JP3246939B2 - Silane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

[0003] Further, silane compounds are expected to be used as silane coupling agents or resin modifiers, and therefore, the emergence of new silane compounds is desired.

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

[0005]

[0006]

[0007]

[0008]

[0009]

[0010]

[0011]

[0012]

SUMMARY OF THE INVENTION The present invention is in the first, there is provided a method for producing a novel silane compound represented by the formula (I). That is, reacting cyclopentyltrihalosilane with tert-amyl alcohol,
The silane compound of the above formula (I) is produced by reacting the obtained reaction product with methanol. The starting material cyclopentyltrihalosilane has the following formula:

[0013]

Embedded image (X represents a halogen atom, preferably Cl or B
represented by r a is), from cyclopentene and trihalosilane (H-SiX _3), it can be easily prepared by a hydrosilylation reaction:

[0014]

Embedded image At this time, per mole of cyclopentene, trihalosilane
Use 0.9-1.1 moles. The reaction conditions are, for example,
At a temperature of 100 to 200 ° C. for 10 minutes to 10 hours, and a 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. Further, a solvent can 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 is thought to proceed as follows:

[0016]

Embedded image By this reaction, compound (III) is produced.

In carrying out the above reaction B, 1 to 3 mol of tert-amyl alcohol is used per 1 mol of cyclopentyltrihalosilane (II). The reaction is, for example, 20-
It is carried out at a temperature of 100 DEG C. for 10 minutes to 5 hours, preferably at a temperature of 40 DEG to 70 DEG 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 make the reaction proceed promptly, it is preferable to coexist with a hydrogen halide acceptor. As the hydrogen halide acceptor, tertiary amines,
Nitrogen-containing heterocyclic compounds, such as pyridine, quinoline, isoquinoline and the like. Among them, pyridine and quinoline are preferably used. The hydrogen halide acceptor is used in an amount of 1 per mole of cyclopentyltrihalosilane.
It is preferably used in an amount of .about.1.5 mol.

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

[0020]

Embedded image In this reaction, 2 to 3 mol of methanol 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 to 2 hours. Also in the reaction C, it is preferable to coexist a hydrogen halide acceptor in order to promptly proceed the reaction. As the hydrogen halide acceptor, the reaction B
Can be used.
The hydrogen halide acceptor used here may be the same or different from the compound used in the previous reaction,
Usually, the same one is used. The hydrogen halide acceptor is preferably used in an amount of 2 to 3 mol per 1 mol of compound (III).

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

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

The present invention also provides a different method for producing the silane compound represented by the above formula (I). That is, a method for producing a compound of the formula (I) by subjecting cyclopentyltrimethoxysilane and tert-amyl alcohol to an alcohol exchange reaction:

[0024]

Embedded image In the above reaction formula, 1 mol of compound (IV) is
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 20 hours. In the case of this alkoxyl group exchange reaction, an acid,
Those which react with alcohols to form acids, such as trifluoroborane-ether complexes and toluenesulfonic acid, or trimethylchlorosilane; or bases,
For example, alkali metal alkoxides, metal hydroxides and the like can be used.

The starting material cyclopentyltrimethoxysilane (IV) can be produced by reacting cyclopentyltrichlorosilane with methanol to produce hydrogen chloride. The silane compound, which is the object of the present invention,
The product (I) has a boiling point of 95 ° C./1.9 mmHg. This
Has a structure of GC-MS, 1H-NMR,
It can be confirmed by infrared absorption spectrum (IR) etc.
it can. For example, using 1H-NMR, compound (I)
Is analyzed, tert-amyl is obtained when δ = 0.7 to 1.5.
Oxy group, cyclopentyl group at δ = 1.5 to 2.2, δ
= 3.52, a signal based on a methoxy group was observed.
You. From the analysis by IR spectrum, 1100
Large absorption due to SiOC bond is observed around ^-1
You. When this silane compound (I) is used as a catalyst,
Stereoregular polypropylene and polybutene
Refining polymers can be produced under high polymerization activity.
Wear. The silane compound (I) has a hydrolyzable group.
Silane coupling agent, polymerizable
It can be used as a mer and resin modifier.

