阅读说明：本技术 一种全氯甲硫醇的合成方法 (Synthetic method of perchloromethylmercaptan ) 是由 王庆振 吕寻伟 马松 马德龙 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种全氯甲硫醇的合成方法,以三氯甲烷和二氯化硫为反应原料,有机碱为催化剂和缚酸剂得到全氯甲硫醇。本方法方法安全简单,可操作性强,避免了二硫化碳和氯气的使用,有效解决了由于二硫化碳和氯气的使用而存在的安全隐患,安全性更高,所得产品外观为黄色油状液体,收率在85%以上,密度在1.69以上,符合使用要求,具有工业化应用价值。(The invention discloses a synthetic method of perchloromethylmercaptan, which is obtained by taking trichloromethane and sulfur dichloride as reaction raw materials, organic base as a catalyst and an acid-binding agent. The method is safe and simple, has strong operability, avoids the use of carbon disulfide and chlorine, effectively solves the potential safety hazard caused by the use of carbon disulfide and chlorine, has higher safety, ensures that the obtained product is yellow oily liquid in appearance, has the yield of more than 85 percent and the density of more than 1.69, meets the use requirement, and has industrial application value.)

1. A synthetic method of perchloromethylmercaptan is characterized by comprising the following steps: using trichloromethane and sulfur dichloride as substrates, and synthesizing the perchloroethane in the presence of organic alkali.

2. The method of synthesis according to claim 1, comprising the steps of:

(1) mixing trichloromethane and organic alkali, and then dropwise adding sulfur dichloride for reaction;

(2) and treating the reaction liquid after the reaction to obtain perchloromethylmercaptan.

3. The synthesis method according to claim 1 or 2, wherein: the organic base is triethylamine, pyridine or urotropin.

4. The synthesis method according to claim 1 or 2, wherein: the organic base is triethylamine.

5. The synthesis method according to claim 1 or 2, wherein: the molar ratio of the nitrogen in the trichloromethane, the sulfur dichloride and the organic base is 1.05-1.2: 1: 1-1.2, preferably 1.05-1.1: 1:1.

6. the method of synthesis according to claim 2, wherein: in the step (1), sulfur dichloride is dripped at the temperature of 0-20 ℃, and the heat preservation reaction is continuously carried out at the temperature after the dripping is finished.

7. The synthesis method according to claim 2 or 6, wherein: in the step (1), the dripping time of the sulfur dichloride is 1-3h, and the reaction is continued for 1-2h after the dripping of the sulfur dichloride is finished.

8. The method of synthesis according to claim 2, wherein: the post-treatment process of the reaction liquid comprises the following steps: and after the reaction, filtering to remove salts formed in the reaction, washing the residual reaction solution with water to remove unreacted organic alkali, and distilling the residual reaction solution to remove trichloromethane to obtain perchloromethylmercaptan.

Technical Field

The invention relates to a synthetic method of perchloromethylmercaptan as an organic chemical raw material, in particular to a synthetic method of perchloromethylmercaptan, which has the advantages of simple and safe production process, small waste water amount, environmental protection and high product yield, and belongs to the technical field of organic synthesis.

Background

The perchloromethylmercaptan is an important chemical raw material for pesticide bactericides such as captan, folpet, terrazole and the like, and the perchloromethylmercaptan is also a key synthetic raw material of a rubber scorch retarder V.E (also called as a scorch retarder E). The scorch retarder V.E is developed by Bayer company in Germany and is dedicated to light-colored rubber vulcanization, is pollution-free and non-colored, does not foam during high-temperature mixing, is effective for sulfenamides, and is more suitable for vulcanization systems of mercaptan and thiuram accelerators. The rubber is widely applied to various industries such as daily life, medical industry, rail transit industry and the like at present, and has an irreplaceable effect in the life of people. Natural rubber and synthetic rubber are widely used in the current society and daily life, and with the continuous development of economy, the demand of rubber in various industries is continuously increased, so that the demand of the scorch retarder V.E is also continuously increased, which also results in the large increase of the demand of perchloromethylmercaptan.

