阅读说明：本技术 一种双（乙胺基）二环戊基硅烷的合成方法 (Synthesis method of bis (ethylamino) dicyclopentyl silane ) 是由 李辉宁 张才山 张扬 李明成 于 2020-06-23 设计创作，主要内容包括：一种双(乙胺基)二环戊基硅烷的合成方法,涉及化工合成技术领域,先通过氯代环戊烷和金属镁进行格氏反应生成环戊基氯化镁,然后格氏试剂和四氯化硅进行格氏偶联反应,得二环戊基二氯硅烷。二环戊基二氯硅烷和乙胺进行氨解反应,生成双(乙胺基)二环戊基硅烷。本发明产率高,工艺较可控,原料易得,成本低,生产过程易操作,适于工业化生产。(A synthetic method of bis (ethylamino) dicyclopentyl silane relates to the technical field of chemical synthesis, firstly, chloro-cyclopentane and magnesium metal are subjected to Grignard reaction to generate cyclopentyl magnesium chloride, and then Grignard reagent and silicon tetrachloride are subjected to Grignard coupling reaction to obtain dicyclopentyl dichlorosilane. And (3) carrying out ammonolysis reaction on dicyclopentyldichlorosilane and ethylamine to generate bis (ethylamino) dicyclopentylsilane. The method has the advantages of high yield, controllable process, easily obtained raw materials, low cost, easy operation of the production process and suitability for industrial production.)

1. A method for synthesizing bis (ethylamino) dicyclopentyl silane is characterized in that: the preparation method comprises the steps of mixing magnesium chips, cyclopentyl chloride and silicon tetrachloride with n-butyl ether as a solvent at 65-75 ℃ for reaction to obtain a mixture containing dicyclopentyldichlorosilane, and reacting dicyclopentyldichlorosilane with ethylamine at the temperature of less than 20 ℃ to generate bis (ethylamino) dicyclopentylsilane.

2. The method of synthesizing bis (ethylamino) dicyclopentylsilane according to claim 1, wherein: when the mixture containing dicyclopentyldichlorosilane is prepared, magnesium chips, n-butyl ether and cuprous cyanide are mixed, the temperature is increased to 65-75 ℃, and then mixed liquid consisting of cyclopentyl chloride, n-butyl ether and silicon tetrachloride is dripped to react.

3. The method of synthesizing bis (ethylamino) dicyclopentylsilane according to claim 2, wherein: the feeding mass ratio of the magnesium chips, the cyclopentyl chloride and the silicon tetrachloride is 36: 142.5: 105-121.

4. The method of claim 3, wherein the bis (ethylamino) dicyclopentylsilane comprises: the feeding mass ratio of the magnesium chips to the cuprous cyanide is 36: 0.3-0.4.

5. The method for synthesizing bis (ethylamino) dicyclopentylsilane according to claim 1, 2, 3 or 4, wherein: and cooling the mixture containing the dicyclopentyldichlorosilane, carrying out suction filtration, washing a filter cake with n-butyl ether, combining the filtrates, and evaporating the n-butyl ether under reduced pressure to obtain the dicyclopentyldichlorosilane.

6. The method of synthesizing bis (ethylamino) dicyclopentylsilane according to claim 1, wherein: in the reaction process of dicyclopentyldichlorosilane and ethylamine, tetrahydrofuran or butyl ether is used as solvent.

7. The method of claim 6, wherein the bis (ethylamino) dicyclopentylsilane is prepared by the following steps: in the reaction process of dicyclopentyldichlorosilane and ethylamine, tetrahydrofuran is used as a solvent.

8. The method for synthesizing bis (ethylamino) dicyclopentylsilane according to claim 1, 6 or 7, wherein: the generated bis (ethylamino) dicyclopentylsilane was subjected to a purification treatment: and (3) carrying out suction filtration on the mixture after reaction, washing a filter cake with butyl ether, merging filtrate, carrying out desolventizing rectification, receiving at the bottom of a kettle at 160 ℃, and cooling to 195 ℃ to obtain the pure bis (ethylamino) dicyclopentylsilane.

Technical Field

The invention relates to the technical field of chemical synthesis.

Background

Bis (ethylamino) dicyclopentylsilane is one kind of olefin polymerizing catalyst with high catalytic activity and high polymer yield and stereoregularity.

As disclosed in US20120053310, EP1908767B1 and the like, the main preparation process of bis (ethylamino) dicyclopentyl silane at home and abroad at present is: the catalyst is synthesized by taking dicyclopentyldimethoxysilane, butyl lithium and ethylamine as raw materials, and has the following reaction formula:

the process uses the butyl lithium which is flammable and explosive, has high chemical activity and high price, so the process is dangerous in the implementation process, and the product cost is high, which is not beneficial to the process amplification and the industrial production.

