JP2862365B2 - Novel silane compound and method for producing the same - Google Patents

Description

Description: 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 novel silane compound. It relates to a manufacturing method.

(Problems to be Solved by Conventional Techniques and Inventions) It has been known that, when performing propylene polymerization, 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.

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

Accordingly, 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.

(Means for Solving the Problems) The present invention firstly provides the following formula (I): (Wherein, R represents a tert-butyl group or an isopropyl group), that is, tert-butoxy-
It provides 2-cyclopentenyldimethoxysilane or isopropoxy-2-cyclopentenyldimethoxysilane.

This silane compound (I) had a boiling point of 78 ° C./3.7 mmHg when R = tert-butyl group, and 80 ° C./7 mmHg when R = isopropyl group. The structure of this silane compound is represented by GC-MS, ¹ H-NMR, infrared absorption spectrum (IR)
And so on.

For example, when the compound (I) is analyzed using ¹ H-NMR, when R is a tert-butyl group, a tert-butoxy group at δ1.32, a cyclopentenyl group at δ1.7 to 2.6 and 5.71, A signal based on a methoxy group was observed at δ3.55. When R is an isopropyl group, δ 1.62, 1.
Signals based on isopropoxy group at 27 and 3.9 to 4.6, cyclopentenyl group at δ 1.7 to 2.6 and 5.73, and methoxy group at δ 3.57 were observed.

In addition, according to the analysis by the IR spectrum, in all the compounds, a large absorption based on the SiOC bond was observed around 1100 cm ⁻¹ .

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

The present invention secondly provides a method for producing a novel silane compound represented by the above formula (I). That is, the silane compound of the above formula (I) is produced by reacting 2-cyclopentenyltrihalosilane with ROH (R is as defined above) and then reacting the obtained reaction product with methanol. The starting material 2-cyclopentenyltrihalosilane has the following formula: (X represents a halogen atom, preferably a is Cl or Br) is represented by, from cyclopentadiene and trihalosilane (H-SiX _3), can be easily prepared by a hydrosilylation reaction: At this time, 0.9 to 1.1 mol of trihalosilane is used per 1 mol of cyclopentadiene. The reaction conditions are, for example,
The temperature is 100 to 200 ° C. for 10 minutes to 10 hours, and it is preferable to use a palladium-based catalyst such as tetrakistriphenylphosphine palladium or a phosphine complex derived from bis (benzonitrile) dichloropalladium and triphenylphosphine. Further, a solvent can be used, and examples thereof include benzene and toluene.

According to the invention, the 2-cyclopentenyltrihalosilane (II) thus obtained is reacted with ROH, ie tert-butyl alcohol or isopropyl alcohol: In carrying out this reaction, ROH is used in an amount of 1 to 3 mol per 1 mol of 2-cyclopentenyltrihalosilane (II). The reaction is carried out, for example, at a temperature of 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, it is preferable to coexist a dehydrohalogenating agent in order to promptly progress the reaction. Examples of the dehydrohalogenating agent include tertiary amines and nitrogen-containing heterocyclic compounds such as pyridine, quinoline, and isoquinoline. Among them, pyridine and quinoline are preferably used. The dehydrohalogenating agent is preferably used in an amount of 1 to 1.5 mol per 1 mol of 2-cyclopentenyltrihalosilane.

Next, 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.

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. Is preferably coexisted. As the dehydrohalogenating agent, the reaction B
The dehydrohalogenating agents exemplified in (1) can be used. The dehydrohalogenating agent used here may be the same or different from the compound used in the previous reaction, but usually the same one is used. The dehydrohalogenating agent is preferably used in an amount of 2 to 3 mol based on 1 mol of the compound (III).

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

According to the above-mentioned production method, the 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, 2-cyclopentenyltrimethoxysilane and
This is a method for producing a compound of the formula (I) by subjecting ROH (R is as defined above) to an alcohol exchange reaction: In the above reaction formula, 1 mol of compound (IV) is
Use 1 to 2 moles of ROH. The reaction is carried out, for example, at a temperature of 50 to 100 ° C for 2 to 20 hours. In this alcohol exchange reaction, an acid such as trifluoroborane-ether complex, toluenesulfonic acid; or a base such as alkali metal alkoxides and metal hydroxides can be used as a catalyst.

Further, 2-cyclopentenyltrimethoxysilane (IV) as a starting material can be produced by a dehydrochlorination reaction between 2-cyclopentenyltrichlorosilane and methanol.

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

Example 1 Production of tert-butoxy-2-cyclopentenyldimethoxysilane In a 500 ml pressure vessel, 13.2 g of cyclopentadiene (0.20 g) was added.
0 mol), 28.4 g (0.210 mol) of trichlorosilane and 0.05 g of tetrakistriphenylphosphine palladium
(Palladium content 4.3 × 10 ^-5 mol)
By stirring for an hour, 2-cyclopentenyltrichlorosilane was obtained quantitatively.

500ml with magnetic stir bar, cooling tube and dropping funnel
Was charged with 250 ml of 2-cyclopentenyltrichlorosilane and hexane obtained above, and a mixture of 49.8 g (0.630 mol) of pyridine and 17.8 g (0.240 mol) of tert-butyl alcohol was added at room temperature. The mixture was added dropwise over 30 minutes with stirring.

