CN111574415B

CN111574415B - Synthetic method of perchloromethylmercaptan

Info

Publication number: CN111574415B
Application number: CN202010461258.7A
Authority: CN
Inventors: 王庆振; 吕寻伟; 马松; 马德龙
Original assignee: Shandong Yanggu Huatai Chemical Co Ltd
Current assignee: Shandong Yanggu Huatai Chemical Co Ltd
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2021-12-14
Anticipated expiration: 2040-05-27
Also published as: CN111574415A

Abstract

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.

Description

Synthetic method of 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.

Example 1

154.10g of trichloromethane and 124.39g of triethylamine are added into a 1L reaction kettle, the temperature is controlled to be 10 ℃, stirring is started, 126.58g of sulfur dichloride is slowly dripped into the system, after about 2 hours, the dripping of the sulfur dichloride is finished, the temperature is kept, stirring is continued for about 2 hours, and the reaction is finished. And (3) carrying out suction filtration on the obtained reaction liquid to remove a byproduct triethylamine hydrochloride, then adding about 100g of water to wash to remove trace unreacted triethylamine, then heating the collected lower layer liquid to 65 ℃, distilling off trace unreacted trichloromethane to finally obtain 210.6g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 92.21% in terms of sulfur dichloride, and the density is 1.69 by detection.

The synthetic experiment of the scorch retarder E is carried out by taking perchloromethylmercaptan as a raw material, and the specific method comprises the following steps: controlling the system temperature to be 10 ℃, dropwise adding perchloromethylmercaptan into a reaction system containing N-phenyl benzene sulfonamide, solvent oil and a sodium hydroxide solution, centrifuging and drying after the reaction is finished, wherein the purity of the obtained antiscorching agent E is 99.15%, and the yield and purity of the antiscorching agent E are similar to those of the antiscorching agent E synthesized by purchased perchloromethylmercaptan, so that the use requirement is met.

Example 2

151g of trichloromethane and 116.34g of triethylamine are added into a 1L reaction kettle, the temperature is controlled to be 10 ℃, stirring is started, 118.39g of sulfur dichloride is slowly dripped into the system, after about 2 hours, the dripping of the sulfur dichloride is finished, the temperature is kept, stirring is continued for about 2 hours, and the reaction is finished. And carrying out suction filtration on the obtained reaction liquid to remove a byproduct triethylamine hydrochloride, then adding about 100g of water for washing to remove trace unreacted triethylamine, then heating the collected lower layer liquid to 65 ℃, distilling out trace unreacted trichloromethane, and finally obtaining 199.2g of yellow oily liquid, namely perchloromethane thiol, wherein the yield is 93.25% in terms of sulfur dichloride, and the density is 1.69 through detection, so that the use requirement is met.

Example 3

167.28g of trichloromethane and 118.15g of triethylamine are added into a 1L reaction kettle, the temperature is controlled to be 0 ℃, stirring is started, 120.23g of sulfur dichloride is slowly dripped into the system, after about 1 hour, the dripping of the sulfur dichloride is finished, the temperature is kept, stirring is continued for about 1 hour, and the reaction is finished. And (3) carrying out suction filtration on the obtained reaction liquid to remove a byproduct triethylamine hydrochloride, then adding about 100g of water for washing to remove trace unreacted triethylamine, then heating the collected lower layer liquid to 65 ℃, distilling out trace unreacted trichloromethane, and finally obtaining 195.78g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 90.24% in terms of sulfur dichloride, and the detected density is 1.69, so that the use requirement is met.

Example 4

Adding 135.63g of trichloromethane and 104.50g of triethylamine into a 1L reaction kettle, controlling the temperature to be 20 ℃, starting stirring, slowly dropwise adding 106.34g of sulfur dichloride into the system, after about 2 hours, completing dropwise adding of sulfur dichloride, keeping the temperature, continuously stirring for about 2 hours, and completing the reaction. And (3) carrying out suction filtration on the obtained reaction liquid to remove a byproduct triethylamine hydrochloride, then adding about 100g of water for washing to remove trace unreacted triethylamine, then heating the collected lower layer liquid to 65 ℃, distilling out trace unreacted trichloromethane, and finally obtaining 175.21g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 91.31% in terms of sulfur dichloride, and the detected density is 1.69, so that the use requirement is met.

