CN105085335A - Method for preparing 3-mercapto-propionate - Google Patents
Method for preparing 3-mercapto-propionate Download PDFInfo
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- CN105085335A CN105085335A CN201510569558.6A CN201510569558A CN105085335A CN 105085335 A CN105085335 A CN 105085335A CN 201510569558 A CN201510569558 A CN 201510569558A CN 105085335 A CN105085335 A CN 105085335A
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Abstract
A method for preparing 3-mercapto-propionate is as below: subjecting a main raw material of 3-mercaptopropionic acid and an alcohol compound to a heating esterification reaction in the presence of an acidic catalyst to prepare a 3-mercaptopropionic acid ester compound crude product; and then extracting and purifying the target product by using the differences in solubility of 3-mercaptopropionate and 3-mercaptopropionic acid residue and catalyst to choose the appropriate solvent. Compared with the prior art, the invention has the beneficial effects that the preparation process of 3-mercaptopropionic ester avoids the defects of dangerous operation of hydrogen sulfide introduction under high pressure and difficult treatment of wastewater in the traditional production process of 3-mercaptopropionate. The method provided by the invention is a green chemical synthesis method, which has no pollution and high raw material utilization rate.
Description
Technical field
The present invention relates to a kind of industrial chemicals for the production of fields such as high-performance epoxy resin solidifying agent and urethane high refractive index optical materials, the production method of 3-mercaptopropionic acid ester specifically.
Background technology
3-mercaptopropionic acid ester has been widely used in producing the field such as high-performance epoxy resin solidifying agent and urethane high refractive index optical material as a kind of sulfydryl class raw material monomer, but the ordinary method of synthesis 3-mercaptopropionic acid ester is because reaction needed is carried out in autoclave, higher to equipment requirements, and pass into gas under elevated pressure conditions, there is certain danger, and complicated operation, the defects such as industrialization difficulty is comparatively large, and the technique of traditional mode of production 3-thiohydracrylic acid ester compound exists that trade effluent is many in addition, catalyzer and excess raw material cannot reuse.
Patent 97126452.X describes one and has under the existence of basic guanidine functional group solid carrier, the method of 3-mercaptopropionic acid ester is synthesized by the addition reaction of hydrogen sulfide and vinylformic acid corresponding esters, because using vinylformic acid in this technique, more serious to equipment corrosion, simultaneously because the hydrogen sulfide used is hypertoxic gas, operational hazards coefficient is higher, and industrialization difficulty is larger.
Patent CN102675170 reports a kind of under S-WAT existent condition, by hydrogen sulfide and 3, the method of 3-mercaptopropionic acid ester is prepared in the reaction of 3-dithio dipropyl dimethyl phthalate, in the prior art, yield is lower, in addition because the use of hypertoxic gas vulcanization hydrogen also makes operation have certain danger.
In a word, produce the method complex process of 3-mercaptopropionic acid ester at present, discharged volume of industrial waste water is large, yield is low.
Summary of the invention
The technical problem that the present invention mainly solves overcomes above-mentioned prior art Problems existing, provides a kind of preparation method of pollution-free, simple to operate, 3-mercaptopropionic acid ester that raw material availability is high.
The technical solution used in the present invention is for achieving the above object: with 3-thiohydracrylic acid for main raw material and alcohol compound are under an acidic catalyst effect, heating is carried out esterification and is prepared 3-thiohydracrylic acid ester compound crude product, then utilize the solvability difference of 3-mercaptopropionic acid ester and residual raw materials 3-thiohydracrylic acid and catalyzer, select suitable extraction solvent to carry out separating-purifying to target product; The preparation method of a kind of 3-mercaptopropionic acid ester of the present invention, is characterized in that: the preparation method of 3-mercaptopropionic acid ester comprises the following steps:
A) in the enamel reaction still being provided with stirrer, reflux cooling water separator, thermometer, raw material 3-thiohydracrylic acid is added, mol ratio according to 1:0.004 ~ 0.005 adds catalyzer, then the water entrainer of raw material weight 20 ~ 25% is added, open and stir catalyst dissolution, according to 1:0.23 ~ 1 after catalyst dissolution is complete, mol ratio alcohol compound is added in reaction solution, heating, reflux at 110 DEG C, in reaction process, the water of generation is discharged outside system continuously, no longer include after moisture goes out, stopped reaction, cooling, is cooled to room temperature;
Wherein catalyzer is tosic acid;
Wherein water entrainer is toluene;
Wherein alcohol compound is CH
3oH
B) after being cooled to room temperature, the water entrainer adding raw material weight 17% in reaction solution dilutes, and obtains reactant crude product;
Wherein water entrainer is toluene;
C) reactant crude product is placed in enamel still, washs three times with alkaline solution, each alkaline solution consumption is 25% of reactant crude product amount, and collect organic phase, then with distilled water, organic phase is washed three times, each distilled water consumption is 17% of organic phasor, obtains clean organic phase;
Wherein alkaline solution is saturated sodium bicarbonate solution;
D) clean organic phase underpressure distillation is removed the water of water entrainer and trace, obtain 3-mercaptopropionic acid ester.
