阅读说明：本技术 一种二硫代二丙酸二烷基酯的制备方法 (Preparation method of dialkyl dithiodipropionate ) 是由 袁沩明 潘锦 张玉华 范明磊 杨忠义 张满中 于 2021-08-06 设计创作，主要内容包括：本发明提供了一种二硫代二丙酸二烷基酯的制备方法,包括以下步骤：(a)将硫磺粉和氨水溶液充分混合后得到混合液a,将混合液a加入到搅拌的丙烯酸烷基酯中,混合均匀后,边搅拌边通入硫化氢气体,温度保持在15℃-55℃,压力0-1MPa,反应20min-40min后经分离获得混合酯；(b)将亚硫酸钠固体和氨水溶液充分混合后得到混合液b,将混合液b加入到搅拌的步骤(a)得到的混合酯中,搅拌升温,温度保持在40℃-80℃,压力0-1MPa,30min-40min后得到粗二硫代二丙酸二烷基酯产品,经提纯后得到二硫代二丙酸二烷基酯产品。本发明适用于高压釜或管道式连续化反应器,操作简单,成本低,产率高,适宜于工业化生产。(The invention provides a preparation method of dialkyl dithiodipropionate, which comprises the following steps: (a) fully mixing sulfur powder and an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred alkyl acrylate, uniformly mixing, introducing hydrogen sulfide gas while stirring, keeping the temperature at 15-55 ℃, keeping the pressure at 0-1MPa, reacting for 20-40 min, and separating to obtain mixed ester; (b) and (2) fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution b, adding the mixed solution b into the mixed ester obtained in the stirring step (a), stirring and heating, keeping the temperature at 40-80 ℃, keeping the pressure at 0-1MPa, obtaining a crude dialkyl dithiodipropionate product after 30-40 min, and purifying to obtain the dialkyl dithiodipropionate product. The invention is suitable for high-pressure autoclave or pipeline type continuous reactor, has simple operation, low cost and high yield, and is suitable for industrial production.)

1. A preparation method of dialkyl dithiodipropionate is characterized by comprising the following steps:

(a) fully mixing sulfur powder and an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred alkyl acrylate, uniformly mixing, introducing hydrogen sulfide gas while stirring, keeping the temperature at 15-55 ℃, keeping the pressure at 0-1MPa, reacting for 20-40 min, and separating to obtain mixed ester; (b) and (2) fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution b, adding the mixed solution b into the mixed ester obtained in the stirring step (a), stirring and heating, keeping the temperature at 40-80 ℃, keeping the pressure at 0-1MPa, obtaining a crude dialkyl dithiodipropionate product after 30-40 min, and purifying to obtain the dialkyl dithiodipropionate product.

2. The method according to claim 1, wherein in the step (a), the alkyl group in the alkyl acrylate is an alkyl group having 1 to 8 carbon atoms.

3. The method according to claim 1, wherein the concentration of the aqueous ammonia solution in the steps (a) and (b) is 0.1 to 25 wt%.

4. The process according to claim 1, wherein in step (a), the mass ratio of the sulfur powder to the aqueous ammonia solution is between 1:1.43 and 1: 10; the mass ratio of the mixed liquid a to the alkyl acrylate is 1:0.1 to 1: 10.

5. The production method according to claim 1, wherein in the step (a), the aeration rate of the hydrogen sulfide is 325g/h to 395 g/h.

6. The method according to claim 1, wherein in the step (a), the reaction time is 30 min.

7. The process according to claim 1, wherein in step (b), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1:4 and 1:1.9, and the mass ratio of the sodium sulfite to the mixed ester b is between 1:7 and 1: 2.37.

8. The method of claim 1, wherein in step (b), the temperature of the reaction is 60 ℃ to 65 ℃; the reaction time was 30 min.

9. The preparation method according to claim 1, wherein in the step (a), the mixed ester is obtained by separating liquid, and ammonia water in waste liquid can be recycled; in the step (b), the crude dialkyl dithiodipropionate product is distilled and purified to obtain a dialkyl dithiodipropionate product, the sodium thiosulfate in the waste liquid is recovered by evaporation and crystallization, and the ammonia water in the waste liquid can be recycled.

