JP2002012597A - Organic silicon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic silicon compound active to perform hydrosilylation reaction with a compound having vinyl group, useful as a crosslinking agent and giving a hydrosilylated derivative resistant to decomposition under acidic or alkaline condition because of the lack of a siloxane-type Si-O-Si bond. SOLUTION: The organic silicon compound is expressed by general formula 1 [(a) and (b) are each 0 or 1; Z is H, R, M or Q-Rf when one of (a) and (b) is 0 and Z is Q, Rf' or Q-Rf'-Q when both of (a) and (b) are 1; R is a univalent hydrocarbon group; M is a group of general formula 2 ((m) is an integer of 1-4; R is same as defined above); Q is a bivalent hydrocarbon group; Rf is a univalent perfluoroalkyl or perfluoroxyalkyl; Rf' is a bivalent perfluoroalkylene or perfluoroxyalkylene; (s) is an integer of 1-3; and (t) is an integer of 0-3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel organosilicon compound which is effective as a crosslinking agent for an addition reaction.

[0002]

2. Description of the Related Art An addition-curable rubber composition generally comprises a base polymer having an alkenyl group such as a vinyl group and a hydrogen atom directly bonded to a silicon atom (ie, a SiH group). And an addition reaction catalyst such as a platinum-based catalyst, wherein the SiH group is added to the alkenyl group of the base polymer to cure.

For example, known organic silicon compounds having a SiH group include the following. That is, as shown by the following formula, S having a fluoroalkyl substituent
It has a structure in which a SiH group is bonded to an i atom via an oxygen atom (Japanese Patent Application Laid-Open No. 3-197484).

[0004]

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This compound can undergo a hydrosilylation reaction with another substance having a vinyl group, and is useful as a raw material for synthesizing various derivatives. For example, it can be used as a raw material for a modifier, a crosslinking agent for a resin or rubber, a surfactant or an additive.

However, since this compound has a siloxane type Si—O—Si bond in the molecule, the siloxane bond can be cleaved under severe conditions such as exposure to a high temperature in the presence of an acid or an alkaline substance. There was a problem that it easily occurred.

The present invention has been made in view of the above circumstances, and has a SiH group that can undergo a hydrosilylation reaction with a compound having a vinyl group and that the derivative after hydrosilylation is hardly decomposed under acidic or alkaline conditions. An object is to provide an organosilicon compound.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an alkylene group or the like is substituted for an oxygen atom in a Si-O-Si bond. By introducing the compound, a hydrosilylation reaction with a compound having a vinyl group can be carried out, and it has been found that an organosilicon compound in which a derivative after the hydrosilylation reaction is hardly decomposed under acidic or alkaline conditions can be obtained, and the present invention is achieved. Reached.

Hereinafter, the present invention will be described in more detail.
The organosilicon compound of the present invention is represented by the following general formula (1).

[0010]

Embedded image Wherein a and b are 0 or 1, but a and b are not 0 at the same time. When either a or b is 0, Z
Is a hydrogen atom, -R, -M or -Q-Rf;
Is 1 when Z is -Q-, -Rf'- or -Q-
Rf'-Q- is shown. R is the same or different and has 1 to 6 carbon atoms.
Is a monovalent hydrocarbon group, M is the following formula (2)

Embedded image (Where m is an integer of 1 to 4, R is the same as described above), Q is a divalent hydrocarbon group having 1 to 15 carbon atoms which may contain an ether bond, and Rf is a monovalent par A fluoroalkyl group or a perfluorooxyalkyl group, Rf ′ is 2
A perfluoroalkylene group or a perfluorooxyalkylene group. s is 1, 2, or 3, t is 0, 1,
2 or 3. ]

Here, when either a or b is 0, Z is a monovalent group, and represents a hydrogen atom, -R, -M or-.
Z represents a divalent group when both a and b are 1, and -Q-, -Rf'- or -Q-Rf'-Q
Indicates-.

R may be the same or different,
Shows a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, alkyl group such as hexyl group, vinyl group, alkenyl group such as allyl group, phenyl group and the like. And a methyl group and a phenyl group are particularly preferable.