According to the preparation method of above-described a kind of 3-mercaptopropionic acid ester, it is characterized in that: described alcohol compound is CH
3oH, C
6h
14o
3, C
5h
12o
4in one.
The present invention solidifies by photocuring reaction synthesis UV the application performance that glue tests 3-mercaptopropionic acid ester prepared by the present invention, and concrete synthetic method is as follows:
According to formula, a certain amount of benzophenone, 3-mercaptopropionic acid ester, acrylate, Resorcinol are added in beaker under lucifuge condition, stirring makes entirely molten, then puts into baking oven, and ambient temperature in vacuum is dry till bubble-free, sealed by material after drying terminates, low temperature lower seal is preserved.
Characterized by the solidification glue of thermogravimetic analysis (TGA) method to synthesis, find that temperature is 426.5 DEG C when thermal weight loss rate is 5%, illustrate that the 3-mercaptopropionic acid ester that the present invention synthesizes and the UV curing system that alkene is formed have higher resistance toheat, the service requirements of sizing agent can be met.
Gordian technique of the present invention is the control of the esterification process of 3-mercaptopropionic acid ester, esterification is the organic reaction of class classics, reaction generates ester and water, this reaction is a balanced reaction, the ester generated can be hydrolyzed to alcohol and acid again under the catalysis of strong acid, move to the direction generating ester to make reaction, the water of generation must be removed in reaction process, balance is moved right, obtain the product that transformation efficiency is higher, the main method dewatered in the present invention is by adding water entrainer backflow, water entrainer and water is made to form azeotrope, recycling water entrainer is separated with density difference with the immiscible property of water, improve reaction efficiency.
The water entrainer selected in preparation method of the present invention is toluene, by controlling the amount of toluene, making temperature of reaction and a point water yield all reach optimum value, ensureing yield and the purity of product.
The present invention's beneficial effect is compared with prior art:
The risky operation, the factory effluent that pass into hydrogen sulfide under the technique that the present invention prepares 3-mercaptopropionic acid ester avoids traditional mode of production 3-mercaptopropionic acid ester technique mesohigh are difficult to the defects such as process, are a kind of green chemical synthesis method of pollution-free, 3-mercaptopropionic acid ester that raw material availability is high.
Embodiment
Embodiment 1
A preparation method for 3-mercaptopropionic acid ester, comprises the following steps:
A) in the 3000L enamel reaction still being provided with stirrer, reflux cooling water separator, thermometer, 3-thiohydracrylic acid 700kg is added, add the agent of 17.4kg Catalyzed by p-Toluenesulfonic Acid, then 480kg toluene is added, open to stir and acid catalyst is dissolved, by 211kg alcohol compound CH after catalyst dissolution is complete
3oH is added in reaction solution, heating, refluxes, discharged continuously outside system by the water of generation in reaction process at 110 DEG C, and no longer include after moisture goes out, stopped reaction, cooling, is cooled to room temperature;
B) reaction terminates, and after being cooled to room temperature, adding 400kg toluene and dilutes, obtain reactant crude product in reaction solution;
C) reactant crude product is placed in 3000L enamel still, washs three times with saturated sodium bicarbonate solution, each saturated sodium bicarbonate solution consumption is 600L, collect organic phase, finally with distilled water, organic phase is washed three times, each distilled water consumption is 400L, obtains clean organic phase;
D) water of underpressure distillation removing water entrainer and trace, obtains 3-mercaptopropionic acid ester.
