JPH0753573A - Silane compound and its production - Google Patents

Abstract

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

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-propoxy) dimethoxysilane (I-1) and cyclopentylbis (1-methoxy-2-propoxy) methoxysilane (I-2).

This silane compound (I-1) has a boiling point of 6
1 ° C / 0.1 mmHg, (I-2) has a boiling point of 103
° 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 2.4, a cyclopentyl group and a methyl group bonded to a carbon atom, δ Signals based on hydrogen atoms on carbon bonded to oxygen atoms were observed at = 2.8 to 4.5.

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): 203 (32.95), 179 (97.3), 159 (21.25),
149 (13.11), 135 (72.66), 131 (39.83), 121 (100), 107 (13.6
2), 91 (78.6), 77 (17.38), 45 (22.43) Compound (I-2): 237 (69.39), 217 (100), 179 (12.26), 1
59 (21.77), 149 (25.68), 131 (26.03), 121 (45.98), 107 (15.
23), 91 (33.95), 77 (16.34), 45 (22.98) When this silane compound (I) is used as a catalyst component, olefin polymers having high stereoregularity such as polypropylene and polybutene 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-propanol, 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-propanol:

[0017]

[Chemical 7] (Here, R and n have the same meanings as above.) In carrying out this reaction, 1 to 3 mol of 1-methoxy-2-propanol 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
It is carried out for 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 ˜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 transalcoholization reaction with 1-methoxy-2-propanol to introduce a 1-methoxy-2-propoxy group to the above 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-Use 1-20 mol of propanol. 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-propoxy) dimethoxide
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 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 1- A mixture of 20.0 g (0.222 mol) of methoxy-2-propanol 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 salt formed was removed by filtration, hexane was then distilled off, and the residue was distilled under reduced pressure to give a boiling point of 61 ° C./0.1 mmHg (digital vacuum gauge, manufactured by Hayasaka Riko Co., Ltd.,
40.2 g (0.162 mol) of liquid having a resolution of 0.1 mmHg) was obtained. GC-MS shows that this product is cyclopentyl (1-methoxy-2-propoxy) dimethoxysilane.
Confirmed by ¹ H-NMR and IR. ¹ H-NM
The measurement results of R and IR are shown in FIGS. 1 and 2, respectively. The yield was 88%.

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-propoxy) meth
Production of xysilane (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-propanol 40.0
A mixture of g (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 distilled off, and the residue was distilled under reduced pressure to obtain 52.8 g (0.173 mol) of a liquid having a boiling point of 103 ° C./0.1 mmHg. This product is cyclopentylbis (1-methoxy-2-
GC-MS, ¹ H-NMR and I measured under the same conditions as in Example 1 to be propoxy) methoxysilane.
Confirmed by R. ^{The 1} H-NMR and IR measurement results are shown in FIGS. 3 and 4, respectively. The yield was 94%. Example 3 Cyclopentyl (1-methoxy-2-propoxy) dimethoxide
(2) In a 100-ml three-necked flask equipped with a magnetic stirrer and a reflux condenser, 12 g of cyclopentyltrimethoxysilane (6
3.2 mmol), 1-methoxy-2-propanol 8.8 g (9
8 mmol) and 70 mg of sodium methoxide (1.3
(Mmol) and charged for reaction for 3 hours at room temperature. Then, the alkali was neutralized by adding trimethylchlorosilane, and then distilled under reduced pressure to obtain 13.5 g (54 mmol) of cyclopentyl (1-methoxy-2-propoxy) dimethoxysilane. The structure was confirmed in the same manner as in Example 1. The yield was 85%. Example 4 Cyclopentylbis (1-methoxy-2-propoxy) meth
Production of xysilane (2) A container similar to that used in Example 3 was charged with 12 g (63.2 mmol) of cyclopentyltrimethoxysilane, 17.6 g (195 mmol) of 1-methoxy-2-propanol and 140 mg (2.6 mmol) of sodium methoxide. The reaction was allowed to stir at room temperature for 5 hours. Then, by adding trimethylchlorosilane to neutralize the alkali, and then vacuum distilling, cyclopentylbis (1-methoxy-2-
16.8 g (55 mmol) of propoxy) methoxysilane were obtained. The structure was confirmed in the same manner as in Example 2. Yield 87
%Met.

[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-propoxy) dimethoxysilane produced in Example 1.

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

FIG. 3 ¹ H-NMR of cyclopentylbis (1-methoxy-2-propoxy) methoxysilane produced in Example 2.
It is a chart which shows the result of a spectrum analysis.

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Nomura 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside 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. The method for producing a silane compound according to claim 1, wherein cyclopentyltrihalosilane is reacted with 1-methoxy-2-propanol, and then the obtained reaction product is reacted with methanol. 3. Cyclopentyltrimethoxysilane and 1-
The method for producing a silane compound according to claim 1, wherein a 1-methoxy-2-propoxy group is introduced into the silane compound by an alcohol exchange reaction with methoxy-2-propanol.