JPH06248084A - Organic silicon compound containing ethynyl group - Google Patents

Abstract

(57) [Summary] [Objective] An ethynyl group-containing organosilicon compound which is relatively easy to obtain and is useful as a platinum catalyst inhibitor in hydrosilylation or as an intermediate in the synthesis of pharmaceuticals and agricultural chemicals, and as a novel silicone material. I will provide a. [Structure] General formula (1) (Wherein R represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and m represents a number of 0, 1, or 2) in the molecule. An ethynyl group-containing organosilicon compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ethynyl group-containing organosilicon compound and an ethynyl group-modified siloxane polymer.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION AND ITS PROBLEMS Conventionally, 1,1,3,3-tetramethyl-1,3-dietinyldisiloxane has been known as an ethynyl group-containing organosilicon compound, and the siloxane bond It is useful as a molecular chain terminating agent and is widely used as a molecular weight regulator during the synthesis of silicone oil, silicone rubber, silicone varnish and the like. The ethynyl group in the siloxane is ≡Si in the presence of a catalyst such as an organic peroxide or a transition metal compound.
It reacts with H-containing compounds to form a ≡SiCH = CH-Si≡ structure, so it is applied to the modification of silicone oil, the crosslinking of silicone rubber, the curing of silicone varnish, and the like. It is also a platinum catalyst inhibitor or ethynyl in hydrosilylation. Since the group has biological activity, it is widely used as an intermediate for medicines, agricultural chemicals and the like. 1,1,3,3-tetramethyl-
As a method for synthesizing 1,3-diethynyldisiloxane, a method in which sodium acetylide or ethynylmagnesium bromide is partially reacted with dimethyldichlorosilane to hydrolyze is known. However, this method has a drawback that the yield of ethynyldimethylchlorosilane produced as an intermediate is very low, and thus there remains a problem as a method for industrially obtaining an ethynyl group-containing organosilicon compound.

[0003]

OBJECTS OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to be relatively easy to obtain, and to be useful as a platinum catalyst inhibitor in hydrosilylation or as an intermediate for the synthesis of pharmaceuticals and agricultural chemicals. An object is to provide an ethynyl group-containing organosilicon compound useful as a silicone material.

[0004]

The present inventor has conducted extensive studies to achieve such an object. As a result, for example, diethynyldimethylsilane and dialkylchlorosilane are reacted in the presence of a platinum catalyst to further hydrolyze the reaction product. It was found that the novel ethynyl group-containing organosilicon compound thus obtained meets this purpose and is useful for introducing an ethynyl group into siloxane and can also provide a new silicone material, thereby completing the present invention. Came to. That is, the present invention, the general formula (1)

[0005]

[Chemical 3]

(In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, m represents a number of 0, 1, 2) in the molecule. An organosilicon compound containing an ethynyl group. By using the ethynyl group-containing organosilicon compound of the present invention, it is possible to easily introduce an ethynyl group into a siloxane polymer. The ethynyl group-containing organosilicon compound of the present invention can be synthesized from sodium acetylide as a raw material by the following method. That is, a suspension of sodium acetylide in xylene and a mineral oil is added dropwise to a dialkyldichlorosilane under cooling conditions to produce a diethynyldialkylsilane, which is then purified by distillation. An ethynyl group-containing organosilicon compound can be obtained by reacting this compound with a silane compound having a SiH group and a hydrolyzable group in the presence of a platinum catalyst and further hydrolyzing the silane compound. More specifically, a suspension of sodium acetylide xylene and mineral oil is cooled to about 0 ° C. or lower, to which dialkyldichlorosilane is added dropwise. After the dropping is completed, the temperature is raised to about 5 ° C. and the mixture is stirred for several hours to produce diethynyldialkylsilane. The produced diethynyldialkylsilane is separated and purified by distillation. The molar ratio of dialkyldichlorosilane and sodium acetylide is preferably about 1 to 2 times that of dialkyldichlorosilane with respect to sodium acetylide in order to completely eliminate sodium acetylide in terms of post-treatment of the reaction. Further, since heat is generated during the reaction, it is desirable to cool the reaction and keep the reaction temperature at 0 ° C or lower. This is because the ethynyl group is decomposed when the reaction temperature is 40 ° C or higher. There is a possibility that unreacted dialkyldichlorosilane is mixed in the diethynyldialkylsilane obtained by distillation, but it can be easily removed by adding city water. Another method for synthesizing diethynyldialkylsilane is by the Grignard synthesis method using ethynylmagnesium bromide instead of sodium acetylide. The difference from the case of sodium acetylide is the treatment with mineral acid after the reaction of ethynylmagnesium bromide and dialkyldichlorosilane. Isolated by distillation after treatment with mineral acid. As the dialkyldichlorosilane, dimethyldichlorosilane is preferable because it is easily available.