Example 5

172.97g of trichloromethane and 133.28g of triethylamine are added into a 1L reaction kettle, the temperature is controlled to be 10 ℃, stirring is started, 135.62g of sulfur dichloride is slowly dripped into the system, after about 3 hours, the dripping of the sulfur dichloride is finished, the temperature is kept, stirring is continuously carried out for about 2 hours, and the reaction is finished. And (3) carrying out suction filtration on the obtained reaction liquid to remove a byproduct triethylamine hydrochloride, then adding about 100g of water for washing to remove trace unreacted triethylamine, then heating the collected lower layer liquid to 65 ℃, distilling out trace unreacted trichloromethane, and finally obtaining 231.25g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 94.50% in terms of sulfur dichloride, and the detected density is 1.69, so that the use requirement is met.

Example 6

152.86g of trichloromethane and 98.77g of pyridine are added into a 1L reaction kettle, the temperature is controlled to be 10 ℃, stirring is started, 128.57g of sulfur dichloride is slowly dripped into the system, after about 2 hours, the dripping of the sulfur dichloride is finished, the temperature is kept, the stirring is continued for about 2 hours, and the reaction is finished. And (3) carrying out suction filtration on the obtained reaction liquid to remove a byproduct, namely pyridine hydrochloride, then adding about 100g of water for washing to remove trace unreacted pyridine, then heating the collected lower layer liquid to 65 ℃, distilling out unreacted trichloromethane, and finally obtaining 207.26g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 89.34% in terms of sulfur dichloride, and the detected density is 1.69, so that the use requirement is met.

Example 7

142.87g of trichloromethane and 47.93g of urotropine are added into a 1L reaction kettle, the temperature is controlled to be 10 ℃, stirring is started, 117.36g of sulfur dichloride is slowly dripped into the system, after about 2 hours, the dripping of the sulfur dichloride is finished, the temperature is kept, the stirring is continued for about 2 hours, and the reaction is finished. And (3) carrying out suction filtration on the obtained reaction liquid, removing byproducts, namely urotropine hydrochloride and unreacted urotropine, adding about 100g of water for washing, heating the collected subnatant to 65 ℃, and distilling out unreacted trichloromethane to finally obtain 185.36g of yellow oily liquid, namely perchloromethylmercaptan, wherein the yield is 87.53% in terms of sulfur dichloride, and the detected density is 1.69, so that the use requirement is met.

Comparative example 1

Perchloromethylmercaptan was synthesized according to the procedure of example 2, except that: the dropwise addition and the reaction temperature were controlled to 40 ℃. The yield of the obtained product is 80.23%, the detected density is 1.67, and the purity of the synthesized V.E is 95.23%, which does not meet the use requirement.

Comparative example 2

Perchloromethylmercaptan was synthesized according to the procedure of example 2, except that: the molar ratio of trichloromethane to sulfur dichloride to triethylamine is 1.3:1: 1.1. The product yield was 93.30%, with a detected density of 1.69. It can be seen that the product yield does not change much with increasing chloroform dosage, but the cost is increased.

Comparative example 3

Perchloromethylmercaptan was synthesized according to the procedure of example 2, except that: n, N-dimethylaniline is used for replacing triethylamine, and the materials are fed according to the molar ratio of 1.05:1:1 of trichloromethane, sulfur dichloride and N, N-dimethylaniline. The yield of the obtained product is 73.65 percent, the detected density is 1.66, and the use requirement is not met.

Comparative example 4

Perchloromethylmercaptan was synthesized according to the procedure of example 2, except that: azodiisopropylnitrile is used for replacing triethylamine, and the materials are fed according to the molar ratio of 1.05:1:1 of trichloromethane, sulfur dichloride and azodiisopropylnitrile. The yield of the obtained product is 42.36 percent, and the detected density is 1.63, so that the use requirement is not met.

Claims

1. A synthetic method of perchloromethylmercaptan is characterized by comprising the following steps: mixing trichloromethane and organic alkali, dripping sulfur dichloride at 0-20 ℃, and continuing to perform heat preservation reaction at the temperature after dripping; the organic base is triethylamine, pyridine or urotropin.

2. The method of synthesis according to claim 1, wherein: also comprises the step of 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.

4. 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.

5. The method of synthesis according to claim 4, wherein: the molar ratio of the nitrogen in the trichloromethane, the sulfur dichloride and the organic base is 1.05-1.1: 1:1.

6. the synthesis method according to claim 1 or 2, wherein: 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.

7. 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.