JPH09104690A - Organosilicon compound having cyclic ether group and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new compound useful for providing a hydrophilic silicone polymer such as a hydrophilic silicone oil, a varnish and a rubber and producible in high yield. SOLUTION: This compound is represented by formula I (R<1> and R<2> are each a 1-6C alkyl), e.g. [3- (1,4-dioxan-2-yl) methoxy}propyl]methyldimethoxysilane. The compound is obtained by reacting a methyldialkoxysilane represented by formula II with a 2-allyloxymethyl-1,4- dioxane represented by formula III in the presence of an addition reactional catalyst (preferably a platinum-based or a rhodium-based catalyst), preferably without a solvent. The reactional temperature is preferably 20-150 deg.C and the reactional time is preferably 2-6hr. The compound represented by formula II is obtained from, e.g. methyldichlorosilane and an alcohol. The compound represented by formula III is preferably prepared by reacting ethylene chlorohydrin with allyl glycidyl ether in the presence of a stannic chloride catalyst and an SiO-containing compound and then intramolecularly cyclizing the resultant compound in the presence of the SiO-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel organosilicon compound having a cyclic ether group (1,4-dioxanyl group), which is useful as a raw material for hydrophilic silicone oil, varnish, rubber and the like, and a method for producing the same. More specifically, it relates to [3-{(1,4-dioxan-2-yl) methoxy} propyl] methyldialkoxysilane represented by the following general formula (1) and a method for producing the same.

[0002]

Embedded image (In the formula, R ¹ and R ² are the same or different from each other and have 1 to 6 carbon atoms.
Represents an alkyl group. )

[0003]

2. Description of the Related Art
In the molecule, hydrophilic silicone with ether group
On ≡SiCH_TwoCH_TwoCH_TwoO (C_TwoH_FourO) _a(C_ThreeH₆O)
_bR (however, R = H, -CH_Three, -C_FourH₉Or -COCH
_Three, A, b = an integer of 1 to 1000)
Known foam stabilizers with an ether group.
Is used as (Reference: Kunio Ito, "Silicone"
Handbook ", Nikkan Kogyo Shimbun, 179 pages, 199.
0 years) is a cyclic ether group, especially 1,4-dioxanyl
Organosilicon compounds having groups have not been reported.

[0004]

Means for Solving the Problems and Embodiments of the Invention In view of the need for hydrophilic silicone oils, silicone varnishes and silicone rubbers in the art, the present inventors have proposed hydrophilic silicones. As a result of diligent research on a novel organosilicon compound which gives a compound, S of methyldialkoxysilane represented by the following general formula (2)
An iH group and a -CH = CH ₂ group of ₂ -allyloxymethyl-1,4-dioxane represented by the following formula (3) are platinum-based,
By carrying out an addition reaction in the presence of an addition reaction catalyst such as a rhodium-based compound, a novel organosilicon compound represented by the following general formula (1), namely [3-{(1,4-dioxane-2-
It has been found that (yl) methoxy} propyl] methyldialkoxysilane is usually obtained in a high yield of 85% or more. When the dialkoxysilane having the 1,4-dioxanyl group of the formula (1) is hydrolyzed and then polymerized, the characteristic of the 1,4-dioxanyl group is exerted, and the hydrophilic silicone oil or silicone The present invention has been completed by finding that varnish and silicone rubber can be manufactured.

[0005]

Embedded image (However, in the formula, R ¹ and R ² are the same or different from each other and have 1 carbon atoms.
To 6 alkyl groups. )

Therefore, the present invention provides an organosilicon compound having a cyclic ether represented by the general formula (1), a methyldialkoxysilane having an alkoxy group having 1 to 6 carbon atoms, and 2-allyloxymethyl-1. And 4-dioxane are subjected to an addition reaction in the presence of an addition reaction catalyst.

The present invention will be described in more detail below. The cyclic ether group-containing silicon compound according to the present invention is represented by the following general formula (1).

[0008]

Embedded image (In the formula, R ¹ and R ² are the same or different from each other and have 1 to 6 carbon atoms.
Represents an alkyl group. )

Here, R ¹ and R ² may have a carbon number of 7 or more, but as a use, since they are used as silicone oils, varnishes and rubbers in the form of polysiloxane, lower alkyls are required. It may be a group, and a specific example thereof is a linear or branched alkyl group having 6 or less carbon atoms as shown below.

