JP2903487B2 - Cyclopentadienyl group-containing silane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a modifier for various synthetic resins, especially ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EPM), and also has various functional groups. The present invention relates to a cyclopentadienyl group-containing silane compound which is a novel substance useful as a raw material for synthesizing a silane compound, and a method for producing the same.

[0002]

2. Description of the Related Art Among various synthetic resins, ethylene-propylene-diene copolymer (EPD) of olefin rubber is used.
M) and ethylene-propylene copolymer (EPM) are very excellent in heat resistance, weather resistance and ozone resistance as compared with diene rubber. Therefore, especially automotive parts and industrial products,
For example, ethylene-propylene-diene copolymer (EP) is used for tires, belts, weather strips, various sealing materials, tubes, hoses, gaskets, electric wires, and the like.
DM) and ethylene-propylene copolymer (EPM) are suitably used, and in recent years, their demand has been greatly increased.

[0003] However, ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EPM) are required to further improve heat resistance, weather resistance, cold resistance and oil resistance as a subject of future technical development. Has been requested. As a modifier for further improving the physical properties,
Cyclopentadienyl group-containing silane compounds are known, and ethylene-propylene-diene copolymer (EPD)
M) or an ethylene-propylene copolymer (EPM), the copolymer may be blended with the compound, or the compound may be mixed with ethylene and propylene as a third component diene monomer for crosslinking. For example, a means of copolymerizing with the polymer is used.

Conventionally, cyclopentadienyl group-containing silane compounds used for the above-mentioned applications include cyclopentadienyl group-containing alkoxysilanes and ω-cyclopentadienyl described in JP-A-61-47493. Alkyl-containing alkoxysilanes, and J. Org.Chem., 25, 1986-90 (196
0), the following silane compounds (a), (b) and (c) are known,

[0005]

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[0006] These compounds are not sufficiently compatible with the resin, and have a difficulty in blending with the resin. Further, the modification of the flexibility of the resin with the compound was not at a satisfactory level. Accordingly, there has been a demand for a novel cyclopentadienyl group-containing silane compound that can solve the above-mentioned problems.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is intended to provide various synthetic resins, particularly ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer (EPM). It is an object of the present invention to provide a cyclopentadienyl group-containing silane compound which is useful as a modifier for a silane compound and also useful as a raw material for synthesizing a silane compound having various functional groups, and a simple production method thereof.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to meet the above-mentioned demand, and as a result, the chemical formula (2)

[0009]

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A halogen-containing silane compound represented by the formula:
By reacting sodium cyclopentadienyl under anhydrous conditions in a neutral polar organic solvent, the chemical formula (1)

[0011]

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A cyclopentadienyl group-containing silane compound represented by the formula [X in the above formulas (1) and (2) is a halogen atom, R2, R3 and R4 are the same or different and have 1 to 4 carbon atoms. An alkyl group or a phenyl group, m is an integer of 0 to 3] is reliably and easily obtained, and the cyclopentadienyl group or ω
A compound of the formula (1) in which three triorganosilyloxy groups are bonded to a silicon atom to which a cyclopentadienylalkyl group is bonded solves the above problem, and various synthetic resins, particularly ethylene-propylene- Diene copolymer (E
PDM) and ethylene-propylene copolymer (EPM) modifiers, which can be used more effectively. In addition, this compound can be added to the cyclopentadienyl group contained in the molecule by another Diels-Alder reaction. Can be introduced as a raw material for synthesizing a novel silane compound having various functional groups, and the present invention has been completed.

The novel substance of the present invention has the chemical formula (1)

[0014]

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A cyclopentadienyl group-containing silane compound represented by the formula (R2, R3 and R4 are the same or different and are each an alkyl or phenyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 3). .

The cyclopentadienyl group-containing silane compound is selected from R1, R2 and R3 in view of the availability of raw materials.
And those in which R4 is a methyl group, for example, the following can be exemplified.

[0017]

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The method for producing the cyclopentadienyl group-containing silane compound represented by the chemical formula (1) is as follows. Chemical formula (2),

[0019]

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(X is a halogen atom, R2, R3 and R4
Are the same or different and are an alkyl group or phenyl group having 1 to 4 carbon atoms, m is an integer of 0 to 3), and cyclopentadienyl sodium under anhydrous conditions. After reacting in a neutral polar organic solvent, water is added for washing.