The diethynyldialkylsilane obtained as above is further treated with one SiH group and
A silane compound having a hydrolyzable group bonded to a Si atom or a chlorine atom (hereinafter simply referred to as "silane compound") is reacted in the presence of a platinum catalyst. Examples of such silane compounds include chlorosilanes such as dimethylchlorosilane, methyldichlorosilane, trichlorosilane, diethylchlorosilane, ethyldichlorosilane, diphenylchlorosilane, and phenyldichlorosilane, and alkoxys such as methyldimethoxysilane, dimethylmethoxysilane, and trimethoxysilane. Examples include silanes. In order to selectively react only one of the ethynyl groups, it is preferable to add a silane compound having one SiH group in one molecule to the diethynyldialkylsilane. The molar ratio of the diethynyldialkylsilane and the silane compound is preferably dropped. It is necessary to add 1 to 2 times the amount of diethynyldialkylsilane to the silane compound. It is preferably 1 to 1.2 times. This is because if it is less than 1-fold, two ethynyl groups may co-react, and even if it is added in excess of 2-fold, a large amount of unreacted diethynyldialkylsilane remains, which is uneconomical.
Although the reaction is exothermic, it is preferable to control the dropping rate to about 40 ° C. or lower in order to avoid side reactions. The platinum catalyst used may be one generally used for hydrosilylation reaction. In particular,
Lamoreau's catalyst (platinum-octanol complex, US Patent No.
4743377), Ashibi's catalyst (platinum-vinyl tetramer complex, U.S. Pat. No. 4,288,345) and Karlstedt's catalyst (platinum-vinyl dimer complex, U.S. Pat.
No. 0) is exemplified. The reaction produces a compound in which the diethynyldialkylsilane and a portion of the silane compound other than the SiH group and the two ethynyl groups react with each other. Therefore, by distillation, the hydrolyzable bond of the 2- (ethynyldialkylsilyl) ethenyl group and the Si atom A silane compound having a group or a chlorine atom (hereinafter simply referred to as "ethynyl group-containing silane compound") is isolated.

The ethynyl group-containing silane compound thus obtained is hydrolyzed or cohydrolyzed alone or together with other hydrolyzable silane compounds to obtain the ethynyl group-containing organosilicon compound of the present invention. Examples of the other hydrolyzable silane compounds include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, organochlorosilanes such as triphenylchlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, and the like. Examples of the alkoxysilanes such as ethyl silicate and organoalkoxysilanes known to those skilled in the art, which are called silane coupling agents, can be easily obtained as a commercial product. The hydrolysis method can be achieved by a general method known to those skilled in the art. That is, the ethynyl group-containing silane compound is hydrolyzed or co-hydrolyzed alone or with a hydrolyzable silane compound under acidic conditions to give a linear, cyclic or branched siloxane, that is, ethynyl of the present invention. It is possible to obtain group-containing organosilicon compounds. If the hydrolyzable group such as an alkoxy group is difficult to hydrolyze, the reaction easily proceeds by using a mineral acid such as hydrochloric acid. For example, the [2- (ethynyldialkylsilyl) ethenyl] tetraalkyldisiloxane of the present invention (hereinafter referred to as "dimer") can be obtained by hydrolyzing the ethynyl group-containing silane compound alone. This dimer can also be synthesized by reacting the obtained diethynyldialkylsilane with 1,1,3,3-tetramethyldisiloxane in the presence of a platinum catalyst. The dimer can be used as it is as a hydrosilylation reaction inhibitor, and if it is used as a molecular chain end terminating agent, an ethynyl-modified polymer of siloxane can be synthesized. The ethynyl-modified siloxane polymer is synthesized according to the usual siloxane polymer synthesis method. For example, isolated bis [2-
(Ethynyldialkylsilyl) ethenyl] tetraalkyldisiloxane (dimer) and octamethylcyclotetrasiloxane are polymerized in the presence of an alkali catalyst. As the alkali catalyst, cesium hydroxide, rubidium hydroxide, potassium hydroxide, sodium hydroxide and lithium hydroxide which are generally used for polymerizing siloxane polymers are used. The polymerization conditions depend on the respective catalyst characteristics. Further, after neutralization with an inorganic acid such as phosphoric acid or an organic acid such as ethylene chlorohydrin, an ethynyl group-containing polymer is obtained by stripping and filtration. It is also possible to further increase the molecular weight of the obtained cohydrolyzate, octamethylcyclotetrasiloxane and the like in the presence of an alkali catalyst. The method for increasing the molecular weight may also follow the usual siloxane polymer synthesis method.