At present, the synthesis process of perchloromethylmercaptan generally adopts a method of introducing chlorine gas into carbon disulfide, and the process has the problems of long reaction time, low product yield and escape of carbon disulfide and chlorine gas from a system in the reaction process, the escape of carbon disulfide has certain potential safety hazard, the escape of chlorine gas needs a tail gas absorption device, and simultaneously has larger smell, thus influencing the physical health of an operator and improving the production cost.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a synthetic method of perchloromethylmercaptan, which takes trichloromethane and sulfur dichloride as substrates and takes organic base as a catalyst and an acid-binding agent, so that the perchloromethylmercaptan is conveniently and rapidly synthesized.

The specific technical scheme of the invention is as follows:

a process for synthesizing perchloromethylmercaptan features that trichloromethane and sulfur dichloride are used as substrate and the perchloromethylmercaptan is synthesized in the presence of organic alkali. The organic base is used as a catalyst and an acid-binding agent, so that the action of activating the trichloromethane is achieved, the leaving of hydrogen is promoted, and the reaction activity of the trichloromethane is improved; on the other hand, the reaction kettle plays a role in capturing by-product hydrogen chloride so as to ensure that the reaction is carried out in a forward direction.

Further, the organic base may be any organic base which can react with hydrogen chloride to form a salt and has a promoting effect on the activity of chloroform, and may be triethylamine, pyridine, urotropine and the like, and the commonly used organic base is triethylamine.

Furthermore, when the organic base is triethylamine, the yield of the product is higher, and the operability is stronger. The reaction equation is as follows:

further, in the above synthesis method, the molar ratio of nitrogen in chloroform, sulfur dichloride and organic base is 1.05-1.2: 1: 1-1.2, preferably 1.05-1.1: 1:1.

furthermore, the synthesis method does not need to carry out reaction in an organic solvent, and the cost is lower. The method specifically comprises the following steps:

(1) mixing trichloromethane and organic alkali, and then dropwise adding sulfur dichloride for reaction;

(2) and treating the reaction liquid after the reaction to obtain perchloromethylmercaptan.

Further, in the step (1), sulfur dichloride is dripped at the temperature of 0-20 ℃, and the heat preservation reaction is continuously carried out at the temperature after the dripping is finished. The dripping time of the common sulfur dichloride is controlled to be 1-3h, and the heat preservation reaction is continued for 1-2h after the dripping of the sulfur dichloride is finished. After the reaction, the reaction solution contains perchloromethane alcohol and organic base hydrochloride, and also contains a trace amount of unreacted trichloromethane and organic base.

Further, in the step (2), the post-treatment process of the reaction solution is as follows: and after the reaction, filtering to remove salts formed in the reaction, washing the residual reaction solution with water to remove unreacted organic alkali, and distilling the residual reaction solution to remove trichloromethane to obtain perchloromethylmercaptan.

Compared with the traditional process for preparing perchloromethylmercaptan by introducing chlorine gas, carbon disulfide and dilute hydrochloric acid, the method has the following advantages:

1. trichloromethane and sulfur dichloride are used as substrates, so that the use of carbon disulfide and chlorine is avoided, the potential safety hazard caused by the use of carbon disulfide and chlorine is effectively solved, and the safety is higher.

2. The invention uses organic alkali as catalyst and acid-binding agent, which is more beneficial to the forward reaction, the reaction temperature is lower, and the reaction time is short.

3. The method has the advantages of safe and simple production process and strong operability, the obtained product is yellow oily liquid in appearance, the yield is more than 85 percent, the density is more than 1.69, the use requirement is met, and the method has industrial application value.

4. The method does not need to use an organic solvent, has lower cost, simple post-treatment and less generated waste water, and is more environment-friendly.

Detailed Description

The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to be limiting.

In the following examples, the yield was calculated as: quality of the obtained product/theoretical quality of the product.