M is a monovalent group represented by the following formula (2). In the formula (2), R is the same as described above;
m is an integer of 1 to 4.

[0014]

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Q is a divalent hydrocarbon group having 1 to 15, preferably 1 to 12, and more preferably 1 to 10, carbon atoms which may contain an ether bond (-O-).
Methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, phenylene group, tolylene group, xylylene group, naphthylene group,
Examples include an arylene group such as a biphenylene group, and a group to which these groups are bonded. Another example of Q is a divalent group containing an oxygen atom in the main chain structure. In this case, an oxygen atom can be interposed as —O—.

Rf is a monovalent perfluoroalkyl group or a perfluorooxyalkyl group, and Rf 'is a divalent perfluoroalkylene group or a perfluorooxyalkylene group. In this case, as the, C _g F _{2g +} 1 1 monovalent perfluoroalkyl group - (g 1 to 20, preferably an integer of 2 to 10) as is preferably, a divalent perfluoroalkylene group, -C _g F _2g - _(g 1 to 20, preferably an integer of 2 to 10) preferably.

The monovalent perfluorooxyalkyl group has 1 to 500 carbon atoms, more preferably 1 to 500 carbon atoms.
00, more preferably 1 to 200. Preferred examples include the following.

[0018]

Embedded image (H is an integer of 1 to 5)

Further, the divalent perfluorooxyalkylene group may have 1 to 500 carbon atoms, more preferably 1 to 500 carbon atoms.
It is preferably 300, more preferably 1 to 200, and preferably the following.

[0020]

Embedded image (I + j is 2 to 100 _{integer) - (CF 2 O) e} - (CF 2 CF 2 O) f -CF 2 - (e, an integer of f are each 1 to 50)

Preferred examples of the organosilicon compound include those represented by the following general formulas (3) and (4).

[0022]

Embedded image (Where R 'is a lower alkyl group or a phenyl group, k is 1
And integers of p to 8, p and q are 1, 2 or 3. )

[0023]

Embedded image (However, R, Rf, and Q are the same as above, and n is 1 to 4
And x is an integer of 1 to 3. )

Hereinafter, the organosilicon compounds of the present invention will be exemplified, but these are representative examples, and the organosilicon compounds of the present invention are not limited thereto. In the following, a methyl group is abbreviated as Me, and a phenyl group is abbreviated as Ph.

[0025]

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[0026]

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[0027]

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The organosilicon compound of the formula (1) of the present invention is
When a and b are each 1, for example, it can be synthesized by adding monochlorosilane of the following general formula (6) to a polyfunctional vinyl compound represented by the following general formula (5) and then reducing.

[0029]

Embedded image (However, R, Z, s, and t are the same as above.)

In this case, to obtain the compound of the formula (3), a polyfunctional vinyl compound of the following formula (5a) and a monochlorosilane of the following formula (6a) can be used.

[0031]

Embedded image (However, R 'and k, p, and q are the same as above.)

For example, a reaction scheme using a polyfunctional vinyl compound of the formula (5a) wherein p and q are 3 is as follows.

[0033]

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Here, the addition reaction using the above-mentioned Pt compound can be performed by a known method and conditions. In the above reduction reaction, LiAlH ₄ or the like can be used as a reducing agent, and this reduction reaction can also be performed by a known method and conditions.

On the other hand, in the case of obtaining an organosilicon compound in which one of a and b in formula (1) is 0 (a =
1, when b = 0), for example, a compound of the following general formula (7) is used.

[0036]

Embedded image (However, R, Z, and s are the same as above.)

When a compound of the formula (4) is specifically obtained, it can be synthesized according to the following scheme using a compound of the following general formula (7a).

[0038]

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In the general formula (4), when n = 1,
An organosilicon compound can be produced by preparing a Grignard reagent of chloromethyldimethylsilane and reacting it with the chlorosilane of the formula (7a). The Grignard reagent is prepared by reacting magnesium and chloromethyldimethylsilane in tetrahydrofuran (THF). Thereafter, the Grignard reagent and chlorosilane are reacted. At this time, the chlorosilane is preferably used in an amount of 0.70 to 0.95 equivalent of the Grignard reagent.