[0009]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. Example 1 Synthesis of diethynyldimethylsilane 100 m equipped with cooling tube, dropping funnel, thermometer and stirrer
28.6g of dimethyldichlorosilane in a 3-neck flask of l
(0.22 mol) was charged, and the entire flask was cooled to -10 ° C with an ethylene glycol-dry ice bath. While vigorously stirring the content, a 18 wt% suspension of sodium acetylide in xylene-mineral oil was added dropwise over 30 minutes. After completion of dropping, the flask was stirred for 3 hours while being cooled to 5 ° C with ice water. From the reaction mixture, 41 g of a xylene solution of diethynyldimethylsilane and unreacted dimethyldichlorosilane was distilled off (70 ° C to 135 ° C). Furthermore, in order to remove unreacted dimethyldichlorosilane, city water
50 g was dropped and left for 1 hour. After separating the organic layer and the aqueous layer, the organic layer was left to dry with anhydrous sodium sulfate for one day. . Sodium sulfate is removed by filtration and distilled (73
10.8g (purity)
99%, yield 91%). Synthesis of 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane 10.0 g (93 mmol) of diethynyldimethylsilane and 0.06 g of Karstedt's platinum catalyst (platinum content 1.8% by weight) were used as a cooling tube, stirrer, thermometer and dropping funnel. It was charged into a 50 ml three-necked flask equipped with. To this, 7.3 g (77.5 mmol) of dimethylchlorosilane was added dropwise over 30 minutes. At this time, the temperature rises, so cool the entire container with ice water.
It was controlled to be below ℃. After the completion of dropping, the mixture was stirred at room temperature for 1 hour and distilled under reduced pressure (37-42 ° C / 3 mmHg) to give 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane.
The yield was 9.4 g (purity 93%, yield 60%). Bis [2- (ethynyldimethylsilyl) ethenyl]
Synthesis of tetramethyldisiloxane 9.0 g (44.4 mmol) of 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane was dissolved in 9.0 g of THF, and this solution was added with 50 ml of a condenser, a stirrer, a thermometer and a dropping funnel. A 3-neck flask was charged. To this solution, 10 g of city water was added, stirred for 10 minutes, and then separated. Anhydrous sodium sulfate was added to the organic layer, the mixture was allowed to stand for 1 day, filtered, and distilled to obtain 7.6 g of bis [2- (ethynyldimethylsilyl) ethenyl] tetramethyldisiloxane (purity).
90%, yield 98%) was obtained. The IR chart of this product is shown in Fig. 1, and the ¹ H-NMR chart is shown in Fig. 2.
Shown in. The refractive index (25 ° C) was 1.46.

Example 2 5 g (14.3 mm) of bis [2- (ethynyldimethylsilyl) ethenyl] tetramethyldisiloxane obtained in Example 1
ol) and octamethylcyclotetrasiloxane 21g (70.9
mmol) was charged into a three-necked flask equipped with a 50 ml condenser, a stirrer, a thermometer and a dropping funnel. Potassium hydroxide
0.0010 g was further added and the mixture was heated with stirring at 150 ° C. for 8 hours. Then, the temperature was cooled to 90 ° C., 1.0 g of ethylene chlorohydrin was added as a neutralizing agent, and the mixture was stirred for 3 hours.
Then, decompress the produced polymer under the condition of 3 mmHg,
The low fraction was removed by heating to 0 ° C. The amount of the polymer obtained was 15 g. Viscosity is 40 cP, weight average molecular weight is 17
The nonvolatile content (150 ° C x 30 minutes) of 00 was 95%. From the gas chromatography of the obtained product, the raw material disiloxane was completely disappeared. From ¹ H-NMR measurement, 2.
A proton ratio of 27 ppm ethynyl protons and 0.12 ppm SiMe was calculated. As a result, the obtained polymer was 2-
(Ethynyldimethylsilyl) A polymer having about 20 dimethylsiloxy repeating units blocked with an ethenyldimethylsilyl group. The refractive index (25 ° C) was 1.46.

