JPH04182489A - New silane compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is tert-butyl or isopropyl). EXAMPLE:tert-Butoxycyclohexyldimethoxysilane. USE:A catalytic component of propylene polymerization or a silane coupling agent. PREPARATION:A cyclohexyltrihalosilane shown by formula II (X is halogen) is reacted with a compound shown by the formula ROH and then the prepared reaction product is reacted with methanol to give a compound shown by formula I. The compound shown by formula II as the raw material is readily produced by hydrosilylation reaction from cyclohexene and a trihalosilane shown by the formula H-Si-X3.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel silane compound and a method for producing the same. Regarding the manufacturing method.

(Prior art and problems to be solved by the invention) It has been known that when propylene polymerization is carried out, a polymer with high stereoregularity can be produced by using alkoxysilanes as a catalyst component. ing. However, even when propylene is polymerized using a catalyst component manufactured using a conventionally known alkoxysilane or the like, it has not been possible to sufficiently satisfy both high polymerization activity and high stereoregularity.

In addition, silane compounds are expected to be used as silane coupling agents or resin modifiers, and for this reason, the emergence of new silane compounds is desired.

Therefore, an object of the present invention is to provide a novel silane compound that is highly active and highly stereoregular and useful as a propylene polymerization catalyst component or a silane coupling agent, and a method for producing the same.

(Means for Solving the Problems) The present invention first provides a silane compound represented by the following formula (1): (wherein R represents a tert-butyl group or an isopropyl group), that is, tert-butoxycyclohexyl Dimethoxysilane or isopropoxycyclohexyldimethoxysilane is provided.

This silane compound (I> has a boiling point of 71° C. 10.1 mmHg when R= tert-butyl group, and R=
75℃/0.7111mH for isopropyl group
It was g. The structure of this silane compound was determined by GC-MS,
It can be confirmed by 1H-NMR1 infrared absorption spectrum (IR), etc.

For example, when compound (1) is analyzed using 'H-NMR, when R is a tert-butyl group, δ1.32
Signals based on a tert-butoxy group at δ1.1 to 2.0, a cyclohexyl group at δ1.1 to 2.0, and a methoxy group at δ3.55 were observed. Furthermore, when R is an isopropyl group, δ
1.16.1.26 and 3.9 to 4.5 are inpropoxy groups, δ1.1 to 2.0 are cyclohexyl groups, δ3.
A signal based on methoxy group was observed in 56.

Moreover, from the analysis by IR spectrum, large absorption based on the 5iOC bond was observed in the vicinity of 1100CI11-1 for all compounds.

When this silane compound (I) is used as a catalyst component, olefin polymers such as polypropylene and polybutene having high stereoregularity can be produced with high polymerization activity.

Moreover, since this silane compound (I> has a hydrolyzable group), it can be used as a silane coupling agent, a polymerizable monomer, and a resin modifier.

Second, the present invention provides a method for producing a novel silane compound represented by the above formula (I>). That is, cyclohexyltrihalosilane is reacted with ROH (R is the same as defined above), and then the resulting reaction product is The silane compound of the above formula (I>) is produced by reacting with methanol.The cyclohexyltrihalosilane used as a raw material is
The following formula: (X represents a halogen atom, preferably Cj!
or Br), cyclohexene and trihalosilane (HS
Nidichlorohexyltrihalosilane (II), which can be easily produced from iX3) by a hydrosilylation reaction, is commercially available.

The present invention first begins with the above-mentioned cyclohexyltrihalosilane (
IF> is reacted with ROH1, that is, tert-butyl alcohol or isopropyl alcohol. \ 1 to 3 moles of ROH are used per 1 mole of rosilane (■). The reaction is carried out, for example, at a temperature of 20 to 100°C for 10 minutes to 5 hours, preferably at a temperature of 40 to 70°C for 30 minutes to 2 hours. Solvents can also be used, including organic solvents such as hexane, ether, petroleum ether, benzene, and the like.

Here, in order to rapidly advance the reaction, it is preferable to coexist a dehydrohalogenating agent.

Examples of the dehydrohalogenation agent include tertiary amines and nitrogen-containing heterocyclic compounds such as pyridine, quinoline, and inquinoline. Among them, pyridine and quinoline are preferably used. The dehydrohalogenating agent is 1 to 1.5 per mole of cyclohexyltrihalosilane.
Preferably, it is used in molar amounts.

In the present invention, next, the obtained reaction product (III)
The above-mentioned silane compound (I> of the present invention) is produced by reacting with methanol.

In this reaction, 2 to 3 moles of methanol are used per 1 mole of compound (m). The reaction is carried out at a temperature of 0 to 100°C for 10 minutes to 5 hours, preferably at a temperature of 10 to 60°C for 30 minutes to 2 hours. Also in reaction C, it is preferable to coexist a dehydrohalogenating agent in order to speed up the reaction. As the dehydrohalogenating agent, the dehydrohalogenating agents exemplified above in reaction B can be used. The dehydrohalogenating agent used here may be the same as or different from the compound used in the previous reaction, but usually the same one is used. The dehydrohalogenating agent is preferably used in an amount of 2 to 3 mol per 1 mol of compound (III).

In addition, in the above-mentioned reactions B and C, the generated hydrogen halide can be removed from the reaction system by blowing in an inert gas, so that the reaction can proceed quickly.

By the above-described production method, the novel silane compound (I>) can be obtained in high yield.