10. The method according to claim 1, wherein each of the reactions in the steps (a) and (b) is carried out in a reaction vessel or a continuous tubular reactor.

Technical Field

The invention relates to a preparation method of dialkyl dithiodipropionate, belonging to the field of compound preparation.

Background

The dialkyl dithiodipropionate is a chemical which is widely applied in industry and is widely applied to the aspects of medicine mixture, bactericide, cleaning agent and the like. For example, dimethyl dithiodipropionate is a raw material for synthesizing isothiazolinone and metal surface cleaner. At present, the preparation methods of dialkyl dithiodipropionate include the following two methods:

methyl acrylate, sodium polysulfide and sodium bicarbonate are used as raw materials to prepare the dialkyl dithiodipropionate, and the method has the defects of harsh reaction conditions, long reaction time, large amount of three wastes generated in the reaction and no contribution to industrial production.

② the methyl acrylate and hydrogen sulfide are used as raw materials to react to generate crude ester, and then chlorine is introduced into the crude ester under the condition of using n-heptane as solvent to obtain the dialkyl dithiodipropionate.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provide a preparation method of dialkyl thiodipropionate, which has the advantages of simple operation, short time period, high yield and easy industrial production.

In order to achieve the purpose, the invention adopts the following technical means:

the invention provides a preparation method of dialkyl dithiodipropionate, which comprises the following steps:

(a) fully mixing sulfur powder and an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred alkyl acrylate, uniformly mixing, introducing hydrogen sulfide gas while stirring, keeping the temperature at 15-55 ℃, keeping the pressure at 0-1MPa, reacting for 20-40 min, and separating to obtain mixed ester; (b) and (2) fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution b, adding the mixed solution b into the mixed ester obtained in the stirring step (a), stirring and heating, keeping the temperature at 40-80 ℃, keeping the pressure at 0-1MPa, obtaining a crude dialkyl dithiodipropionate product after 30-40 min, and purifying to obtain the dialkyl dithiodipropionate product.

Further, in step (a), the alkyl group in the alkyl acrylate is an alkyl group having 1 to 8 carbon atoms, including but not limited to-CH₃、-C₂H₅、-C₃H₇、-C₄H₉、-C₅H₁₁、-C₆H₁₃、-C₇H₁₅、-C₈H₁₇。

Further, in the step (a), the concentration of the aqueous ammonia solution is 0.1 wt% to 25 wt%.

Further, in the step (a), the mass ratio of the sulfur powder to the ammonia water solution is between 1:1.43 and 1: 10.

Further, in the step (a), the mass ratio of the mixed solution a to the alkyl acrylate is between 1:0.1 and 1: 10.

Further, in step (a), the aeration rate of the hydrogen sulfide is 325g/h to 395 g/h.

Further, in step (a), the time of the reaction is 30 min.

Further, in step (a), the reaction time is not preferably too long, otherwise more impurities are generated.

Further, in the step (a), the mixed ester is obtained by separating liquid, the ammonia water solution in the waste liquid can be recycled, and when the concentration of ammonia is lower than 0.1 wt%, the content of ammonia is supplemented.

Further, in the step (b), the concentration of the aqueous ammonia solution is 0.1 wt% to 25 wt%, which can promote the cleavage of the-S-bond.

Further, in the step (b), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1:4 and 1:1.9, and the mass ratio of the sodium sulfite to the mixed ester b is between 1:7 and 1: 2.37.

Further, in step (b), the temperature of the reaction is 60 ℃ to 65 ℃.

Further, in step (b), the time of the reaction is 30 min.

Further, in the step (b), the crude dialkyl dithiodipropionate product is distilled and purified to obtain a dialkyl dithiodipropionate product, sodium thiosulfate in the waste liquid is recovered by evaporation and crystallization, ammonia water in the waste liquid is recovered by distillation, and the recovered ammonia water solution can be recycled.

Further, each reaction in step (a) and step (b) is carried out in a reaction vessel or a pipeline type continuous reactor.