After heating under reflux for 2 hours, 14.4 g of methanol (0.4%
49 mol), and the mixture was further refluxed for 1 hour, and the reaction was terminated.

The resulting salt was removed by filtration, and then hexane was distilled off.
36.9 g (0.160 mol) of Hg liquid were obtained. This product is tert
-Butoxy-2-cyclopentenyldimethoxysilane was confirmed by GC-MS, ¹ H-NMR and IR. ¹ H-NMR and IR measurement results are shown in FIGS. 1 and 2, respectively. The yield was 80%.

In addition, ¹ H-NMR and IR were measured under the following conditions. ¹ H-NMR measurement device: HITACHI R-1500 (manufactured by Hitachi, Ltd.)
Measurement solvent: CDCl ₃ , Standard substance: TMS (tetramethylsilane) IR measurement device: IR-810 (manufactured by JASCO Corporation) Measurement method: liquid film method (KBr plate) In addition, GC-MS is HP 5970B (Hewlett-Packard), and the measurement results were as follows: m
/ e (spectral intensity ratio): 230 (0.4), 215 (3), 173
(5), 163 (6), 133 (5), 107 (100), 91 (1
7), 77 (25), 67 (16), 59 (14) Example 2 Preparation of tert-butoxy-2-cyclopentenyldimethoxysilane In a 100 ml three-necked flask equipped with a magnetic stirrer and a condenser, 2 was added. -Cyclopentenyltrimethoxysilane 25.0
g (0.133 mol), 9.86 g of tert-butyl alcohol (0.133
Mol) and 20 mg (0.18 mmol) of potassium tert-butoxy. After cooling, the alkali is neutralized by adding ammonium chloride and then distilled under reduced pressure to obtain te.
rt-butoxy 2-cyclopentenyldimethoxysilane 6.
13 g (0.0266 mol) were obtained. The structure was confirmed in the same manner as in Example 1. Yield was 20%.

Example 3 Preparation of isopropoxy-2-cyclopentenyldimethoxysilane 500 ml equipped with magnetic stirrer, condenser and dropping funnel
Prepared in the same manner as in Example 1
40.3 g (0.200 mol) of cyclopentenyltrichlorosilane and 300 ml of hexane are charged, and pyridine 5
3.8 g (0.680 mol) and 13.2 g of isopropyl alcohol
(0.220 mol) was added dropwise over 30 minutes at room temperature with stirring. After further stirring for 30 minutes, 14.1 g (0.440 mol) of methanol was added thereto, and stirring was continued for another 30 minutes, and then the reaction was terminated.

The resulting salt was removed by filtration, then hexane was distilled off, and the residue was distilled under reduced pressure, so that the boiling point was 80 ° C / 7 mmHg.
35.0 g (0.162 mol) of a liquid were obtained. The product was confirmed to be isopropoxy-2-cyclopentenyldimethoxysilane by GC-MS, ¹ H-NMR and IR. The measurement results of ¹ H-NMR and IR are shown in FIGS. 3 and 4, respectively. The yield was 81%.

The results of GC-MS were as follows: m / e (spectral intensity ratio): 216 (4), 201 (4), 149 (41), 13
5 (3), 107 (100), 91 (15), 77 (32), 67
(7), 59 (11) Example 4 Production of isopropoxy-2-cyclopentenyldimethoxysilane In the same apparatus as in Example 2, 25.0 g (0.133 mol) of 2-cyclopentenyltrimethoxysilane, 7.99 g of isopropyl alcohol ( 0.133 mol) and 20 mg (0.18 mmol) of potassium tert-butoxide were treated in the same manner as in Example 2 to obtain 4.89 g (0.0226 mol) of isopropoxy-2-cyclopentenyldimethoxysilane. The structure was confirmed in the same manner as in Example 3. The yield was 17%.

(Effect of the Invention) According to the present invention, a novel silane compound useful as a polymerization catalyst component such as an olefin, a silane coupling agent, and the like, and a method for producing the same can be obtained.

[Brief description of the drawings]

FIGS. 1 and 2 show the te produced in Example 1, respectively.
FIGS. 3A and 3B are ¹ H-NMR and IR charts of rt-butoxy-2-cyclopentenyldimethoxysilane, and FIGS. 3 and 4 respectively show the isopropoxy-2-cyclopentenyldimethoxysilane prepared in Example 3. ¹ is a chart of ¹ H-NMR and IR.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Rinko Aoki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Institute (72) Inventor Yoshiharu Okumura Nishi-Tsuruga, Oi-machi, Iruma-gun, Saitama 1-3-1 Oka, Tonen Co., Ltd. Research Institute (56) References JP-A-2-270888 (JP, A) Organometall chem. , 149 (1978), 29-36 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] 1. The following formula (I): (Wherein, R represents a tert-butyl group or an isopropyl group). 2. The method according to claim 2, wherein the 2-cyclopentenyltrihalosilane is RO
H (R is as defined in claim 1);
The method for producing a silane compound according to claim 1, wherein the obtained reaction product is reacted with methanol. 3. The method according to claim 2, wherein the reaction is carried out in the presence of a dehydrohalogenating agent. 4. The method for producing a silane compound according to claim 1, wherein 2-cyclopentenyltrimethoxysilane and ROH (R is as defined in claim 1) are subjected to an alcohol exchange reaction.