The reaction between the halogen-containing silane compound of the formula (2) and sodium cyclopentadienyl is a desalination reaction represented by the following formula (3). This reaction is carried out by dropping a halogen-containing silane compound into a solution of cyclopentadienyl sodium synthesized by reacting sodium metal and cyclopentadiene monomer in a neutral polar organic solvent with stirring. Done.

[0022]

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R1, R2, R3 and R4 of the halogen-containing silane compound represented by the chemical formula (2) may be a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an aryl group such as a phenyl group. Preferred, particularly industrially, is a methyl group. Further, the halogen atom X in the chemical formula (2) is preferably, for example, a chlorine atom, a bromine atom, an iodine atom and the like. The chemical formula (2)
Examples of the halogen-containing silane compound include the following.

ClSi (OSi (CH ₃ ) ₃ ) ₃ , ClCH ₂ Si (OSi (CH ₃ ) ₃ ) ₃ ClCH ₂ CH ₂ CH ₂ Si (OSi (CH ₃ ) ₃ ) ₃ , ISi (OSi (CH ₃ ) ₃ ) ₃ ) ₃ , ICH ₂ Si
(OSi (CH ₃ ) ₃ ) ₃ ICH ₂ CH ₂ CH ₂ Si (OSi (CH ₃ ) ₃ ) ₃ , ClSi (CH ₃ ) (OSi (CH ₃ ) ₃ ) ₂ ClCH ₂ Si (CH ₃ ) (OSi ( _{CH 3) 3) 2, ClCH} 2 CH 2 CH 2 Si (CH 3) (OSi (C
H ₃ ) ₃ ) ₂ ISi (CH ₃ ) (OSi (CH ₃ ) ₃ ) ₂ , ICH ₂ Si (CH ₃ ) (OSi (CH ₃ ) ₃ ) ₂ ICH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OSi (CH ₃ ) ₃ ) _{2 As the} neutral polar organic solvent used in the reaction of the production method, for example, ether solvents such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and ethylene glycol dimethyl ether are preferable. . Further, a mixed solvent of the ether solvent and a saturated hydrocarbon solvent or an aromatic solvent may be used. Examples of the saturated hydrocarbon solvent include n-pentane, n-hexane, n-heptane, isooctane, and cyclohexane. Examples of the aromatic solvent include benzene, toluene, xylene, and mesitylene. Among the neutral polar organic solvents, tetrahydrofuran is particularly preferable because it can be removed by washing with water, and is inexpensive and easy to handle.

Since the reaction in the above production method is carried out under anhydrous conditions, the reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium or argon. When the reaction is carried out in the presence of water, side reactions such as loss due to hydrolysis of sodium cyclopentadienyl and hydrolysis and condensation of chlorosilanes occur, and the yield decreases.

After the completion of the reaction in the above-mentioned production method, sodium halide and some unreacted cyclopentadienyl sodium produced by the reaction shown in the chemical reaction formula (3) are removed by washing with water, and then the solvent is washed with water or distilled. After removal, the product cyclopentadienyl group-containing silane compound is finally isolated and purified, for example, by distillation under reduced pressure.

In the reaction of the above-mentioned production method, various conditions may be set as follows. The amounts of the halogen-containing silane compound and cyclopentadienyl sodium, which are the raw materials, are sufficient because the reaction proceeds almost quantitatively as shown by the chemical reaction formula (3).

The reaction temperature may be set as follows. When the halogen-containing silane compound is dropped, the temperature is usually from -50C to the boiling point of the solvent, preferably from 0C to room temperature. After the completion of the dropwise addition until the completion of the reaction, usually -5
0 ° C. to the boiling point of the solvent, preferably 0 ° C. to the boiling point of the solvent.

The reaction time can be freely selected usually in the range of 1 to 80 hours. Since the reaction proceeds sufficiently at atmospheric pressure, the reaction may be carried out usually at normal pressure, and may be carried out under pressure if necessary.