As the chlorosilane of the formula (7a), for example, those having the following structures can be suitably used.

[0041]

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The reaction between the chlorosilane of the formula (7a) and the Grignard reagent of chloromethyldimethylsilane is carried out in 30 to
It is good to perform at 70 ° C. for about 1 to 20 hours. After the reaction,
The reaction mixture is poured into dilute hydrochloric acid to dissolve the magnesium salt, and the organic phase containing the target substance is separated from the aqueous phase. At this time, it is preferable to use an excess amount of hydrochloric acid so as to keep the aqueous phase acidic. By distilling the separated organic phase, the organosilicon compound of the formula (4) of the present invention can be isolated.

When n = 2, a vinyl Grignard reagent such as CH ₂ is added to the corresponding chlorosilane of the formula (7a).
After reacting ビ ニ ル CHMgCl or CH ₂ ＣＨCHMgBr to introduce a vinyl group, chlorodimethylsilane is added and further reduced to produce an organosilicon compound.

The reaction between the chlorosilane of the formula (7a) and the vinyl Grignard reagent can be carried out by adding chlorosilane to a THF solution of the prepared vinyl Grignard reagent. At this time, the amount of the chlorosilane of the formula (7a) is preferably 0.80 to 0.95 equivalent of the Grignard reagent. Also in this case, the chlorosilane exemplified above can be suitably used. The reaction between the chlorosilane of the formula (7a) and the vinyl Grignard reagent is preferably performed at 30 to 70 ° C. for about 10 minutes to 2 hours. After completion of the reaction, the reaction mixture is poured into dilute hydrochloric acid to dissolve the magnesium salt, and the organic phase containing the target substance is separated from the aqueous phase. The intermediate (a) into which the target vinyl group has been introduced can be obtained by distilling the separated organic phase.

Next, chlorodimethylsilane is added to the intermediate (a) to obtain an intermediate (b). This reaction can be carried out by adding chlorodimethylsilane to a mixture of the intermediate (a) and the chloroplatinic acid catalyst. This reaction may be performed at 50 to 80 ° C. for about 10 minutes to 2 hours.

At this time, the reaction can be carried out using a solvent. As the solvent, hexane, toluene, xylene,
Butyl ether, THF, bistrifluoromethylbenzene and the like are preferred.

The obtained intermediate (b) is reduced to obtain the organosilicon compound of the present invention. In this case, the reducing agent is L
iAlH ₄ is preferred. This reaction is based on the T of LiAlH ₄ .
This is performed by dropping the intermediate (b) into the HF solution. At this time, the dropping speed is preferably adjusted so that the temperature of the reaction mixture is 20 to 50 ° C. After completion of the dropwise addition, the organic mixture containing the target substance is taken out by pouring the reaction mixture into dilute hydrochloric acid, and the organic phase is distilled to obtain the organosilicon compound of the present invention.

The organosilicon compound of the present invention can be used for various purposes, such as a crosslinking agent and an intermediate for modification.

[0049]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 In a 1,000 ml four-necked flask equipped with a stirrer, a thermometer, a Dim funnel and a dropping funnel, 98.4 g of bis (trivinylsilyl) ethane (0.4 g) was added.
4 mol) and a toluene solution of divinyltetramethyldisiloxane complex of chloroplatinic acid (Pt equivalent concentration: 0.5 wt.
%) And heated to 90 ° C. while stirring. Then, 249.5 g of dimethylchlorosilane (2.
(64 mol) was dropped from the dropping funnel over 90 to 100 ° C / 2 hours, followed by aging at 90 to 100 ° C / 3 hours. After cooling, distillation under reduced pressure gave a boiling point of 240 to 250.
286 g of a fraction having a temperature of 2.5 ° C / 2.5 × 10 ^-4 Torr was obtained. When this fraction was analyzed by ¹ H-NMR, it was confirmed to be the following compound. ¹ H-NMR analysis result (TMS standard, ppm) δ 0.05 (≡Si-CH ₃ : 18H) δ 0.35 (≡Si-CH _2- : 14H)

[0051]

