JPH06345782A - Silane compound and its production - Google Patents

Abstract

PURPOSE:To provide a highly active new compound useful as a catalytic component for obtaining polypropylene of high stereoregularity, a silane coupling agent, etc. CONSTITUTION:The objective compound, cyclopentylbis(2-ethoxyethoxy) ethoxysilane of formula I, which can be obtained by the following process: (A) a cyclopentyltrihalosilane of formula II (X is halogen) is reacted with (B) 2-ethoxyethanol at a molar ratio B/A of >=2, in a solvent (e.g. hexane) if needed, pref. in the presence of a hydrogen halide acceptor (e.g. pyridine) at 20-100 deg.C for 10min to 5hr to produce (C) a compound of formula III, which, in turn, is reacted with (D) ethanol at a molar ratio D/C of 1-1.6 pref. in the presence of the same hydrogen halide acceptor as the above at 0-100 deg.C for 10min to 5hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silane compound and a method for producing the same, and more particularly to a novel silane compound used as a propylene polymerization catalyst component, a silane coupling agent and the like and a method for producing the same.

[0002]

2. Description of the Related Art It has been conventionally known that a polymer having a high stereoregularity can be produced by using an alkoxysilane as a catalyst component in carrying out propylene polymerization. However, even if propylene is polymerized using a catalyst component produced using a conventionally known alkoxysilane or the like, both high polymerization activity and high stereoregularity cannot be sufficiently satisfied.

Further, the silane compound is expected to be used as a silane coupling agent or a resin modifier, and therefore, a new silane compound is desired to appear.

Therefore, an object of the present invention is to provide a novel silane compound having high activity and high stereoregularity, which is useful as a propylene polymerization catalyst component or a silane coupling agent, and a method for producing the same.

[0005]

The present invention firstly provides the following formula (I):

[0006]

[Chemical 2] And a cyclopentyl bis (2-ethoxyethoxy) ethoxysilane.

This silane compound (I) has a boiling point of 76 ° C.
/0.1 mmHg. The structure of this silane compound is GC
-MS, ¹ H-NMR, infrared absorption spectrum (IR)
Etc. can be confirmed.

For example, when the compound (I) is analyzed by using ¹ H-NMR, a methyl group bonded to a carbon atom at δ = 1.0 to 1.4, a cyclopentyl group at δ = 1.4 to 2.2, and δ
= 3.4 to 4.4, a signal based on the methylene group bonded to the oxygen atom was observed.

Further, from the analysis by IR spectrum,
A large absorption due to the SiOC bond was observed near 1100 cm ^-1 .

From the analysis by GC-MS, the following m
/ E (spectral intensity ratio) was observed: 275 (3.67), 25
1 (100), 231 (40.37), 207 (1.03), 177 (58.35), 163 (8.28), 1
49 (43.2), 123 (13.19), 79 (16.03), 63 (15.69).

By using this silane compound (I) as a catalyst component, an olefin polymer having high stereoregularity such as polypropylene or polybutene can be produced with high polymerization activity.

Since the silane compound (I) has a hydrolyzable group, it can be used as a silane coupling agent, a polymerizable monomer and a resin modifier.

The present invention secondly provides a method for producing a novel silane compound represented by the above formula (I). That is, 1 mole of cyclopentyltrihalosilane is reacted with 2 moles or more of 2-ethoxyethanol, and then the obtained reaction product is reacted with ethanol to produce a silane compound of the above formula (I). is there. The raw material cyclopentyltrihalosilane has the following formula:

[0014]

[Chemical 3] (X represents a halogen atom, preferably Cl or B
is r) and can be readily prepared from cyclopentene and trihalosilane (H—SiX ₃ ) by a hydrosilylation reaction:

[0015]

[Chemical 4] At this time, per mol of cyclopentene, trihalosilane
Use 0.9 to 1.1 moles. The reaction conditions are, for example,
The temperature is 100 to 200 ℃, 10 minutes to 10 hours, platinum-based catalyst, such as chloroplatinic acid, platinum-1,1,3,3-tetramethyl-
It is preferable to use a 1,3-divinyldisiloxane complex or the like. A solvent can also be used, and examples thereof include benzene and toluene.

In the present invention, the cyclopentyltrihalosilane (II) thus obtained is reacted with 2-ethoxyethanol:

[0017]

[Chemical 5] When carrying out this reaction, 2-ethoxyethanol is used in an amount of 2 mol or more, preferably 2 to 2.6 mol, relative to 1 mol of cyclopentyltrihalosilane (II). The reaction is carried out, for example, at a temperature of 20 to 100 ° C for 10 minutes to 5 hours, preferably 40
Perform at a temperature of ~ 70 ° C for 30 minutes to 2 hours. It is also possible to use solvents, for example hexane, ether, petroleum ether,
An organic solvent such as benzene can be used.

Here, in order to allow the reaction to proceed rapidly, it is preferable to coexist with a hydrogen halide acceptor. As the hydrogen halide acceptor, tertiary amines,
And nitrogen-containing heterocyclic compounds such as pyridine, quinoline, isoquinoline and the like. Of these, pyridine and quinoline are preferably used. The hydrogen halide acceptor is 2 moles per mole of cyclopentyltrihalosilane.
It is preferably used in an amount of ˜3 mol.

In the present invention, the obtained reaction product (III) is then reacted with ethanol to produce the above-mentioned silane compound (I) of the present invention.