When m = 1 to 3 in the halogen-containing silane compound represented by the chemical formula (2), the reaction time with cyclopentadienyl sodium represented by the chemical reaction formula (3) is as follows when X = chlorine atom. Requires several days to complete the reaction, and may take several hours when X = iodine. Therefore, in order to obtain a high-yield target product in a short time, an iodine-substituted halogen-containing silane compound is preferably used. m
A method for producing an iodine-substituted halogen-containing silane compound having an average of 1 to 3 is as follows. By reacting the corresponding chlorine-substituted halogen-containing silane compound and sodium iodide in a ketone-based solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone at the reflux temperature of the solvent, the iodine-substituted halogen-containing silane compound can be easily produced. Can be obtained quantitatively.

[0031]

The action of the compound of the present invention in the application of a novel functional silane compound to a raw material for synthesis is as follows.

The cyclopentadienyl group possessed by the cyclopentadienyl group-containing silane compound of the present invention has a compound in which at least one electron-withdrawing group is bonded to a carbon atom of a double bond (dienophile). ) Can be easily added by the Diels-Alder reaction.
Therefore, the cyclopentadienyl group-containing silane compound represented by the chemical formula (1) of the present invention can be a novel functional silane compound synthesis raw material. Examples of the dienophile that can be added to the cyclopentadienyl group by the Diels-Alder reaction include thiophene, benzoquinone, acrylic acid, methacrylic acid, maleic anhydride, and acrylonitrile. By adding the dienophile, a novel functional silane compound having each functional property can be obtained.

[0033]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1 Synthesis of γ-cyclopentadienylpropyltris (trimethylsilyloxy) silane 500 m equipped with a thermometer, a stirrer, and a Dimroth condenser
The interior of the four-necked glass reactor is sufficiently replaced with nitrogen in advance. Thereafter, 108.5 g (containing 0.23 mol of cyclopentadienyl sodium) of a 2.0 mol / l tetrahydrofuran (THF) solution of sodium cyclopentadienyl was added to the reactor, and the mixture was stirred under water-cooled stirring. While maintaining the temperature range of 28 ° C., γ-iodopropyltris (trimethylsilyloxy) silane 108.3.
g (0.22 mol) was added dropwise over 2 hours. Heat generation occurred with the dropping, and at the same time, a large amount of red bean-colored fine crystals precipitated. Next, after stirring was further continued at room temperature for 1 hour, the internal composition was measured by GC (gas chromatography). As a result, the raw material γ-iodopropyltris (trimethylsilyloxy) silane was completely consumed. Next, 100 ml of water was added to the solution to crush unreacted sodium cyclopentadienyl, and then washed with water until the aqueous layer became neutral. Next, T
After distilling out HF, distillation under reduced pressure is performed at 94 to 97 ° C / 1m.
57.9 g of a compound having a boiling point of mHg were obtained. Mass spectrum (MS), nuclear magnetic resonance spectrum of this compound
( ¹ HNMR) and infrared absorption spectrum (IR) were measured, and the following results were obtained, thereby confirming that the target substance was γ-cyclopentadienylpropyltris (trimethylsilyloxy) silane. The yield was 65%.

Measurement results Mass spectrum (MS): m / z (spectral intensity ratio, assignment) 402 (38, M ⁺ ), 387 (72, M-CH ₃ ), 295 (100, Si (OSi (C
H ₃ ) ₃ ) ₃ ⁺ ), 279 (24), 265 (14), 249 (6), 233 (4), 208 (98), 193 (56), 179 (1
2), 165 (66), 137 (26), 121 (8), 106 (12), 91 (12), 73 (98, Si (CH 3) 3 +), 59 (40),
45 (14) ・ Nuclear magnetic resonance spectrum ( ¹ HNMR): δ (ppm)

[0036]