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Next, 150 g of toluene and 30.1 g (0.79 mol) of LiAlH ₄ were charged into a 1,000 ml four-necked flask equipped with a stirrer, thermometer, Dim funnel and dropping funnel, and 300 g of THF was stirred. After dropping from the dropping funnel, 286 g of the fraction obtained above (0.
35 mol) and 500 g of toluene were dropped from a dropping funnel. After aging at <30 ° C. for 2 hours, 80 g of ethyl acetate was added dropwise from a dropping funnel. Then, the reaction product was added to 3 L of 1N hydrochloric acid, washed with water, and only the upper layer was taken out by liquid separation. After distillation under reduced pressure, a fraction 1 having a boiling point of 186 to 189 ° C./2.5×10 ⁻⁴ Torr 1
87.3 g (yield: 87.8%) were obtained. The result of analyzing this fraction by ¹ H-NMR and IR is shown below. ¹ H-NMR analysis result (TMS standard, ppm) δ0.05 (≡Si-CH ₃ : 18H) δ0.35 (≡Si-CH _2- : 14H) δ3.70 (≡Si-H: 3H) Infrared Absorption spectrum (FIG. 1) 2,109 cm ^-1 @ Si-H The equivalent weight of the functional group of this compound was determined to be 9.9.
It was 4 × 10 ⁻³ mol / g, and it was confirmed that the obtained compound was an organosilicon compound represented by the following structural formula.

[0053]

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Example 2 9.3 g of magnesium powder,
120 ml of THF and a small amount of iodine were heated with stirring to reflux THF. When the brown color of iodine completely disappeared, chloromethyldimethylsilane.
0 g was gradually added dropwise. When the temperature of the reaction mixture during dropping is 5
The dropping speed was adjusted so as to be 0 to 60 ° C. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 1 hour. Then, n
The _{-C 8 F 17 CH 2 CH 2} SiCl 3 50.8g 50~60
The mixture was added dropwise at 20 ° C over 20 minutes. After completion of the dropwise addition, stirring was continued at 65 ° C. for about 15 hours. The reaction mixture was poured into a 2N-hydrochloric acid aqueous solution, and the organic phase was taken out and washed with water.
Distillation was performed to obtain a product represented by the following formula. Boiling point 140 ° C./1 mmHg, yield 43.9 g, yield 72
% FIG. 2 shows the IR spectrum of the product.

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Example 3 2 mol CH ₂ ＣＨCHMgB
A THF solution containing r was prepared. N-C ₈ F
349 g of ₁₇ CH ₂ CH ₂ SiCl _{3 was} added dropwise at 30 to 50 ° C. After dropping, stirring was continued for about 2 hours. The reaction mixture was poured into a 1N aqueous hydrochloric acid solution, the organic phase was taken out, washed with water, and distilled to obtain an intermediate (1) having the following structure. Boiling point: 130 ° C./20 mmHg, yield: 270 g, yield: 81
%

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250 g of the intermediate (1) obtained above, 150 g of toluene and a butanol solution of chloroplatinic acid (Pt
0.2 g of the mixture was heated to 70 ° C.
140 g of chlorodimethylsilane was added dropwise with stirring. During the addition, the addition speed was adjusted so that the temperature of the reaction mixture was 70 to 100 ° C. After the completion of the dropwise addition, the mixture was allowed to stand for about 1 hour, and the reaction mixture was distilled as it was to obtain an intermediate (2) having the following structure. Boiling point 193 ° C / 1mmHg, yield 362g, yield 96%

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13.6 g of LiAlH _{4 was} added to 250 g of THF.
Is prepared, and 250 g of the intermediate (2) is added thereto.
And a mixture of 250 g of toluene were dropped. The reactor was cooled so that the temperature of the reaction mixture during the dropping became 20 to 30 ° C., and the dropping rate was adjusted. Stirring was continued for about 1 hour after the completion of the dropping. The reaction mixture is then
It was put into an N-hydrochloric acid aqueous solution. The organic phase was separated, washed with water and distilled to obtain a product having the following structure. Boiling point: 162 ° C./1 mmHg, yield: 114 g, yield: 52% FIG. 3 shows the IR spectrum of the product.

