JP3115061B2 - Production method of new silane compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an manufacturing <br/> method for producing novel silane compounds, more specifically, the polymerization catalyst component of propylene, a method of manufacturing a novel silane compound used as a silane coupling agent.

[0002]

2. Description of the Related Art It has been known that when propylene polymerization is carried out, a polymer having a 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 fully 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]

According to the present invention, there is provided the following formula (I):

[0006]

Embedded image The present invention provides a method for producing a silane compound represented by the formula, that is, cyclopentyloxycyclopentyldimethoxysilane.

This silane compound (I) has a boiling point of 125
° C / 6 mmHg. The structure of this silane compound is G
C-MS, ¹ H-NMR, infrared absorption spectrum (I
R) and the like.

For example, when the compound (I) is analyzed by using ¹ H-NMR, it is found that a carbon atom directly bonded to an oxygen atom among cyclopentyl groups and cyclopentyloxy groups at δ = 1.1 to 1.9. The signal of the hydrogen atom based on the portion excluding was observed . Further, a signal of a methoxy group at δ = 3.47 and a signal of a hydrogen atom bonded to a carbon atom directly bonded to an oxygen atom among cyclopentyloxy groups at δ = 4.40 were observed.

From the analysis by IR spectrum,
A large absorption based on SiOC bonding was observed around 1100 cm ^-1 .

When this silane compound (I) is used as a catalyst component, olefin polymers such as polypropylene and polybutene having high stereoregularity 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.

[0012] The present invention provides a process for the production of the novel silane compound represented by the formula (I). That is, the silane compound of the above formula (I) is produced by reacting cyclopentyl trihalosilane with cyclopentyl alcohol and then reacting the obtained reaction product with methanol. The starting material cyclopentyltrihalosilane has the following formula (II) :

[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, 0.9 to 1.1 mol of trihalosilane is used per 1 mol of cyclopentene. The reaction conditions are, for example, a temperature of 100 to 200 ° C. for 10 minutes to 10 hours, and a platinum-based catalyst such as chloroplatinic acid, platinum-1,1,1
It is preferable to use a 3,3-tetramethyl-1,3-divinyldisiloxane complex or the like. Further, a solvent can be used, and examples thereof include benzene and toluene.

According to the invention, the cyclopentyltrihalosilane (II) thus obtained is reacted with cyclopentyl alcohol:

[0016]

Embedded image When performing this reaction, 1 to 3 mol of cyclopentyl alcohol is used per 1 mol of cyclopentyl trihalosilane (II). The reaction is, for example, 20 to 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 make the reaction proceed rapidly, 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 up to 1.5 mol.

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

[0019]

Embedded image In this reaction, methanol is used in an amount of 2 to 3 mol per 1 mol of the compound (III). Reaction is 0-100 ° 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 hydrogen halide acceptors exemplified in Reaction B above can be used. The hydrogen halide acceptor used here may be the same or different from the compound used in the previous reaction, but usually the same is used. The hydrogen halide acceptor is preferably used in an amount of 2 to 3 mol based on 1 mol of the compound (III).

In the above-described reactions B and C, the generated hydrogen halide can be removed from the reaction system by blowing an inert gas to allow the reaction to proceed rapidly.

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 cyclopentyl alcohol to an alcohol exchange reaction:

[0023]

Embedded image In the above reaction formula, 1 to 20 mol of cyclopentyl alcohol is used per 1 mol of compound (IV). The reaction is performed, for example, at a temperature of 0 to 100 ° C. for 10 minutes to 2 hours.
Perform for 0 hours. In the case of this alkoxyl group exchange reaction,
Catalysts include acids, such as trifluoroborane-ether complexes and toluenesulfonic acid, or those that react with alcohols to produce acids, such as trimethylchlorosilane; or bases, such as 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.

[0025]

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

[0026]

Embodiment 1Cyclopentyloxycyclopentyl dime
Production of Toxisilane (1)  13.9 g of cyclopentene in a 100 ml pressure vessel
(0.204 mol), 25.1 g of trichlorosilane
(0.185 mol) and 0.077 mmol / ml
25 μl of chloroplatinic acid in isopropyl alcohol (white
Gold content 1.92 × 10^-6Mol) at 150 ° C
By stirring for 30 minutes, cyclopentyl trichloro
Rosilane was obtained 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 previously obtained were placed.
Where 49.3 g (0.623 mol) of pyridine and 19.1 g (0.1%) of cyclopentyl alcohol were added.
(222 mol) was added dropwise over 30 minutes at room temperature with stirring.

After heating under reflux for 2 hours, 18.4 g (0.574 mol) of methanol was added thereto, and the reflux was continued for further 1 hour to terminate the reaction.

The salt formed was removed by filtration, and then hexane was distilled off, followed by distillation under reduced pressure to obtain 31.0 g (0.127 mol) of a liquid having a boiling point of 125 ° C./6 mmHg. GC-MS confirmed that this product was cyclopentyloxycyclopentyldimethoxysilane.
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 69%.

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

[0031]¹ H-NMR  Measuring device: HITACHI R-24B (Hitachi, Ltd.)
Manufacturing Co., Ltd.), Measurement solvent: CCl₄, Standard substance: CHCl
₃, Tetramethylsilane (TMS)IR  Measuring device: 1600 series FT-IR (Perkin-L)
Measurement method: liquid film method (KBr plate) In addition, GC-MS is HP 5970B (Hewlett
 (Packard) and the measurement results are as follows
M / e (spectral intensity ratio): 177
(7), 176 (11), 175 (67), 147 (5
8), 131 (11), 109 (22), 107 (10
0), 91 (21), 77 (23), 67 (12).

[0032]

Embodiment 2Cyclopentyloxycyclopentyl dime
Production of Toxisilane (2)  50 ml 3-neck with magnetic stir bar and reflux condenser
In the flask, add cyclopentyltrimethoxysilane 5.0
g (0.0262 mol), cyclopentyl alcohol 2
2.5 g (0.262 mol) and sodium methoxy
18.6 mg (0.34 mmol) were added at room temperature.
The mixture was reacted by stirring for 2 hours. Then trimethylchloro
Neutralize the alkali by adding silane, then
By vacuum distillation, cyclopentyloxycyclo
5.4 g of pentyl dimethoxysilane (0.0223
Le). The structure was confirmed in the same manner as in Example 1.
The yield was 85%.

[0033]

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

[Brief description of the drawings]

FIGS. 1 and 2 are ¹ H-NMR and IR charts of the cyclopentyloxycyclopentyldimethoxysilane produced in Example 1, respectively.

Continuation of front page (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Pref. JP-A-4-175310 (JP, A) JP-A-6-184215 (JP, A) JP-A-5-310825 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7 / 18 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) cyclopentyltrihalosilane is
Reaction with pentyl alcohol, then the resulting reaction
Reacting the product with methanol, characterized by the following formula (I): A method for producing a silane compound represented by the formula: 2. A cyclopentenone trimethoxysilane and shea <br/> black top by alcohol exchange reaction of pentyl alcohol
Introducing a cyclopentyloxy group into the silane compound.
The following formula (I) characterized by the following: A method for producing a silane compound represented by the formula: