阅读说明：本技术 烯丙基三甲基硅烷的制备方法 (Preparation method of allyltrimethylsilane ) 是由 吴国栋 袁青海 李伟锋 陈剑君 李金生 于 2021-11-11 设计创作，主要内容包括：本发明公开了一种烯丙基三甲基硅烷的制备方法,其特点是包括如下步骤：将镁箔、铝箔和溶剂加入反应瓶中,向反应瓶中滴加氯丙烯和三甲基氯硅烷的混合溶液,滴加过程中控制温度为45～85℃；滴加结束后加热至回流状态继续反应4～8小时,反应结束后过滤反应液,滤液进行常压精馏分离提纯,得到烯丙基三甲基硅烷。本发明的有益效果是采用镁箔和铝箔混合物与氯丙烯和三甲基氯硅烷混合液直接反应,反应路线短,操作流程简单,不可控因素少,反应过程无需添加含碘或溴等元素的催化剂,降低了后续纯化难度最终成品可以达到电池电解液使用要求。(The invention discloses a preparation method of allyl trimethylsilane, which is characterized by comprising the following steps: adding a magnesium foil, an aluminum foil and a solvent into a reaction bottle, dropwise adding a mixed solution of chloropropene and trimethylchlorosilane into the reaction bottle, and controlling the temperature to be 45-85 ℃ in the dropwise adding process; and after the dropwise addition, heating to a reflux state, continuing to react for 4-8 hours, filtering the reaction solution after the reaction is finished, and performing normal-pressure rectification, separation and purification on the filtrate to obtain the allyl trimethylsilane. The method has the advantages that the mixture of the magnesium foil and the aluminum foil is directly reacted with the mixed solution of the chloropropene and the trimethylchlorosilane, the reaction route is short, the operation process is simple, the uncontrollable factors are few, a catalyst containing elements such as iodine or bromine is not required to be added in the reaction process, the subsequent purification difficulty is reduced, and the final finished product can meet the use requirement of the battery electrolyte.)

1. The preparation method of the allyltrimethylsilane is characterized by comprising the following steps: adding a magnesium foil, an aluminum foil and a solvent into a reaction bottle, dropwise adding a mixed solution of chloropropene and trimethylchlorosilane into the reaction bottle, and controlling the temperature to be 45-85 ℃ in the dropwise adding process; and after the dropwise addition, heating to a reflux state, continuing to react for 4-8 hours, filtering the reaction solution after the reaction is finished, and performing normal-pressure rectification, separation and purification on the filtrate to obtain the allyl trimethylsilane.

2. The method for preparing allyltrimethylsilane according to claim 1, wherein: the molar ratio of the magnesium foil to the aluminum foil is any ratio of 8: 2-9: 1.

3. The method for producing allyltrimethylsilane according to claim 2, wherein: the ratio of the total mole number of the magnesium foil and the aluminum foil to the mole number of the chloropropene is 1.1: 1-1.2: 1 in any ratio.

4. The method for producing allyltrimethylsilane according to claim 3, wherein: the mol ratio of the chloropropene to the trimethylchlorosilane is any ratio of 1: 1.1-1: 1.2.

5. The method for producing allyltrimethylsilane according to claim 4, wherein: in the step of dropwise adding the mixed solution of chloropropene and trimethylchlorosilane into the reaction bottle, the dropping speed is 1 drop per second.

6. The process for preparing allyltrimethylsilane according to any of claims 1 to 2, wherein: the solvent is one or more of divinyl ether, diethyl ether, allyl ethyl ether, methyl tert-butyl ether, ethyl propyl ether and tetrahydrofuran.

7. The method for producing allyltrimethylsilane according to claim 6, wherein: the using amount of the solvent is 4-6 times of the mass of chloropropene.

Technical Field

The invention belongs to the technical field of preparation of compounds containing C-Si bonds, and particularly relates to a preparation method of allyl trimethylsilane.

Background

With the vigorous promotion of 'carbon peak reaching' and 'carbon neutralization' plans in China, a new energy industry chain can be developed vigorously, and the new energy industry chain comprises industries such as new energy automobiles, renewable energy storage of photovoltaic energy, wind power energy and the like. The new energy industry is finally unable to keep away with high-performance lithium ion batteries. As the industry continues to iterate through the electrolyte formulations necessary to develop a battery, various new additives have been developed. Allyltrimethylsilane is a highly effective novel additive among the preferred additives. Its main function is to help eliminate HF and H in the electrolyte₂And O, the etching and the damage of HF to the interface film of the positive and negative electrode surface phases are avoided, the dissolution of transition metal elements in the positive electrode material and the damage of a crystal lattice structure are inhibited, in addition, redox polymerization reaction can be carried out, and a stable and compact passivation film is formed on the surfaces of the positive electrode and the negative electrode. In the prior art, allyl trimethylsilane is prepared by a Grignard reagent method, which comprises the steps of firstly preparing a Grignard reagent corresponding to corresponding alkyl halide, then reacting with trimethylchlorosilane, adding catalysts such as iodine or 1, 2-dibromoethane and the like during the reaction, and quenching the reaction with water after the reaction is finished. Chinese patent application, application No. CN201510773403.4, application No. 2015.11.14, application publication No. CN106699794A, application publication No. 2017.05.24, discloses a production process for preparing allyl trimethylsilane based on the format reagent method, the brief introduction of the process flow is: preparing an allyl magnesium bromide Grignard reagent; preparing allyl trimethylsilane; and thirdly, rectifying under normal pressure. The method has the defects that the reaction process for preparing the allyl trimethyl silane by the Grignard reagent method needs to be carried out in two steps, the iodine, 1, 2-dibromoethane and other halogenated elements added in the reaction process cause certain separation difficulty and are difficult to purify to high-purity allyl trimethyl silane, and the residual of the iodine, bromine and other elements can cause irreversible damage to the battery electrolyte.

Disclosure of Invention

1. Technical problem to be solved

Aiming at the problems that in the prior art, the reaction process for preparing allyl trimethylsilane by a Grignard reagent method needs to be carried out in two steps, iodine or halogenated elements such as 1, 2-dibromoethane and the like added in the reaction process cause certain separation difficulty and are difficult to purify to high-purity allyl trimethylsilane, and the residual of the elements such as iodine, bromine and the like cause irreversible damage to battery electrolyte and the like, the invention aims to provide a preparation method of allyl trimethylsilane.

2. Technical scheme

In order to achieve the purpose and achieve the technical effect, the invention adopts the following technical scheme:

the preparation method of the allyl trimethylsilane is characterized by comprising the following steps: adding a magnesium foil, an aluminum foil and a solvent into a reaction bottle, dropwise adding a mixed solution of chloropropene and trimethylchlorosilane into the reaction bottle, and controlling the temperature to be 45-85 ℃ in the dropwise adding process; and after the dropwise addition, heating to a reflux state, continuing to react for 4-8 hours, filtering the reaction solution after the reaction is finished, and performing normal-pressure rectification, separation and purification on the filtrate to obtain the allyl trimethylsilane.

In a specific embodiment of the invention, the molar ratio of the magnesium foil to the aluminum foil is any ratio of 8: 2 to 9: 1.

In a specific embodiment of the present invention, the ratio of the total moles of the magnesium foil and the aluminum foil to the moles of the chloropropene is 1.1: 1-1.2: 1 in any ratio.

In a specific embodiment of the invention, the mol ratio of the chloropropene to the trimethylchlorosilane is 1: 1.1-1: 1.2.

In a specific embodiment of the invention, the dropping speed in the step of dropping the mixed solution of chloropropene and trimethylchlorosilane into the reaction bottle is 1 drop per second.

In a specific embodiment of the present invention, the solvent is one or more of divinyl ether, diethyl ether, allyl ethyl ether, methyl tert-butyl ether, ethyl propyl ether, and tetrahydrofuran.

In a specific embodiment of the invention, the amount of the solvent is 4-6 times of the mass of the chloropropene.

The allyl trimethylsilane is prepared by the method, wherein the purity of the allyl trimethylsilane is more than or equal to 99.1 percent, the water content is less than or equal to 100ppm, the chloride ion is less than or equal to 10ppm, the bromide ion is less than or equal to 10ppm, the iodide ion is less than or equal to 10ppm, and the chroma is less than or equal to 10 Hazl. The water content is detected by a Karl Fischer method conventional moisture meter, the chlorine, bromine, iodine and the like are detected by a total chlorine meter, and the chromaticity is detected by comparing with a standard solution.

The invention also aims to provide application of the allyltrimethylsilane prepared by the preparation method of the allyltrimethylsilane as an additive in an electrolyte formula.

The reaction principle of the invention is as follows: firstly, magnesium and chloropropene generate chloropropene magnesium, but the activity of magnesium is weaker, so that a part of chloropropene does not participate in reaction, at the moment, a small amount of aluminum foil which is added in a matching manner can generate trichloro tri-allyl-di-aluminum, a small amount of triallyl aluminum and the like with chloropropene which does not participate in reaction again, then the chloropropene magnesium, the trichloro tri-allyl-di-aluminum, a small amount of triallyl aluminum and the like are subjected to coupling reaction with trimethylchlorosilane, and finally the allyl trimethyl silane is generated.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that: the mixture of the magnesium foil and the aluminum foil is directly reacted with the mixed liquid of the chloropropene and the trimethylchlorosilane, the reaction route is short, the operation process is simple, the uncontrollable factors are few, a catalyst containing elements such as iodine or bromine is not required to be added in the reaction process, the quenching reaction with water is not required, the subsequent purification difficulty is reduced, and the final finished product can meet the use requirement of the battery electrolyte.

Detailed Description

The present invention will be described in further detail with reference to specific examples, so that the advantages of the present invention will be more apparent. It should be understood that the description is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.

Example 1

The preparation method of allyl trimethylsilane comprises the steps of adding magnesium foil (25 g, 1.028 mol), aluminum foil (6.9 g, 0.257 mol) and solvent divinyl ether (300 g) into a reaction bottle, and dropwise adding a mixed solution of chloropropene (89.3 g, 1.168 mol) and trimethylchlorosilane (139.5 g, 1.284 mol) into the reaction bottle, wherein the temperature is controlled to be 50 +/-5 ℃ during dropwise adding; after the dropwise addition, the reaction solution is heated to a reflux state and continuously reacted for 5 hours, after the reaction is finished, the reaction solution is filtered, and the filtrate is subjected to normal pressure rectification separation and purification to obtain 106 g of allyltrimethylsilane, wherein the content is 99.4% by using gas chromatography analysis, the yield is 79%, the water content is 60ppm, the chloride ion content is 1.1ppm, the bromide ion content is 1.3ppm, the iodide ion content is 1.2ppm, and the chroma is 10 Hazl.

Example 2

A preparation method of allyl trimethylsilane comprises the steps of adding magnesium foil (28 g, 1.156 mol), aluminum foil (3.4 g, 0.128 mol) and 350 g of allyl ethyl ether serving as a solvent into a reaction bottle, dropwise adding a mixed solution of chloropropene (81.9, 1.07 mol) and trimethylchlorosilane (139.4 g, 1.284 mol) into the reaction bottle, controlling the temperature to be 70 +/-5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 7 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 100 g of allyl trimethylsilane, wherein the content is 99.2% by using gas chromatography analysis, the yield is 81%, the water content is 50ppm, the chloride ion is 1.2ppm, the bromide ion is 1.1ppm, the iodide ion is 1.3ppm, and the chroma is 10 Hazl.

