JPH0753574A - Silane compound and its production - Google Patents

Abstract

PURPOSE:To obtain new silane compounds, a cyclopentyl(1-methoxy-2-butoxy) dimethoxysilane and a cyclopentyl-bis(1-methoxy-2-butoxy)methoxysilane. CONSTITUTION:A cyclopentyl(1-methoxy-2butoxy)dimethoxysilan or a cyclopentyl-bis(1-methoxy-2-butoxy)dimethoxysilane of formula I (R is formula II; (n) is 1 or 2). These silane compounds can be obtained by the following methods: (1) a cyclopentyltrigalosilane is reacted with 1-methoxy-2-butanol followed by reaction of the reactional product with methanol; or (2) 1- methoxy-2-butoxy group is introduced into a cyclopentyltrimethoxysilane by alcohol interchange reaction between thc silane compound and 1-methoxy-2- butanol.

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 3] (Where R is the following formula:

[0007]

[Chemical 4] Represents a group represented by and n is 1 or 2, that is, cyclopentyl (1-methoxy)
-2-Butoxy) dimethoxysilane (I-1) and cyclopentylbis (1-methoxy-2-butoxy) methoxysilane (I-2).

The silane compound (I-1) has a boiling point of 7
6 ° C / 0.1 mmHg, (I-2) has a boiling point of 115
° C / 0.1 mmHg. The structures of these silane compounds can be confirmed by GC-MS, ¹ H-NMR, infrared absorption spectrum (IR) and the like.

For example, when analyzed using ¹ H-NMR, in both compounds (I-1) and (I-2), δ = 0.8 to 2.2, cyclopentyl group, methyl group bonded to carbon atom, carbon Methylene group attached to an atom, δ
== 3.0-4.4, the signal based on the hydrogen atom on the carbon atom bonded to the oxygen atom was observed.

From the analysis by IR spectrum,
In each of the compounds (I-1) and (I-2), large absorption based on the SiOC bond was observed near 1100 cm ^-1 .

From the analysis by GC-MS, the following m
/ E (spectral intensity ratio) was observed. Compound (I-1): 231 (1.71), 217 (53.50), 201 (6.21), 1
91 (100), 159 (25.07), 149 (95.25), 139 (19.64), 131 (46.1
0), 121 (79.45), 107 (21.89), 91 (80.30), 77 (21.31), 45 (3
8.04) Compound (I-2): 265 (79.44), 231 (100), 217 (53.50), 1
63 (17.87), 159 (15.48), 151 (12.74), 131 (14.12), 121 (16.
56), 107 (10.14), 91 (16.65), 77 (8.56) When this silane compound (I) is used as a catalyst component, olefinic polymers such as polypropylene and polybutene having high stereoregularity can be highly polymerized. Can be manufactured below.

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, the cyclopentyltrihalosilane is reacted with 1-methoxy-2-butanol, and then the obtained reaction product is reacted with methanol to produce the silane compound of the above formula (I). The raw material cyclopentyltrihalosilane has the following formula:

[0014]

[Chemical 5] (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 6] 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 1-methoxy-2-butanol:

[0017]

[Chemical 7] (Here, R and n have the same meanings as above.) In carrying out this reaction, 1 to 1 mol of 1-methoxy-2-butanol is used with respect 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 minutes.
It is carried out at a temperature of 40 to 70 ° C. for 30 minutes to 2 hours. A solvent can also be used, and examples thereof include organic solvents such as hexane, ether, petroleum ether, and benzene.

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 1 mole to 1 mole of cyclopentyltrihalosilane.
It is preferably used in an amount of ˜3 mol.

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

[0020]

[Chemical 8] (Here, R and n have the same meanings as described above.) In this reaction, 1 mol of the compound (III) was added to 1 mol of methanol.
Use 5 moles. The reaction is carried out at a temperature of 0 to 100 ° C for 10 minutes
It is carried out for 5 hours, preferably at a temperature of 10 to 60 ° C. for 30 minutes to 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. Hydrogen halide acceptor is a compound
It is preferably used in an amount of 1 to 3 mol with respect to 1 mol of (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, cyclopentyltrimethoxysilane
A method for producing a compound of formula (I) by transalcoholizing 1-methoxy-2-butanol to introduce a 1-methoxy-2-butoxy group into the silane compound:

[0024]

[Chemical 9] (Wherein R and n have the same meanings as described above) In the above reaction formula, 1-methoxy is added to 1 mol of the compound (IV).
-2-1 to 20 mol of butanol is used. The reaction is carried out, for example, at a temperature of 0 to 100 ° C. for 10 minutes to 20 hours. In this alcohol exchange reaction, a catalyst such as an acid, for example, a trifluoroborane-ether complex, toluenesulfonic acid, or a compound which reacts with an alcohol to generate an acid, for example, trimethylchlorosilane; or a base, for example, an alkali metal alkoxide , Metal hydroxides and the like can be used.

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

[0026]

The present invention will be described in more detail by the following examples. Example 1 Cyclopentyl (1-methoxy-2-butoxy) dimethoxy
Production of silane (1) In a 100 ml pressure vessel, 13.9 g (0.204 mol) of cyclopentene, 25.1 g (0.185 mol) of trichlorosilane 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 cyclopentyl trichlorosilane obtained above and 300 ml of hexane were charged into a 500 ml three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, and 49.3 g (0.623 mol) of pyridine and 1- A mixture of 23.1 g (0.222 mol) of methoxy-2-butanol was added dropwise at room temperature with stirring for 30 minutes. After refluxing for 2 hours, 18.4 g (0.575 mol) of methanol was added thereto,
After refluxing was continued for another hour, the reaction was terminated.

The produced salt was removed by filtration, hexane was then 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.,
40.1 g (0.153 mol) of a liquid having a resolution of 0.1 mmHg) was obtained. According to GC-MS, ¹ that this product is cyclopentyl (1-methoxy-2-butoxy) dimethoxysilane.
Confirmed by 1 H-NMR and IR. ¹ H-NMR
The measurement results of IR and IR are shown in FIGS. 1 and 2, respectively. The yield was 83%.

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

¹ H-NMR measuring device: HITACHI R-1500 (manufactured by Hitachi, Ltd.), measuring solvent: C ₆ D ₆ , standard substance: residual benzene IR measuring device: 1600 series FT-IR (manufactured by Perkin Elmer Co., Ltd.) ) Measuring method: Liquid film method (KBr plate) GC-MS measuring apparatus: HP 5970B (manufactured by Hewlett Packard Co.) Example 2 Cyclopentylbis (1-methoxy-2-butoxy) methoxy
Production of silane (1) 500 equipped with magnetic stirrer, reflux condenser and dropping funnel
Into a 3 ml flask of 3 ml, 37.6 g (0.185 mol) of cyclopentyltrichlorosilane obtained in the same manner as in Example 1 and 300 ml of hexane were charged, and 49.3 g of pyridine was added thereto.
(0.623 mol) and 1-methoxy-2-butanol 46.2g
A mixture of (0.444 mol) was added dropwise at room temperature with stirring for 30 minutes. After refluxing for 2 hours, 9.2 g of methanol was added here.
(0.288 mol) was added and reflux was continued for another hour before terminating the reaction.

The produced salt was removed by filtration, hexane was then distilled off, and the residue was distilled under reduced pressure to obtain 53.1 g (0.159 mol) of a liquid having a boiling point of 115 ° C./0.1 mmHg. This product is cyclopentylbis (1-methoxy-2-
Butoxy) methoxysilane, which was measured under the same conditions as in Example 1 by GC-MS, ¹ H-NMR and IR
Confirmed by. ^{The 1} H-NMR and IR measurement results are shown in FIGS. 3 and 4, respectively. The yield was 86%. Example 3 Cyclopentyl (1-methoxy-2-butoxy) dimethoxy
Silane production (2) Cyclopentyltrimethoxysilane 12g (6g) was added to a 100ml three-necked flask equipped with a magnetic stir bar and a reflux condenser.
3.2 mmol), 1-methoxy-2-butanol 10.2 g (98
(Mmol) and 70 mg (1.3 mmol) of sodium methoxide were charged and reacted at room temperature with stirring for 3 hours.
Then, trimethylchlorosilane was added to neutralize the alkali, and then distilled under reduced pressure to obtain 13.8 g (53 mmol) of cyclopentyl (1-methoxy-2-butoxy) dimethoxysilane. The structure was confirmed in the same manner as in Example 1. The yield was 84%. Example 4 Cyclopentylbis (1-methoxy-2-butoxy) methoxy
Production of silane (2) In a container similar to that used in Example 3, 12 g (63.2 mmol) of cyclopentyltrimethoxysilane, 20.3 g (195 mmol) of 1-methoxy-2-butanol and sodium methoxide were added.
140 mg (2.6 mmol) was charged and reacted at room temperature for 5 hours with stirring. Then, the alkali was neutralized by adding trimethylchlorosilane, and then vacuum distillation was performed to obtain 17.0 g (51 mmol) of cyclopentylbis (1-methoxy-2-butoxy) methoxysilane.
The structure was confirmed in the same manner as in Example 2. The yield was 81%.

[0032]

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 cyclopentyl (1-methoxy-2-butoxy) dimethoxysilane produced in Example 1.

FIG. 2 is a chart showing the results of IR spectrum analysis of cyclopentyl (1-methoxy-2-butoxy) dimethoxysilane produced in Example 1.

FIG. 3 is a chart showing the results of ¹ H-NMR spectrum analysis of cyclopentylbis (1-methoxy-2-butoxy) methoxysilane produced in Example 2.

FIG. 4 is a chart showing the results of IR spectrum analysis of cyclopentylbis (1-methoxy-2-butoxy) methoxysilane produced in Example 2.

 ─────────────────────────────────────────────────── ─── 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): (Where R is the following formula: Represents a group represented by, and n is 1 or 2). 2. A cyclopentyltrihalosilane is reacted with 1-methoxy-2-butanol and then the resulting reaction product is reacted with methanol.
A method for producing the silane compound described. 3. Cyclopentyltrimethoxysilane and 1-
The method for producing a silane compound according to claim 1, wherein a 1-methoxy-2-butoxy group is introduced into the silane compound by an alcohol exchange reaction with methoxy-2-butanol.