JPH05294976A - Silane compound and method for producing the same - Google Patents

Abstract

(57) [Summary] (Modified) [Object] To provide tert-amyloxycyclopentyldiethoxysilane, which is a novel silane compound useful as a propylene polymerization catalyst component, a silane coupling agent, and a method for producing the same. [Structure] Cyclopentyltrihalosilane is reacted with tert-amyl alcohol, and then the obtained reaction product is reacted with ethanol, or cyclopentyltriethoxysilane and tert-amyl alcohol are subjected to an alcohol exchange reaction to give a compound of formula (I ) The above silane compound is produced. (Where t-Amyl represents the tert-amyl group)

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 In propylene polymerization, it has hitherto been known that a polymer having high stereoregularity can be produced by using an alkoxysilane as a catalyst component. ing. However, even if propylene is polymerized using a catalyst component produced using a conventionally known alkoxysilane or the like, it is not possible to sufficiently satisfy both high polymerization activity and high stereoregularity.

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 provides the following formula (I):

[0006]

[Chemical 2] (Wherein t-Amyl represents a tert-amyl group), that is, tert-amyloxycyclopentyldiethoxysilane.

This silane compound (I) has a boiling point of 132 ° C.
/ 24 mmHg. The structure of this silane compound is GC-M
It can be confirmed by S, ¹ H-NMR, infrared absorption spectrum (IR) and the like.

For example, when the compound (I) is analyzed by using ¹ H-NMR, δ = 0.5 to 2.0, the cyclopentyl group, the tert-amyloxy group, and the —C H in the ethoxy group.
_A signal based on ₃ was observed, and additionally δ = 3.5-4.
0 -C H ₂ in ethoxy groups - Signal based on is observed.

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

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

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.

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 tert-amyl alcohol, and then the obtained reaction product is reacted with ethanol to produce the silane compound of the above formula (I). The raw material cyclopentyltrihalosilane has the following formula:

[0013]

[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:

[0014]

[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 tert-amyl alcohol. Tert-amyl alcohol itself is known and commercially available. The reaction between the two may proceed as follows:

[0016]

[Chemical 5] This reaction produces compound (III).

When carrying out the above reaction B, 1 to 3 mol of tert-amyl alcohol is used with respect to 1 mol of cyclopentyltrihalosilane (II). The reaction is, for example, 20 to
It is carried out at a temperature of 100 ° C. for 10 minutes to 5 hours, preferably 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 .about.1.5 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, ethanol is used in an amount of 2 to 3 mol per 1 mol of the 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 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 reaction B was previously used.
The hydrogen halide acceptor exemplified in 1) can be used.
The hydrogen halide acceptor used here may be the same as or different from the compound used in the previous reaction,
Normally, the same one is used. The hydrogen halide acceptor is preferably used in an amount of 2 to 3 mol per 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, a method for producing a compound of formula (I) by transesterifying cyclopentyltriethoxysilane and tert-amyl alcohol:

[0024]

[Chemical 7] In the above reaction formula, relative to 1 mol of compound (IV),
1 to 20 mol of tert-amyl alcohol are used. The reaction is carried out, for example, at a temperature of 0 to 150 ° C. for 10 minutes to 30 hours. In the case of this alkoxyl group exchange reaction, an acid,
For example, a trifluoroborane-ether complex and toluenesulfonic acid, or a compound which reacts with an alcohol to form an acid, such as trimethylchlorosilane; or a base,
For example, alkali metal alkoxides, metal hydroxides and the like can be used.

The starting material cyclopentyltriethoxysilane (IV) can be produced by the reaction of cyclopentyltrichlorosilane and ethanol to produce hydrogen chloride.

[0026]

The present invention will be described in more detail by the following examples.

[0027]

Example 1 of tert-amyloxycyclopentyldiethoxysilane
Production (1) Cyclopentene 15.2 g (0.223 mol), trichlorosilane 27.2 g (0.201 mol) and 0.077 in a 100 ml pressure vessel.
Charge 25 μl of a mmol / ml chloroplatinic acid solution in isopropyl alcohol (platinum content 1.92 × 10 ^-6 mol) at 150 ° C.
Cyclopentyltrichlorosilane was quantitatively obtained by stirring for 30 minutes.

In a 500 ml three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, the cyclopentyltrichlorosilane obtained above and 300 ml of hexane were charged, and 54.2 g (0.69 mol) of pyridine and A mixture of 25.2 g (0.29 mol) of tert-amyl alcohol was added dropwise at room temperature with stirring for 30 minutes.

After heating under reflux for 2 hours, ethanol is added here.
27.7 g (0.602 mol) was added, and the mixture was refluxed for another hour, and then the reaction was terminated.

The salt formed is removed by filtration, hexane is then distilled off, and the residue is distilled under reduced pressure to obtain the boiling point.
38.7 g (0.141 mol) of a liquid at 132 ° C / 24 mmHg was obtained. It was confirmed by GC-MS, ¹ H-NMR and I that this product was tert-amyloxycyclopentyldiethoxysilane.
Confirmed by R. ^{The 1} H-NMR and IR measurement results are shown in FIGS. 1 and 2, respectively. The yield was 70%.

¹ H-NMR and IR were measured under the following conditions.

¹ H-NMR measuring device: HITACHI R-24B (manufactured by Hitachi, Ltd.), measuring solvent: CCl ₄ , standard substance: CHCl ₃ , tetramethylsilane (TMS) IR measuring device: 1600 series FT-IR (Perkin Elmer Co., Ltd.) Measurement method: Liquid film method (KBr plate) Further, GC-MS was HP 5970B (manufactured by Hewlett Packard Co.), and the measurement results were as follows: m / e (spectrum) Intensity ratio): 63 (28), 79 (30),
119 (15), 135 (100), 159 (12), 177 (10), 187 (28),
205 (15), 245 (24).

[0033]

Example 2 of tert-amyloxycyclopentyldiethoxysilane
Production (2) In a 100 ml three-necked flask equipped with a magnetic stir bar and a reflux condenser, 20.5 g (0.0
882 mol), tert-amyl alcohol 128 g (1.46 mol)
And 0.953 g (14.0 mmol) of sodium ethoxide were charged, and the mixture was reacted by stirring in an oil bath at 105 ° C for 24 hours. Then, trimethylchlorosilane was added to neutralize the alkali, and then distilled under reduced pressure to give tert-
Amyloxycyclopentyldiethoxysilane 19.0g
(0.0693 mol) was obtained. The structure was confirmed in the same manner as in Example 1. The yield was 79%.

[0034]

The present invention provides 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 ¹ H-NMR chart of tert-amyloxycyclopentyldiethoxysilane produced in Example 1.

FIG. 2 is an IR chart for tert-amyloxycyclopentyldiethoxysilane produced in Example 1.

Claims (3)

[Claims] 1. The following formula (I): (Wherein t-Amyl represents a tert-amyl group). 2. A tert-cyclopentyltrihalosilane
The method for producing a silane compound according to claim 1, wherein the reaction product is reacted with amyl alcohol and then the obtained reaction product is reacted with ethanol. 3. Cyclopentyltriethoxysilane and t
The method for producing a silane compound according to claim 1, wherein a tert-amyloxy group is introduced into the silane compound by an alcohol exchange reaction of ert-amyl alcohol.