Example 3

The preparation method of allyl trimethylsilane comprises the steps of adding 300 g of magnesium foil (25 g, 1.028 mol), 6.9 g of aluminum foil (0.257 mol) and solvent divinyl ether into a reaction bottle, dropwise adding a mixed solution of chloropropene (89.3 g, 1.168 mol) and trimethylchlorosilane (152.2 g, 1.401 mol) into the reaction bottle, controlling the temperature to be 50 ℃ plus or minus 5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 113 g of allyl trimethylsilane, wherein the content is 99.3 percent, the yield is 84 percent, the water content is 50ppm, the chloride ion is 1.2ppm, the bromide ion is 1.3ppm, the iodide ion is 1.2ppm, and the chroma is 10Hazl by using gas chromatography.

Example 4

The preparation method of allyl trimethylsilane comprises the steps of adding 300 g of solvent divinyl ether into a reaction bottle, dropwise adding a mixed solution of chloropropene (89.3 g, 1.168 mol) and trimethylchlorosilane (152.2 g, 1.401 mol) into the reaction bottle, controlling the temperature to be 70 ℃ plus or minus 5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 109 g of allyl trimethylsilane, wherein the content is 99.1 percent, the yield is 81 percent, the moisture is 40ppm, the chloride ion is 1.3ppm, the bromide ion is 1.2ppm, the iodide ion is 1.2ppm, and the chroma is 10Hazl by using gas chromatography analysis.

Example 5

The preparation method of allyl trimethylsilane comprises the steps of adding magnesium foil (29.16 g, 1.2 mol), aluminum foil (5.69 g, 0.211 mol) and 300 g of solvent ether into a reaction bottle, dropwise adding a mixed solution of chloropropene (90 g, 1.176 mol) and trimethylchlorosilane (140.4 g, 1.293 mol) into the reaction bottle, controlling the temperature to be 50 ℃ plus or minus 5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 104 g of allyl trimethylsilane, wherein the content is 99.1 percent, the yield is 78 percent, the water content is 30ppm, the chloride ion is 1.9ppm, the bromide ion is 1.1ppm, the iodide ion is 1.6ppm, and the chroma is 10Hazl by using gas chromatography.

Example 6

The preparation method of allyl trimethylsilane comprises the steps of adding magnesium foil (27.9 g, 1.149 mol), aluminum foil (5.4 g, 0.202 mol) and 300 g of solvent methyl tert-butyl ether into a reaction bottle, dropwise adding a mixed solution of chloropropene (90 g, 1.176 mol) and trimethylchlorosilane (140.4 g, 1.293 mol) into the reaction bottle, controlling the temperature to be 60 +/-5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 110 g of allyl trimethylsilane, wherein the content is 99.1 percent by using gas chromatography, the yield is 82 percent, the moisture is 42ppm, the chloride ion is 1.5ppm, the bromide ion is 1.6ppm, the iodide ion is 1.4ppm, and the chroma is 10 Hazl.

Example 7

A preparation method of allyl trimethylsilane comprises the steps of adding magnesium foil (28.2 g, 1.164 mol), aluminum foil (3.4 g, 0.129 mol) and 300 g of solvent ethyl propyl ether into a reaction bottle, dropwise adding a mixed solution of chloropropene (90 g, 1.176 mol) and trimethylchlorosilane (146.8 g, 1.352 mol) into the reaction bottle, controlling the temperature to be 60 +/-5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain 104 g of allyl trimethylsilane, wherein the content is 99.1 percent by using gas chromatography, the yield is 77 percent, the water content is 49ppm, the chloride ion is 2.3ppm, the bromide ion is 1.1ppm, the iodide ion is 1.9ppm, and the chroma is 10 Hazl.