[0026]

The present invention will be described in more detail with reference to the following examples.

[0027]

Example 1 of tert-amyloxycyclopentyldimethoxysilane
Production (1) In a 100 ml pressure vessel, 13.5 g (0.198 mol) of cyclopentene, 24.4 g (0.180 mol) of trichlorosilane and 0.077 mol
25 μl of a solution of chloroplatinic acid in isopropyl alcohol at a concentration of mmol / ml (platinum content: 1.92 × 10 ^-6 mol) was charged at 150 ° C
For 30 minutes to obtain cyclopentyltrichlorosilane quantitatively.

In a 500 ml three-necked flask equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, 300 ml of cyclopentyltrichlorosilane and hexane obtained above were charged, and 47.9 g (0.606 mol) of pyridine and A mixture of 23.2 g (0.264 mol) of tert-amyl alcohol was added dropwise at room temperature with stirring for 30 minutes.

After heating under reflux for 2 hours, methanol
17.9 g (0.558 mol) was added, and reflux was continued for another hour, and then the reaction was terminated.

The salt formed is removed by filtration, and then hexane is distilled off.
34.8 g (0.141 mol) of a liquid at 95 ° C./1.9 mmHg was obtained. This product was identified as tert-amyloxycyclopentyldimethoxysilane by GC-MS, ¹ H-NMR and
Confirmed by R. The measurement results of ¹ H-NMR and IR are shown in FIGS. 1 and 2, respectively. The yield was 78%.

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

¹ H-NMR measuring apparatus: HITACHI R-24B (manufactured by Hitachi, Ltd.), measuring solvent: CCl ₄ , standard substance: CHCl ₃ , tetramethylsilane (TMS) IR measuring apparatus: 1600 series FT-IR (Perkin-Elmer) Measurement method: liquid film method (KBr plate) In addition, GC-MS used HP 5970B (manufactured by Hewlett-Packard), and the measurement results were as follows: m / e (spectrum) Intensity ratio): 231 (6), 217 (19),
177 (6), 159 (16), 149 (12), 131 (16), 107 (100), 91
(22), 77 (23), 59 (16).

[0033]

Example 2 of tert-amyloxycyclopentyldimethoxysilane
Production (2) In a 100 ml three-necked flask equipped with a magnetic stir bar and a reflux condenser, 10.1 g of cyclopentyltrimethoxysilane (0.
0531 mol), 30.6 g (0.347 mol) of tert-amyl alcohol and 86.4 mg (1.6 mmol) of sodium methoxide were stirred and reacted in a 105 ° C. oil bath for 4 hours. Thereafter, the alkali was neutralized by adding trimethylchlorosilane, and then distilled under reduced pressure to obtain tert.
-Amyloxycyclopentyldimethoxysilane 10.7g
(0.0434 mol). The structure was confirmed in the same manner as in Example 1. The yield was 82%.

According to the present invention, a propylene polymerization catalyst component, a silane coupling agent, a polymerizable monomer and a resin
The present invention provides a method for producing a novel silane compound useful as a filler .

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of tert-amyloxycyclopentyldimethoxysilane produced in Example 1.

FIG. 2 is an IR chart of tert-amyloxycyclopentyldimethoxysilane produced in Example 1.

Continuation of the front page (56) References JP-A-3-119004 (JP, A) JP-A-1-156305 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7 / 18

Claims (2)

(57) [Claims] 1. A formula (I): 1] (Here, t-Amyl represents a tert-amyl group.
C) reacting cyclopentyltrihalosilane with tert-amyl alcohol, and then reacting the obtained reaction product with methanol. Wherein formula (I): 1] (Here, t-Amyl represents a tert-amyl group.
C) wherein a tert-amyloxy group is introduced into the silane compound by an alcohol exchange reaction between cyclopentyltrimethoxysilane and tert-amyl alcohol. .