Example 3 9.4 g (4.70 mmol) of 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane obtained in Example 1, 20 g (155.0 mmol) of dimethyldichlorosilane and 10 parts of toluene.
0 ml was charged to a 500 ml round bottom flask equipped with a water cooled condenser, dropping funnel, thermometer and stirrer. To this solution, 100 g of city water was added dropwise over 1 hour with vigorous stirring. Immediately after the completion of the dropping, liquid separation and water washing were carried out, followed by drying with anhydrous sodium sulfate. Further, sodium sulfate was removed by filtration, and stripping was performed under the condition of 150 ° C./10 mmHg. The polymer obtained is 15 g and has a viscosity of 18 c.
P, the weight average molecular weight was 1600. From the gas chromatography of the obtained product, the raw material silane compound was completely disappeared. Further, from the ¹ H-NMR measurement, the proton ratio of 2.27 ppm of ethynyl proton and 0.12 ppm of SiMe was calculated. As a result, the obtained polymer was a polymer having about 15 dimethylsiloxy repeating units blocked with a 2- (ethynyldimethylsilyl) ethenyldimethylsilyl group. The refractive index (25 ° C) was 1.41.

Example 4 Example 1 except that 8.9 g (77.5 mmol) of methyldichlorosilane was used instead of dimethylchlorosilane in the hydrosilylation reaction of diethynyldimethylsilane and dimethylchlorosilane in the presence of a platinum catalyst in Example 1. 2- (ethynyldimethylsilyl) ethenylmethyldichlorosilane was synthesized in the same manner as in. 50g of this silane compound
(224.2 mmol), 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane (5 g, 24.7 mmol) and toluene (100 ml) were placed in a 500 ml round bottom flask equipped with a water cooling condenser, a dropping funnel, a thermometer and a stirrer. To this solution, 100 g of city water was added dropwise over 1 hour with vigorous stirring. Immediately after the completion of the dropping, liquid separation and water washing were carried out, followed by drying with anhydrous sodium sulfate. Further, sodium sulfate was removed by filtration, and stripping was performed under the condition of 150 ° C./3 mmHg. The polymer obtained is 33 g,
The viscosity was 55 cP and the weight average molecular weight was 3,500. From the gas chromatography of the obtained product, the raw material silane compound was completely disappeared. Moreover, from the measurement of ¹ H-NMR, 2.27
A proton ratio of ppm ethynyl protons and 0.12 ppm SiMe was calculated. As a result, the obtained polymer was a polymer having about 18 ethynyldimethylsilylethenylmethylsiloxy repeating units blocked with an ethynyldimethylsilylethenyldimethylsilyl group. Also, the refractive index (25
C) was 1.42.

Example 5 192.8 g of 2- (ethynyldimethylsilyl) ethenyldimethylchlorosilane obtained by the same method as in Example 1
(0.81mol), trimethylchlorosilane 36g (0.33mol),
Orthoethyl silicate 32.7 g (0.157 mol) and toluene 420 g
Was charged into a 3 liter separable flask equipped with a Dimroth condenser, a dropping funnel, a thermometer and a stirrer.
While cooling this separable flask with an ice water bath,
Hydrochloric acid prepared by diluting 150 g of concentrated hydrochloric acid with 210 g of city water was added dropwise over 3 hours. Then, remove the ice-water bath and leave it at room temperature (25 ℃)
The mixture was stirred for 6 hours. The reaction product was transferred to a separating funnel, and the upper organic layer and the lower aqueous layer were separated, and the organic layer was saturated with sodium chloride solution.
0 ml was added, and the contents were heated with stirring until the temperature reached 85 ° C.
Then, the organic layer and the aqueous layer were further separated with a separating funnel. Sodium sulfate was added to the obtained organic layer, and it was left to dry overnight. Then, sodium sulfate was removed, and the low boiling point was distilled off under reduced pressure (150 ° C./7 mmHg). The compound obtained has a weight average molecular weight of 1900, a refractive index (25 ° C) of 1.42, and a viscosity.
It was a 200 cP resin. Furthermore, from the measurement of ¹ H-NMR,
Proton ratio SiMe ethynyl proton and 0.12ppm of 2.27Ppm, the resin was found to be M _'8 M ₄ Q ₆ equivalent compound. Here, M ′ represents a 2- (ethynyldimethylsilyl) ethenyldimethylsiloxy unit, M represents a trimethylsiloxy unit, and Q represents a siloxy unit.

[Brief description of drawings]

FIG. 1 shows the product obtained in Example 1.
It is an IR chart.

FIG. 2 shows the product obtained in Example 1.
^{It is a 1} H-NMR chart.

Claims (2)

[Claims] 1. A general formula (1): (Wherein R represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and m represents a number of 0, 1, or 2) in the molecule. An ethynyl group-containing organosilicon compound. 2. A general formula (2): (In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 1 to 1000.) The ethynyl group-containing organosilicon compound according to claim 1.