Example 8

A preparation method of allyl trimethylsilane comprises the steps of adding 300 g of solvent tetrahydrofuran, 29.5 g of magnesium foil (1.217 mol), 3.6 g of aluminum foil (0.135 mol) and 300 g of solvent tetrahydrofuran into a reaction bottle, dropwise adding a mixed solution of chloropropene (90 g, 1.176 mol) and trimethylchlorosilane (146.8 g, 1.352 mol) into the reaction bottle, controlling the temperature to be 80 ℃ plus or minus 5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification, separation and purification on the filtrate to obtain 111 g of allyl trimethylsilane, wherein the content is 99.1 percent by using gas chromatography, the yield is 83 percent, the moisture content is 44ppm, the chloride ion is 1.8ppm, the bromide ion is 1.7ppm, the iodide ion is 1.5ppm, and the chroma is 10 Hazl.

Comparative example 1

Firstly adding 25 g of magnesium powder and tetrahydrofuran into a reaction bottle, then adding 0.5 g of iodine with a catalytic amount, then firstly dropwise adding a small amount of a tetrahydrofuran solution of chloropropene (containing 15 g of chloropropene) into the reaction system, continuously dropwise adding the rest of the tetrahydrofuran solution of chloropropene (containing 63 g of chloropropene) after the reaction is initiated, dropwise adding a tetrahydrofuran solution of trimethylchlorosilane (containing 128 g of trimethylchlorosilane) after the dropwise adding is finished, heating to reflux reaction for 30 hours after the dropwise adding is finished, dropwise adding a saturated aqueous ammonium chloride solution into the reaction solution after the reaction is finished to adjust the pH to be neutral, then extracting allyl trimethylsilane in an aqueous phase by using ethyl acetate, then drying and dehydrating, rectifying and purifying to obtain 56 g of allyl trimethylsilane, analyzing by using a gas chromatography, wherein the content is 90.5%, the yield is 48%, the moisture content is 1640ppm, the chloride ion is 69ppm, and the bromide ion is 1.2ppm, iodide ion 152ppm, color number 30 Hazl.

Comparative example 2

In a 250ml four-mouth glass round bottom flask with a reflux condenser, a thermometer, a stirrer, a heater and a balance feeder, under the protection of nitrogen, 23 g of magnesium chips, 35 g of chloropropene, 110 g of trimethylchlorosilane and 0.55 g of potassium iodide are added, heating and refluxing are carried out for 4.5 hours, the residual 30 g of chloropropene is added dropwise, the addition is completed in 1 hour, the temperature is kept for 30 minutes after the addition, the reaction is ended, 79 g of allyl trimethylsilane is obtained, and the content is 69 percent, the crude yield is 81 percent, the water content is 240ppm, the chloride ion content is 186ppm, the bromide ion content is 1.2ppm, the iodide ion content is 3125ppm, and the chroma is 50Hazl by using a gas chromatographic analysis.

Comparative example 3

A preparation method of allyl trimethylsilane comprises the steps of adding aluminum foil (34.9 g, 1.293 mol) and solvent toluene 300 g into a reaction bottle, dropwise adding a mixed solution of chloropropene (90 g, 1.176 mol) and trimethylchlorosilane (140.4 g, 1.293 mol) into the reaction bottle, controlling the temperature to be 100 +/-5 ℃ in the dropwise adding process, heating to a reflux state after the dropwise adding is finished, continuing to react for 5 hours, filtering the reaction liquid after the reaction is finished, and carrying out normal-pressure rectification separation and purification on the filtrate to obtain allyl trimethylsilane 130 g, wherein the content is 51.1%, the crude yield is 49%, the moisture is 40ppm, the chloride ion is 12ppm, the bromide ion is 1.7ppm, the iodide ion is 1.5ppm, and the chroma is 10 Hazl.

It will be appreciated that various alterations and modifications of the invention will occur to those skilled in the art upon reading the above teachings, and that such equivalents are intended to fall within the scope of the invention as defined by the appended claims.