Compared with the prior art, the invention has the following advantages:

the reaction adopted by the invention is cheap and easy to obtain.

Secondly, the synthesis route of the invention is simple, the reaction time is greatly shortened, the reaction yield is improved, the overall efficiency is improved, the invention is suitable for a reaction kettle or a pipeline type continuous reactor, the operation is simple, the cost is low, and the industrial production is easy to realize.

And thirdly, the invention can not generate three wastes through the recycling of tail gas.

Drawings

FIG. 1 is a chromatogram of a 3, 3-dithiodipropionic acid dimethyl ester standard;

FIG. 2 is a chromatogram of the dimethyl 3, 3-dithiodipropionate product prepared in example 1 of the present invention;

FIG. 3 is a chromatogram of diethyl 3, 3-dithiodipropionate;

FIG. 4 is a chromatogram of the diethyl 3, 3-dithiodipropionate product prepared in example 2 according to the present invention;

FIG. 5 is a chromatogram of a dibutyl 3, 3-dithiodipropionate standard;

FIG. 6 is a chromatogram of dibutyl 3, 3-dithiodipropionate product prepared in example 3 according to the invention;

FIG. 7 is a chromatogram of a 3, 3-diisooctyl dithiodipropionate standard;

FIG. 8 is a chromatogram of the diisooctyl 3, 3-dithiodipropionate product prepared in example 4 of the present invention.

Detailed Description

The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.

EXAMPLE 1 preparation of the Compound Dithiodipropionic acid dimethyl ester

(a) Preparing sulfur powder, 5 wt% of ammonia water solution and methyl acrylate according to the mass ratio of 1:3.35:3.68, fully mixing the sulfur powder and the ammonia water solution to obtain mixed solution a, placing the methyl acrylate in a reaction kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred methyl acrylate, sealing, uniformly mixing, introducing hydrogen sulfide gas at the aeration speed of 325-395 g/h while stirring, keeping the temperature at 25-30 ℃, keeping the pressure at 0-1MPa, reacting for 30min, separating to obtain mixed ester, and recovering ammonia water in waste liquid by distillation; (b) preparing sodium sulfite solid, 5 wt% of ammonia water solution and the mixed ester obtained in the step (a) according to the mass ratio of 1:2.56:3.17, fully mixing the sodium sulfite solid and the ammonia water solution to obtain mixed solution b, adding the mixed solution b into the mixed ester obtained in the step (a), sealing, continuously stirring and heating, keeping the temperature at 60-65 ℃, keeping the pressure at 0-1MPa, cooling after 30min, separating liquid in a kettle to obtain a crude dimethyl dithiodipropionate product with the content of 93%, purifying the dimethyl dithiodipropionate to more than 99% by using a distillation device, recovering sodium thiosulfate in waste liquid by evaporation and crystallization, and recovering the ammonia water in the waste liquid by distillation for use in the next reaction.

The chromatogram of the standard dimethyl dithiodipropionate is shown in FIG. 1, and the chromatogram of the dimethyl dithiodipropionate product prepared in this example is shown in FIG. 2.

EXAMPLE 2 preparation of the Compound Dithiodipropionic acid diethyl ester

(a) Preparing sulfur powder, 5 wt% of ammonia water solution and ethyl acrylate according to the mass ratio of 1:4.03:4.28, fully mixing the sulfur powder and the ammonia water solution to obtain mixed solution a, placing the ethyl acrylate in a reaction kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred ethyl acrylate, sealing, uniformly mixing, introducing hydrogen sulfide gas at the aeration speed of 325-395 g/h while stirring, keeping the temperature at 30-35 ℃, keeping the pressure at 0-1MPa, reacting for 30min, separating to obtain mixed ester, and recovering ammonia water in waste liquid by distillation; (b) preparing sodium sulfite solid, 5 wt% of ammonia water solution and the mixed ester obtained in the step (a) according to the mass ratio of 1:2.56:3.68, fully mixing the sodium sulfite solid and the ammonia water solution to obtain mixed solution b, adding the mixed solution b into the mixed ester obtained in the step (a), sealing, continuously stirring and heating, keeping the temperature at 60-65 ℃, keeping the pressure at 0-1MPa, cooling after 30min, separating liquid in a kettle to obtain a crude diethyl dithiodipropionate product with the content of 92%, purifying the diethyl dithiodipropionate to more than 99% by a distillation device, recovering sodium thiosulfate in waste liquid by evaporation and crystallization, and recovering ammonia water in the waste liquid by distillation for use in the next reaction.