[0010]

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The silicon compound having a cyclic ether represented by the formula (1) of the present invention can be obtained by the route represented by the following formula, that is, methyldichlorosilane and 2-allyloxymethyl-1,4-dioxane are used as a platinum group compound. Alternatively, after the addition reaction in the presence of a rhodium-based catalyst, it can be obtained by reacting the obtained cyclic ether group-containing dichlorosilane with an alcohol having 6 or less carbon atoms. It is unstable in air.

[0012]

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On the other hand, instead of methyldichlorosilane, methyldialkoxysilane represented by the following general formula (2) was used as a starting material, and 2-allyloxymethyl-1,4-of the formula (3) was used. By carrying out the addition reaction with dioxane in the presence of an addition reaction catalyst, preferably a platinum-based or rhodium-based catalyst, [3-{(1,4
-Dioxan-2-yl) methoxy} propyl] methyl dialkoxysilane can be produced in high yield.
The methyldialkoxysilane represented by the general formula (2) can be obtained by a known method, for example, by reacting methyldichlorosilane and alcohol.

[0014]

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Here, in the reaction of the above reaction formula A, the reaction molar ratio of the methyldialkoxysilane of the formula (2) and the 2-allyloxymethyl-1,4-dioxane of the formula (3) is usually 1: 1. However, the molar ratio in consideration of economic efficiency is preferably 1 to 1 to 2.

The addition reaction catalyst used in this reaction is
As described above, platinum-based catalysts and rhodium-based catalysts are preferable, but platinum-based catalysts that can be used include elemental platinum, chloroplatinic acid, alcohol-treated chloroplatinic acid alcohol products, platinum cyclopropane complexes, platinum ethylene complexes, and the like. is there. On the other hand, rhodium-based catalysts that can be used are rhodium chloride, a triphenylphosphorus complex of rhodium chloride, or a complex of tetrabutylammonium hydride and rhodium chloride. The amount of catalyst used is 1 of the weight of methyl dialkoxy silane used.
~ 10,000 ppm, but a suitable amount is 10-1,
000 ppm.

In this reaction, an aromatic solvent such as toluene or xylene, an aliphatic solvent such as n-heptane or n-hexane, or tetrahydrofuran, dioxane,
Although it may be carried out in the presence of an ether solvent such as diethyl ether, it is preferably carried out without a solvent because the pot yield (kettle yield) is reduced.

The reaction is usually carried out under normal pressure, but it may be carried out under pressure. The reaction temperature is usually 10 to 200 ° C, but a suitable range is 20 to 150 ° C. Usual reaction time is 0.5 to 10 hours, but a suitable range is 2 to 6 hours.

Here, the 2-allyloxymethyl-1,4-dioxane (3) used as the starting material of the present invention can be obtained by a conventionally known method, and particularly ethylene chlorohydrin and allyl glycidyl ether are used. The second chloride
After reacting by contacting in the presence of a tin catalyst, an intramolecular cyclization reaction is caused using a dehydrochlorination agent to produce 2-allyloxymethyl-1,4-dioxane. At the time of the reaction between chlorohydrin and allyl glycidyl ether and the above-mentioned intramolecular cyclization reaction, it is preferable to coexist a silicon compound having at least one SiO bond in the molecule, thereby suppressing the formation of a by-product polymer, 2-Aryloxymethyl-1,4-dioxane can be obtained in high yield.

[0020]

Embedded image

The organosilicon compound represented by the formula (1) of the present invention is particularly useful as a raw material for a siloxane polymer as described above. The organosilicon compound of the present invention has two alkoxy groups in one molecule, can be converted into siloxane by hydrolysis, and is effectively used as a raw material for a siloxane polymer. The polymer having the unit of the following formula (a) obtained by hydrolyzing the organosilicon compound of the formula (1) of the present invention has hydrophobicity-(SiMe ₂ O).
-It has very different surface characteristics from dimethylpolysiloxane having units (Me: methyl group), whereas the latter polymer treated on the glass surface has a contact angle to water of 99 degrees (100Å film). The former, ie the polymer according to the invention, had a contact angle to water of 56 degrees (98).
0Å film thickness). This indicates that the polymer derived from the organosilicon compound of the present invention is easily compatible with water and is useful as a hydrophilic polymer.