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A: 0.10 (27H, s) b: 0.28 to 0.63 (2H, m) c: 1.20 to 1.85 (2H, m) d: 2.10 to 2.55 (2H, m) e: 2.68 to 3.00 (1H, m ) f: 5.77-6.45 (4H, m) ・ Infrared absorption spectrum (IR) :( cm ^-1 ) 3050,2950,2900,1450,1415,1370,1347,1256,1185,1060
(SiOSi), 840, 757,715,680 Example 2 Cyclopentadienyl tris (trimethylsilyloxy)
Synthesis of silane 500m equipped with thermometer, stirrer, Dimroth condenser
The inside of a 1-neck four-neck glass reactor was sufficiently purged with nitrogen in advance. Thereafter, 132.5 g (containing 0.28 mol of cyclopentadienyl sodium) of a 2.0 mol / l solution of cyclopentadienyl sodium in tetrahydrofuran (THF) was added to the reactor, and the mixture was stirred under water-cooled stirring. While maintaining the temperature range of 25 ° C., 92.7 g of chlorotris (trimethylsilyloxy) silane (0.2
8 mol) was added dropwise over 3.3 hours. Heat generation occurred along with the dropping, and at the same time, red bean-colored fine crystal components precipitated. Next, the temperature of the solution was raised and aged at 74 ° C. for 24 hours under reflux of THF. Then, 100 ml of water was added to crush unreacted sodium cyclopentadienyl, and the solution was washed once more with water. Then, the mixture was dehydrated with sodium sulfate, THF was distilled off from this solution by an evaporator, and the mixture was distilled under reduced pressure to obtain a compound having a boiling point of 68 to 70 ° C / 1.5 mmHg. When the mass spectrum (MS), nuclear magnetic resonance spectrum ( ¹ HNMR), and infrared absorption spectrum (IR) of this compound were measured, the following results were obtained, and the desired product, cyclopentadienyl tris (trimethylsilyloxy), was obtained. It was confirmed to be silane. The measurement results are shown below.

Measurement results Mass spectrum (MS): m / z (spectral intensity ratio, assignment) 360 (5, M ⁺ ), 345 (5, M-CH ₃ ), 295 (24, Si (OSi (CH ₃ ) ₃ ) ₃ ⁺ ), 2
57 (8), 241 (4), 207 (100), 191 (5), 123 (55), 95 (5), 73 (70), 59 (5), 4
5 (5), ・ Nuclear magnetic resonance spectrum ( ¹ HNMR): δ (ppm)

[0039]

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A: 0.10 (27H, s) b: 2.90-3.15 (1H, m) c: 6.20-7.00 (4H, m) Infrared absorption spectrum (IR) :( cm ^-1 ) 3060,2955,2890 , 1500,1460,1420,1380,1350,1256,1070
(SiOSi), 955,841,759,700

[0041]

As described in detail above, the cyclopentadienyl group-containing silane compound of the present invention can be used for various synthetic resins, especially ethylene-propylene-diene copolymer (EPDM) and ethylene-propylene copolymer. (EP
It is useful as a modifier of M). Furthermore, the compound of the present invention can be used as a raw material for synthesizing novel various functional silane compounds, since a different kind of functional group can be introduced into the cyclopentadienyl group contained in the molecule by a Diels-Alder reaction. Further, according to the production method of the present invention, a novel cyclopentadienyl group-containing silane compound can be produced reliably in a simple process by using easily available raw materials.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mikio Endo 28-1, Nishifukushima, Oku-ku, Nikushiro-mura, Nakakushiro-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd., Synthetic Technology Research Institute (72) Inventor Toru Kubota, Nakatsugi-gun, Niigata No. 28, Nishifukushima, Kushiro-mura, Japan Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (56) References JP-A-61-47493 (JP, A) US Patent 2957901 (US, A) Chemical Abstracts, 95 (1981) ), 204042 Chemical Abstracts, 96 (1982), 219057 Chemical Abstracts, 89 (1978), 24430 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 CA (STN) REGISTRY (STN) ) WPIDS (STN) BEILSTEIN (STN)

Claims (4)

(57) [Claims] 1. A compound of the general formula (1) (R2, R3 and R4 are the same or different and are each an alkyl group or phenyl group having 1 to 4 carbon atoms;
(An integer of 3) a cyclopentadienyl group-containing silane compound. 2. The cyclopentadienyl group-containing silane compound according to claim 1, wherein R2, R3 and R4 are methyl groups. 3. A compound of the general formula (2) Wherein a halogen-containing silane compound represented by the following formula is reacted with cyclopentadienyl sodium in a neutral polar organic solvent under anhydrous conditions, followed by adding water and washing, wherein the general formula (1) Embedded image [X in the above formulas (1) and (2) is a halogen atom, and R2, R3 and R4 are the same or different from each other and have 1 to 4 carbon atoms. An alkyl group or a phenyl group, m is 0
An integer from 3 to 3]. 4. The process for producing a cyclopentadienyl group-containing silane compound according to claim 3, wherein R2, R3 and R4 are methyl groups.