Disclosure of Invention

The invention aims to provide a method for synthesizing bis (ethylamino) dicyclopentyl silane, which is beneficial to industrial production and has controllable process, economy and higher safety.

The technical scheme of the invention is as follows: firstly, under the condition of 65-75 ℃, magnesium chips, cyclopentyl chloride and silicon tetrachloride are mixed and react by taking n-butyl ether as a solvent at 65-75 ℃ to prepare a mixture containing dicyclopentyl dichlorosilane; and reacting dicyclopentyldichlorosilane with ethylamine at the temperature of less than 20 ℃ to generate bis (ethylamino) dicyclopentylsilane.

The reaction formula of the invention is as follows:

the invention firstly carries out Grignard reaction on chlorocyclopentane and magnesium metal to generate cyclopentyl magnesium chloride, and then carries out Grignard coupling reaction on a Grignard reagent and silicon tetrachloride to obtain dicyclopentyl dichlorosilane. And (3) carrying out ammonolysis reaction on dicyclopentyldichlorosilane and ethylamine to generate bis (ethylamino) dicyclopentylsilane. The method has the advantages of high yield, controllable process, easily obtained raw materials, low cost, easy operation of the production process and suitability for industrial production.

When the mixture containing dicyclopentyl dichlorosilane is prepared, magnesium chips, n-butyl ether and cuprous cyanide are mixed, the temperature is increased to 65-75 ℃, and then mixed liquid consisting of cyclopentyl chloride, n-butyl ether and silicon tetrachloride is dripped to react. In the grignard reaction, the boiling point of tetrahydrofuran is low, so that the loss of the solvent is serious during the suction filtration, and the price of tetrahydrofuran is high, which causes the increase of the cost. The n-butyl ether has a high boiling point, so that loss is reduced during suction filtration, and the n-butyl ether is used as a solvent. Cuprous cyanide plays a catalytic role in the reaction, which is beneficial to the complete reaction of the Grignard coupling reaction. Since the reaction is an exothermic reaction process, the progress of the reaction is controlled by dropping during the reaction process to prevent the accumulation of the back heat, which causes a drastic increase in temperature.

And the mass ratio of the magnesium chips, the cyclopentyl chloride and the silicon tetrachloride is 36: 142.5: 105-121. The charge ratio of the metal magnesium, the cyclopentyl chloride and the silicon tetrachloride is critical, because the three are main raw materials, and the structure and the yield of the product are related. If the silicon tetrachloride is too little, the excessive amount of cyclopentyl magnesium chloride is large, the reaction of the Grignard reagent is incomplete, and the trouble is brought to the post-treatment; if the silicon tetrachloride is excessive, a byproduct of cyclopentyl trichlorosilane can be generated, and the product yield is reduced.

In addition, the feeding mass ratio of the magnesium chips to the cuprous cyanide is 36: 0.3-0.4. The Grignard reagent generated under the proportion is just dissolved in the n-butyl ether to form a solution, which is beneficial to full contact during reaction and complete reaction, and the cuprous cyanide is used as a catalyst in the proportion range, so that the catalytic effect can be effectively realized, and excessive waste can not be caused due to excessive cuprous cyanide.

Further, the invention also reduces the temperature of the mixture containing dicyclopentyl dichlorosilane, then carries out suction filtration, washes a filter cake by n-butyl ether, combines the filtrates, and evaporates the n-butyl ether under reduced pressure to obtain the dicyclopentyl dichlorosilane. After the reaction is finished, magnesium chloride salt is generated in the system, the salt is removed through suction filtration, and meanwhile, the filter cake salt is washed by n-butyl ether, so that the product adsorbed in the salt is fully collected, and the product yield is improved.

During the reaction of dicyclopentyldichlorosilane and ethylamine, n-butyl ether is added as solvent. The n-butyl ether is used as a solvent in the reaction, so that the loss of the solvent in the suction filtration process is reduced, and the product cost is reduced.

Furthermore, in the reaction process of dicyclopentyldichlorosilane and ethylamine, tetrahydrofuran or butyl ether is used as a solvent. And preferably tetrahydrofuran is used as the solvent. Because the solubility of the ethylamine in the tetrahydrofuran is higher than that in the butyl ether, the higher concentration of the ethylamine in the tetrahydrofuran solution is more beneficial to the ammonolysis reaction.

The generated bis (ethylamino) dicyclopentylsilane was subjected to a purification treatment: and (3) carrying out suction filtration on the mixture after reaction, washing a filter cake with butyl ether, merging filtrate, carrying out desolventizing rectification, receiving at the bottom of a kettle at 160 ℃, and cooling to 195 ℃ to obtain the pure bis (ethylamino) dicyclopentylsilane. The solid-liquid separation is carried out by suction filtration, and the filtrate is desolventized and rectified, thus obtaining the bis (ethylamino) dicyclopentylsilane with high content.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of the final product obtained in each example.

Detailed Description