[0020]

[Chemical 6] In this reaction, 1 to 1.6 mol of ethanol is used per 1 mol of compound (III). 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.
Do for ~ 2 hours. Also in the reaction C, it is preferable to coexist with a hydrogen halide acceptor in order to allow the reaction to proceed rapidly. As the hydrogen halide acceptor, the hydrogen halide acceptor exemplified above in the reaction B can be used. The hydrogen halide acceptor 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 hydrogen halide acceptor is preferably used in an amount of 1 to 1.5 mol with respect to 1 mol of the compound (III).

Further, in the above-mentioned reaction B and reaction C, by blowing an inert gas, the produced hydrogen halide can be removed from the reaction system to allow the reaction to proceed rapidly.

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

The present invention also provides a method different from the above for producing the silane compound represented by the above formula (I). That is, cyclopentyl triethoxysilane 1
More than 2 mol of 2-ethoxyethanol is reacted with mol, and the above silane compound is formed by alcohol exchange reaction.
A method of producing a compound of formula (I) by introducing a 2-ethoxyethoxy group:

[0024]

[Chemical 7] In the above reaction formula, relative to 1 mol of compound (IV),
2-Ethoxyethanol is 2 mol or more, preferably 2 to 2
Use 0 mol. The reaction is carried out, for example, at a temperature of 0 to 100 ° C for 10
Do for 20 minutes to 20 minutes. During this alcohol exchange reaction,
As a catalyst, an acid, such as a trifluoroborane-ether complex, toluenesulfonic acid, or one that reacts with an alcohol to form an acid, such as trimethylchlorosilane; or a base, such as an alkali metal alkoxide,
Metal hydroxides and the like can be used.

Cyclopentyltriethoxysilane (IV) which is a starting material can be produced by a reaction of cyclopentyltrichlorosilane and ethanol with generation of hydrogen chloride.

[0026]

The present invention will be described in more detail by the following examples. Example 1 Cyclopentylbis (2-ethoxyethoxy) ethoxy
Production of orchid (1) In a 100 ml pressure vessel, cyclopentene 13.9 g (0.204 mol), trichlorosilane 25.1 g (0.185 mol) and
Charge 25 μl of 0.077 mmol / ml chloroplatinic acid in isopropyl alcohol (platinum content 1.92 × 10 ⁻⁶ mol),
Cyclopentyl trichlorosilane was quantitatively obtained by stirring at 150 ° C. for 30 minutes.

A 500 ml three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel was charged with the cyclopentyltrichlorosilane obtained above and 300 ml of hexane, and 49.3 g (0.623 mol) of pyridine and 2- A mixture of 40.0 g (0.444 mol) of ethoxyethanol was added dropwise at room temperature with stirring for 30 minutes. After refluxing for 2 hours, 13.2 g (0.287 mol) of ethanol was added thereto, and refluxing was continued for another hour, and then the reaction was terminated.

The produced salt was removed by filtration, hexane was distilled off, and the residue was distilled under reduced pressure to give a boiling point of 76 ° C./0.1 mmHg (digital vacuum gauge, manufactured by Hayasaka Riko Co., Ltd.,
44.8 g (0.140 mol) of a liquid having a resolution of 0.1 mmHg) was obtained. This product is cyclopentylbis (2-ethoxyethoxy) ethoxysilane, GC-MS, ¹ H
-Confirmed by NMR and IR. ^{The 1} H-NMR and IR measurement results are shown in FIGS. 1 and 2, respectively. The yield was 76%.

¹ H-NMR, IR and GC-M
S was measured under the following conditions.

[0030]¹ H-NMR Measuring device: HITACHI R-1500 (manufactured by Hitachi, Ltd.)
Constant solvent: C₆D₆, Reference material: residual benzeneIR  Measuring device: 1600 series FT-IR (Perkin Elmer
(Mfd.) Measuring method: Liquid film method (KBr plate)GC-MS Measuring device: HP 5970B (Hewlett Packard Company
Made)Example 2 Cyclopentylbis (2-ethoxyethoxy) ethoxy
Manufacturing of orchids (2) 100 ml 3-neck flap equipped with magnetic stir bar and reflux condenser
Add 15 g of cyclopentyl triethoxysilane (6
4.7 mmol), 13.5 g of 2-ethoxyethanol (150 ml)
Limol) and sodium ethoxide 176 mg (2.6 mg
Limol) was charged and the reaction was carried out by stirring at room temperature for 6 hours.
After that, by adding trimethylchlorosilane,
By neutralizing the alkali, followed by vacuum distillation.
Cyclopentylbis (2-ethoxyethoxy) ethoxy
16.3 g (51 mmol) of silane was obtained. Example structure
Confirmed in the same manner as 1. The yield was 79%.

[0031]

According to the present invention, it is possible to provide a novel silane compound useful as a propylene polymerization catalyst component, a silane coupling agent and the like, and a method for producing the same.

[Brief description of drawings]

FIG. 1 is a chart showing the result of ¹ H-NMR spectrum analysis of cyclopentylbis (2-ethoxyethoxy) ethoxysilane produced in Example 1.

FIG. 2 is a chart showing the results of IR spectrum analysis of cyclopentylbis (2-ethoxyethoxy) ethoxysilane produced in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Satoshi Ueki 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (3)

[Claims] 1. The following formula (I): A silane compound represented by. 2. The silane compound according to claim 1, wherein 2 mol or more of 2-ethoxyethanol is reacted with 1 mol of cyclopentyltrihalosilane, and then the obtained reaction product is reacted with ethanol. Manufacturing method. 3. The above-mentioned silane compound is obtained by reacting 1 mol of cyclopentyltriethoxysilane with 2 mol or more of 2-ethoxyethanol and performing an alcohol exchange reaction.
The method for producing a silane compound according to claim 1, wherein a 2-ethoxyethoxy group is introduced.