The present invention also provides a different method for producing the silane compound of formula (I) above. That is, cyclohexyltrimethoxysilane and ROH (
This is a method for producing a compound of formula (I>) by subjecting a compound (R has the same meaning as above) to an alcohol exchange reaction: In the above reaction formula, 1 to 2 mol of ROH is added to the compound (IV>1 mol). The reaction is carried out, for example, from 50 to
It is carried out for 2 to 2 Ovf at a temperature of 100°C. In this alcohol exchange reaction, an acid such as a trifluoroborane-ether complex or toluenesulfonic acid; or a base such as an alkali metal alkaline earth metal hydroxide can be used as a catalyst.

Further, the starting material cyclohexyltrimethoxysilane (IV) can be produced by a dehydrochlorination reaction between cyclohexyltrichlorosilane and methanol.

(Example) The invention will be explained in more detail by the following examples.

Example 1 500 equipped with magnetic stirrer, cooling tube and dropping funnel
21.8 g (0,100 mol) of cyclohexyltrichlorosilane (manufactured by Tokyo Kasei ■) in a ml three-necked flask.
and hexane 2001111, to which pyridine 26.1 g (0,330 mol) and tert
-butyl alcohol 8.15 g (0,110 mol)
The mixture was added dropwise over 30 minutes with stirring at room temperature.

After heating under reflux for 3 hours, 7.05 g of methanol was added to it.
(0,220 mol) was added, and refluxing was continued for an additional hour, after which the reaction was terminated.

The generated salts were removed by filtration, the hexane was then distilled off, and the boiling point was reduced to 71° C. by distillation under reduced pressure.
17.3 g (0,0702 mol) of m+Hg liquid was obtained. The product was confirmed to be tert-butoxycyclohexyldimethoxysilane by GC-MS, 1H-NM
Confirmed by R and IR. 'H-NMR and I
The measurement results of R are shown in FIG. 1 and FIG. 2, respectively.

The yield was 70%.

Note that 'H-NMR and IR were measured under the following conditions.

one! H-NMR measuring device: Old TACHI R-1500 (manufactured by @J Hitachi), measuring solvent: CDCj! 3. Standard material: TMS (
Tetramethylsilane) IR Measuring device: IR-810 (manufactured by JASCO Corporation) Measuring method: Liquid film method (KBr plate) In addition, GC-MS used HP 5970B (manufactured by Heuret Barakad), and the measurement results were was as follows: m/e (spectral intensity ratio): 246
(1), 231(16), 163(1B), 109
(13), 107 (100), 91 (20), 77 (
22) Example 2 tert-butoxycyclohexyldimethoxysilane Ω
In a 100 ml three-necked flask equipped with an L-layer magnetic stirrer and a condenser, add 25% of cyclohexyltrimethoxysilane.
0 g (0,122 mol), tert-butyl alcohol 9.04 g (0,122 mol) and potassium t
20 mg (0.18 mmol) of ert-butoxide was charged, and the mixture was heated and stirred in an 80° C. oil bath for 10 hours to react. After cooling, the alkali is neutralized by adding ammonium chloride, followed by distillation under reduced pressure.
rt-butoxycyclohexyldimethoxysilane 8.1
2 g (0,0330 mol) were obtained. The structure was confirmed in the same manner as in Example 1. The yield was 27%.

Example 3 In an apparatus similar to Example 1, 21.8 g (0,100 mol) of cyclohexyltrichlorosilane and 2
001 and added 26.1 g of pyridine (0
, 330 mol) and in 10 pyl alcohol 6, 61
g (0,111) mol) was added dropwise over 30 minutes with stirring at room temperature. After continuing stirring for an additional hour, 7.05 g (0,220 mol) of methanol was added thereto, and stirring was continued for an additional hour before the reaction was terminated.

The generated salts are removed by filtration, the hexane is then distilled off, and the boiling point is reduced to 75°C/0 by distilling under reduced pressure.
．． 17.9 g (0,0770 mol) of liquid with a temperature of 7111 mHg was obtained. The product was confirmed to be impropoxycyclohexyldimethoxysilane by GC-MS, 1H-
Confirmed by NMR and IR. The results of 1H-NMR and IR measurements are shown in FIGS. 3 and 4, respectively. The yield was 11%.

In addition, the results of GC-MS were as follows.
(Spectrum intensity ratio): 232(2), 173
(4), 151(14), 149(57), 13
5(13), 117(5), 109(36), 10
7(100), 91(25), 55(17) Example 4 Into the same apparatus as in Example 2, 25.0 g (0,122 mol) of cyclohexyltrimethoxysilane and 7.33 g (0,122 mol) of isopropyl alcohol were added. ) and potassium tert-butoxide (20 mg (0.18 mmol)) were prepared in the same manner as in Example 2, and 4.90 g of isopropoxycyclohexyldimethoxysilane was prepared.
(0,0211 mol) was obtained. The structure was confirmed in the same manner as in Example 3. The yield was 21%.

(Effects of the Invention) According to the present invention, a novel silane compound useful as a propylene polymerization catalyst component, a silane coupling agent, etc., and a method for producing the same can be obtained.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 respectively show the t-shirt manufactured in Example 1.
1H-NMR and IR charts for ert-butoxycyclohexyldimethoxysilane, the third
Figures 4 and 4 respectively show 1 for isopropoxycyclohexyldimethoxysilane prepared in Example 3.
It is a chart of H-NMR and IR.

Claims (4)

[Claims] (1) A silane compound represented by the following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a tert-butyl group or an isopropyl group). (2) The method for producing a silane compound according to claim 1, which comprises reacting cyclohexyltrihalosilane with ROH (R has the same meaning as in claim 1), and then reacting the obtained reaction product with methanol. . (3) The method according to claim 2, wherein the reaction is carried out in the presence of a dehydrohalogenating agent. (4) Cyclohexyltrimethoxysilane and ROH
2. The method for producing a silane compound according to claim 1, wherein R is the same as in claim 1, and is subjected to an alcohol exchange reaction.