The chromatogram of the diethyl dithiodipropionate standard sample is shown in FIG. 3, and the chromatogram of the diethyl dithiodipropionate product prepared in this example is shown in FIG. 4.

EXAMPLE 3 preparation of the Compound dibutyl dithiodipropionate

(a) Preparing sulfur powder, 5 wt% of ammonia water solution and butyl acrylate according to the mass ratio of 1:5.63:5.48, fully mixing the sulfur powder and the ammonia water solution to obtain mixed solution a, placing the butyl acrylate in a reaction kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred butyl acrylate, sealing, uniformly mixing, introducing hydrogen sulfide gas at the aeration speed of 325-395 g/h while stirring, keeping the temperature at 30-35 ℃, keeping the pressure at 0-1MPa, reacting for 30min, separating to obtain mixed ester, and recovering ammonia water in waste liquid by distillation; (b) preparing sodium sulfite solid, 5 wt% of ammonia water solution and the mixed ester obtained in the step (a) according to the mass ratio of 1:2.56:4.72, fully mixing the sodium sulfite solid and the ammonia water solution to obtain mixed solution b, adding the mixed solution b into the mixed ester obtained in the step (a), sealing, continuously stirring and heating, keeping the temperature at 60-65 ℃, keeping the pressure at 0-1MPa, cooling after 30min, separating the liquid in the kettle to obtain a crude dibutyl dithiodipropionate product with the content of 89%, purifying dibutyl dithiodipropionate to more than 99% by using a distillation device, recovering sodium thiosulfate in waste liquid by evaporation and crystallization, recovering the ammonia water in the waste liquid by distillation, and using the distilled dibutyl dithiodipropionate for the next reaction.

The chromatogram of the dibutyl dithiodipropionate standard is shown in FIG. 5, and the chromatogram of the dibutyl dithiodipropionate product prepared in this example is shown in FIG. 6.

EXAMPLE 4 preparation of the Compound Diisooctyl Dithiodipropionate

(a) Preparing sulfur powder, 5 wt% of ammonia water solution and isooctyl acrylate according to the mass ratio of 1:8.42:7.87, fully mixing the sulfur powder and the ammonia water solution to obtain mixed solution a, placing the isooctyl acrylate in a reaction kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred isooctyl acrylate, sealing, uniformly mixing, introducing hydrogen sulfide gas at the ventilation speed of 325-395 g/h while stirring, keeping the temperature at 45-50 ℃, keeping the pressure at 0.6-0.8MPa, reacting for 30min, separating to obtain mixed ester, and recovering the ammonia water in the waste liquid by distillation; (b) preparing sodium sulfite solid, 5 wt% of ammonia water solution and the mixed ester obtained in the step (a) according to the mass ratio of 1:2.56:6.78, fully mixing the sodium sulfite solid and the ammonia water solution to obtain mixed solution b, adding the mixed solution b into the mixed ester obtained in the step (a), sealing, continuously stirring and heating, keeping the temperature at 60-65 ℃, keeping the pressure at 0-1MPa, cooling after 30min, separating liquid in a kettle to obtain a crude diisooctyl dithiodipropionate product with the content of 84%, purifying the diisooctyl dithiodipropionate to more than 99% by a distillation device, recovering sodium thiosulfate in waste liquid by evaporation and crystallization, and recovering the ammonia water in the waste liquid by distillation for the next reaction.

The chromatogram of the diisooctyl dithiodipropionate standard sample is shown in FIG. 7, and the chromatogram of the diisooctyl dithiodipropionate product prepared in the example is shown in FIG. 8.