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Example 4 Magnesium Powder 16.5
g, 200 ml of THF and a small amount of iodine were heated with stirring to reflux THF. When the brown color of iodine has completely disappeared, chloromethyldimethylsilane 7
0.0 g was gradually added dropwise. The dropping speed was adjusted so that the temperature of the reaction mixture during the dropping became 50 to 60 ° C. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 1 hour. Next, a mixture of 22.3 g of Cl ₃ SiCH ₂ CH ₂ SiCl _{3 and} 22.3 g of toluene was added dropwise at 50 to 60 ° C. over 20 minutes. After completion of the dropwise addition, stirring was continued at 62 ° C. for about 24 hours. The reaction mixture was mixed with a 2N aqueous hydrochloric acid solution (500 ml).
And the salt was dissolved. The organic phase is further washed with 500 ml of a 1N aqueous hydrochloric acid solution and the organic phase 63
g was collected. Analysis of this solution by GC-MS confirmed that it contained 23% of a product having the following structure. M ⁺ = 522.

[0059]

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Example 5 Magnesium powder 20.8
g, 300 ml of THF and a small amount of iodine were heated with stirring to reflux THF. When the brown color of iodine has completely disappeared, chloromethyldimethylsilane 8
9.2 g was gradually added dropwise. The dropping speed was adjusted so that the temperature of the reaction mixture during the dropping became 50 to 60 ° C. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 1 hour and 30 minutes.
Then, a compound represented by the following formula

Embedded image A mixture of 100.0 g and 65 g of toluene is heated at 28 to 60 ° C.
For 30 minutes. After the completion of the dropwise addition, stirring was continued at 65 ° C. for about 2 hours to complete the reaction. Next, the reaction mixture was poured into a 2N-hydrochloric acid aqueous solution, the organic phase was taken out, washed with water, and distilled to obtain a product having the following structure.

[0061]

Embedded image Boiling point 205-217 ° C / 1 mmHg, yield 94.4 g,
Yield 75% FIG. 4 shows the IR spectrum of the product.

[0062]

The organosilicon compound of the present invention can undergo a hydrosilylation reaction with a compound having a vinyl group,
Useful as an intermediate. In addition, since this compound does not have a siloxane-type Si-O-Si bond, the derivative after hydrosilylation is characterized in that it is not easily decomposed under acidic or alkaline conditions.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a product in Example 1 of the present invention.

FIG. 2 is an IR spectrum of a product in Example 2 of the present invention.

FIG. 3 is an IR spectrum of a product in Example 3 of the present invention.

FIG. 4 is an IR spectrum of a product in Example 5 of the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yasunori Sakano 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term in the Silicon Electronics Research Laboratory, Shin-Etsu Chemical Co., Ltd. 4H049 VN01 VP04 VP06 VP08 VQ02 VQ11 VQ77 VR11 VR23 VR24 VU17 VW02

Claims (3)

[Claims] 1. An organosilicon compound represented by the following general formula (1). Embedded image Wherein a and b are 0 or 1, but a and b are not 0 at the same time. When either a or b is 0, Z
Is a hydrogen atom, -R, -M or -Q-Rf;
Is 1 when Z is -Q-, -Rf'- or -Q-
Rf'-Q- is shown. R is the same or different and has 1 to 6 carbon atoms.
And M is a monovalent hydrocarbon group represented by the following formula (2): (Where m is an integer of 1 to 4, R is the same as described above), Q is a divalent hydrocarbon group having 1 to 15 carbon atoms which may contain an ether bond, and Rf is a monovalent par A fluoroalkyl group or a perfluorooxyalkyl group, Rf ′ is 2
A perfluoroalkylene group or a perfluorooxyalkylene group. s is 1, 2, or 3, t is 0, 1,
2 or 3. ] 2. The following general formula (3): (Where R 'is a lower alkyl group or a phenyl group, k is 1
And integers of p to 8, p and q are 1, 2 or 3. 2. The organosilicon compound according to claim 1, wherein 3. The following general formula (4): (However, R, Rf, and Q are the same as above, and n is 1 to 4
And x is an integer of 1 to 3. 2. The organosilicon compound according to claim 1, wherein