[0022]

Embedded image

[0023]

INDUSTRIAL APPLICABILITY The novel organosilicon compound of the present invention is useful for obtaining a hydrophilic silicone polymer, and the production method of the present invention can produce such an organosilicon compound in high yield.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 250.0 g (2.354 mol) of methyldimethoxysilane and chloroplatinic acid hexahydrate were placed in a 1000 ml round bottom flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel. .0041g was added and stirred.
To this mixture, 372.5 g (2.355 mol) of 2-allyloxymethyl-1,4-dioxane was added dropwise at 30 ° C. over 3 hours. After the dropping was completed, stirring was continued at 35 ° C. for 2 hours. After the reaction was completed, the product was distilled under reduced pressure to obtain 550.3 g of a colorless transparent liquid material (yield 88.4).
%).

The measurement results of boiling point, refractive index, viscosity, GC-MS spectrum, ¹ H-NMR and infrared absorption spectrum of the obtained liquid are as follows. That is, [3-{(1,4
-Dioxan-2-yl) methoxy} propyl] methyldimethoxysilane.

Boiling point: 125 ° C./4 mmHg Refractive index (n ²⁵ _D ): 1.4414 Viscosity (cs, 25 ° C.): 6.5 GC-MS analysis: (m / e) M ⁺ 264

[0028]

Embedded image IR analysis: An IR chart is shown in FIG.

Example 2 200.0 g (1.490 mol) of methyldiethoxysilane and chloroplatinic acid hexahydrate were placed in a 1000 ml round bottom flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel. 0.0041 g was added and stirred.
2-Aryloxy-1,4-dioxane 2 was added to this mixture.
36.0 g (1.492 mol) was added dropwise at 35 ° C. over 2.5 hours. After the dropping was completed, stirring was continued at 40 ° C. for 2 hours. After the reaction was completed, distillation was performed under reduced pressure to obtain 371.8 g of a colorless transparent liquid material (yield 85.3).
%).

The measurement results of the boiling point, the refractive index, the viscosity, the GC-MS spectrum, the ¹ H-NMR and the infrared absorption spectrum of the obtained liquid are as follows. That is, [3-{(1,4
-Dioxan-2-yl) methoxy} propyl] methyldiethoxysilane.

Boiling point: 139 ° C./4 mmHg Refractive index (n ²⁵ _D ): 1.4390 Viscosity (cs, 25 ° C.): 5.8 GC-MS analysis: (m / e) M ⁺ 292

[0032]

Embedded image IR analysis: IR chart is shown in FIG.

Example 3 The reaction was carried out under the same conditions as in Example 1, except that the chloroplatinic acid hexahydrate used as the catalyst was replaced with 0.0105 g of the rhodium catalyst of the following formula: The desired [3-{(1,4-dioxane-
2-yl) methoxy} propyl] methyldimethoxysilane was obtained with a yield of 88.2%.

[0034]

Embedded image

Example 4 The reaction was carried out under the same conditions as in Example 2, except that the chloroplatinic acid hexahydrate used as the catalyst was replaced with 0.0111 g of the rhodium catalyst of the following formula: The desired [3-{(1,4-dioxane-
2-yl) methoxy} propyl] methyldiethoxysilane was obtained with a yield of 86.2%.

[0036]

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Example 5 In Example 1, H (CH ₃ ) Si (OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C was used instead of methyldimethoxysilane of the SiH group-containing dialkoxysilane.
When the reaction was carried out under the same conditions except that 513.5 g (2.354 mol) of H ₃ ) ₂ was used, the target compound of the following formula was obtained in a yield of 88.1%.

[0038]

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[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the target compound of Example 1.

FIG. 2 is an infrared absorption spectrum of the target compound of Example 2.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minoru Igarashi, Izumi Arashi, Matsuida-cho, Usui-gun, Gunma 1-10 Hitomi, Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Masaharu Takahashi Matsuida-cho, Usui-gun, Gunma Hitomi 1 No. 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Takashi Hirai 1096 Toda, Atsugi City, Kanagawa Prefecture Nakatomi 201 (72) Tadashi Banno 26 Takamura, Hiratsuka City, Kanagawa Prefecture 38 Takamura housing complex −101 (72) Inventor Masayuki Umeno 521-3 Chigasaki, Chigasaki City, Kanagawa Prefecture

Claims (2)

[Claims] 1. An organosilicon compound having a cyclic ether group represented by the following general formula (1). Embedded image (However, in the formula, R ¹ and R ² are the same or different from each other and have 1 carbon atoms.
To 6 alkyl groups. ) 2. A methyldialkoxysilane having an alkoxy group having 1 to 6 carbon atoms and 2-allyloxymethyl-1,
The method for producing an organosilicon compound according to claim 1, wherein 4-dioxane is subjected to an addition reaction in the presence of an addition reaction catalyst.