to the silicon atom of the 0-C bond,
A stable organic group with high steric hindrance may be introduced. Although it is effective to introduce a tert-butyl group as such an organic group, it is necessary to use tert-butyllithium to bond it to a silicon atom, which is not an industrially preferable method.

The present inventor previously discovered ethylidenenorbornyldimethylmethacryloxysilane as a compound that is highly sterically hindered, has controlled hydrolyzability, and is easily synthesized (Japanese Patent Application No. Sho Go-116473). This product has carbon-carbon unsaturated bonds in the ethylidene norbornyl group and the methacryloxy group, and is useful as an intermediate for synthesizing various compounds, but it has poor hydrolyzability between the methacryloxy group and the silicon atom. When using it for the intended purpose,
The reactivity of the double bond of the ethylidene norbornyl group must be taken into consideration, which poses a problem in that it imposes restrictions on its molecular design and use.

[Object of the invention] The object of the present invention is to have controlled hydrolyzability,
The object of the present invention is to provide a methacryloxysilane compound that has no reactive functional groups other than a methacryloxysilyl group and is easy to synthesize.

[Faith of the Invention] That is, the present invention relates to norporonidimethylmethacryloxysilane represented by formula (I).

[1......(1) Norbornyldimethylmethacryloxysilane represented by formula (1) of the present invention has a methacryloxy group and a norbornyl group bonded to a silicon atom, and has a combination of methacrylic acid and It can be produced by reacting norbornyldimethylchlorosilane. The production method is not particularly limited, and the reaction can usually be carried out in a suitable organic solvent in the presence of a hydrogen chloride acceptor.

An example of a preferred manufacturing method is listed below.

Methacrylic acid is stirred homogeneously in an organic solvent such as a hydrocarbon solvent or an aprotic polar solvent. A suitable acceptor for hydrogen chloride is then added, heated and stirred. To the flame, norbornyldimethylchlorosilane dissolved in the above-mentioned soothing solvent is added by a method such as dropping,
The reaction is carried out by further stirring. This norbornyldimethylchlorosilane is, for example, bicyclo(
2,2,1) Hept-2-ene and dimethylchlorosilane can be obtained by hydrosilylation in the presence of a platinum catalyst.

After the reaction is completed, unnecessary silane is removed by an appropriate method such as filtration, and the purified product is dried to obtain norbornyldimethylmethacryloxysilane represented by formula (1).

Hydrocarbon solvents used here include, for example, benzene, toluene, xylene, cyclohexane or n
-Hexane, etc. can be mentioned. Examples of the aprotic polar solvent include tetrahydrofuran and dimethylformamide.

The amount of these organic solvents to be used is preferably at least the same amount as that of silane in the case of benzene, which does not interfere with stirring due to precipitation of amine hydrochloride.

Further, as an acceptor for hydrogen chloride, triethylamine, pyridine or 1,8-diazabicyclo[5
, 4,0] undecene-7, and the like. Since this reaction is exothermic, the dropping rate is controlled to keep the reaction temperature at 35-60°C, preferably about 40°C. After a suitable dropwise addition time to control the above reaction temperature, stirring is continued for at least 10 minutes to complete the reaction.

[Effects of the Invention] Norbornyldimethylmethacryloxysilane obtained in the present invention can be more easily synthesized via norbornyldimethylchlorosilane than dimethylchlorosilane, which is synthesized in large quantities industrially. In addition, trimethylmethacryloxysilane, which is a known compound, and other known silane compounds represented by the general formula % (wherein R represents a monovalent hydrocarbon group not containing an aliphatic unsaturated bond) (Excluding tert-butyldimethylmethacryloxysilane, which is disadvantageous in terms of synthesis) The hydrolysis rate is slower than that of tert-butyldimethylmethacryloxysilane.

The compounds of this invention, due to their methacryloxy groups, are useful as intermediates for reactive polymers.

[Examples] Hereinafter, the present invention will be described in further detail with reference to Reference Examples and Examples. In Reference Examples and Examples, "r parts" are all "parts by weight"
represents.

Reference example Bicyclo(2,2,1>
94 parts of hepto-2-ene and 0 salts of platinic acid as a catalyst.
．． 02 parts were charged and heated to 30°C. Next, 100 parts of dimethylchlorosilane was slowly added dropwise from the dropping funnel, the system was brought to a reflux state, and as the reaction proceeded, the liquid temperature was gradually raised, and finally the temperature was kept at 80°C for 20 hours to carry out the addition reaction.

1 barley was stripped at 70°C under reduced pressure (10 Torr) to remove unreacted substances, and distilled to 169 parts (yield 90%)
of norbornyldimethylchlorosilane was obtained. The physical properties of this product were as follows.

Boiling point 64℃/3Torr Molecule i 188 (Gas mass spectrometry) Example 1 (Synthesis example) Stirrer, condenser, thermometer and cooling jacket 1
400 parts of benzene, 86 parts of methacrylic acid and 0.02 parts of hydroquinone were charged into a reaction vessel equipped with
Stir until homogeneous. 101 parts of triethylamine was added, and the temperature was raised to 50°C ('A).While stirring, 188 parts of norbornyldimethylchlorosilane synthesized in the above reference example was added dropwise over 15 minutes, and stirring was continued for an additional 30 minutes. After the completion of the reaction, the triethylamine hydrochloride was filtered off, and the benzene solution containing the reaction product was distilled to obtain a fraction 176 with a boiling point of 87°C/2 Torr.
I got the department. The physical property values, elemental analysis results, characteristic absorptions, and their attributions of this reaction product are as shown in Table 1, and the infrared absorption spectrum and NMR spectrum of this reaction product are as shown in Figures 1 and 2. And,
This reaction product was confirmed to be norbornyldimethylmethacryloxysilane. The yield was 74% based on the theoretical amount.

(Hereinafter blank) (Hereinafter blank) Example 2, Comparative Examples 1 to 3 (Measurement of hydrolysis rate) Norbornyldimethylmethacryloxysilane obtained in Example 1 and trimethylmethacryloxysilane, tert- Using butyldimethylmethacryloxysilane and decyldimethylmethacryloxysilane, the hydrolysis rate constants were determined and used as a guide to hydrolyzability.

That is, at a temperature of 23°C, 1 of the methacryloxy compounds shown in Table 2 was dropped into 70 mA of water containing 30% by weight of ascent, and the pH in the solution was monitored using a potentiometer to determine the half-life. From this, the reaction rate constant was determined. These values are shown in Table 2.

(Margin below) Table 2 (Margin below)

[Brief explanation of the drawing]

1 and 2 show the infrared absorption spectrum and N)IR spectrum of the compound obtained in Example 1, respectively.

Claims (1)

[Claims] Norbornyldimethylmethacryloxysilane.