3-mercaptopropionic acid ester yield is 86.7%, and adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 97.8%.
Embodiment 2
A preparation method for 3-mercaptopropionic acid ester, comprises the following steps:
A) in the 3000L enamel reaction still being provided with stirrer, reflux cooling water separator, thermometer, 3-thiohydracrylic acid 700kg is added, add the agent of 15kg Catalyzed by p-Toluenesulfonic Acid, then 480kg toluene is added, open to stir and acid catalyst is dissolved, by 204kg alcohol compound C after catalyst dissolution is complete
6h
14o
3be added in reaction solution, heating, reflux, discharged continuously outside system by the water of generation in reaction process at 110 DEG C, no longer include after moisture goes out, stopped reaction, cooling, is cooled to room temperature;
B) reaction terminates, and after being cooled to room temperature, adding 400kg toluene and dilutes, obtain reactant crude product in reaction solution;
C) reactant crude product is placed in 3000L enamel still, washs three times with saturated sodium bicarbonate solution, each saturated sodium bicarbonate solution consumption is 600L, and collect organic phase, finally with distilled water, organic phase is washed three times, each distilled water consumption is 400L;
D) clean organic phase underpressure distillation is removed the water of water entrainer and trace, obtain 3-mercaptopropionic acid ester.
3-mercaptopropionic acid ester yield is 65.3%, and adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 82.5%.
Embodiment 3
A preparation method for 3-mercaptopropionic acid ester, comprises the following steps:
A) in the 3000L enamel reaction still being provided with stirrer, reflux cooling water separator, thermometer, 3-thiohydracrylic acid 700kg is added, add the agent of 17.4kg Catalyzed by p-Toluenesulfonic Acid, then 300kg toluene is added, open to stir and acid catalyst is dissolved, by 224kg alcohol compound C after catalyst dissolution is complete
5h
12o
4be added in reaction solution, heating, reflux, discharged continuously outside system by the water of generation in reaction process at 110 DEG C, no longer include after moisture goes out, stopped reaction, cooling, is cooled to room temperature;
B) reaction terminates, and after being cooled to room temperature, adding 400kg toluene and dilutes, obtain reactant crude product in reaction solution;
C) reactant crude product is placed in 3000L enamel still, washs three times with saturated sodium bicarbonate solution, each saturated sodium bicarbonate solution consumption is 600L, and collect organic phase, finally with distilled water, organic phase is washed three times, each distilled water consumption is 400L.
E) clean organic phase underpressure distillation is removed the water of water entrainer and trace, obtain 3-mercaptopropionic acid ester.
Product yield is 48.9%, and adopt high performance liquid chromatography to analyze compound chromatographic purity, quantitative with normalization method, the content of main peak is 76.8%.
The risky operation, the factory effluent that pass into hydrogen sulfide under the technique that the present invention prepares 3-mercaptopropionic acid ester avoids traditional mode of production 3-mercaptopropionic acid ester technique mesohigh are difficult to the defects such as process, are a kind of green chemical synthesis method of pollution-free, 3-mercaptopropionic acid ester that raw material availability is high.
Claims (2)
1. a preparation method for 3-mercaptopropionic acid ester, is characterized in that: the preparation method of 3-mercaptopropionic acid ester comprises the following steps:
A) in the enamel reaction still being provided with stirrer, reflux cooling water separator, thermometer, raw material 3-thiohydracrylic acid is added, mol ratio according to 1:0.004 ~ 0.005 adds catalyzer, then the water entrainer of raw material weight 20 ~ 25% is added, open and stir catalyst dissolution, according to 1:0.23 ~ 1 after catalyst dissolution is complete, mol ratio alcohol compound is added in reaction solution, heating, reflux at 110 DEG C, in reaction process, the water of generation is discharged outside system continuously, no longer include after moisture goes out, stopped reaction, cooling, is cooled to room temperature;
Wherein catalyzer is tosic acid;
Wherein water entrainer is toluene;
Wherein alcohol compound is CH
3oH
B) after being cooled to room temperature, the water entrainer adding raw material weight 17% in reaction solution dilutes, and obtains reactant crude product;
Wherein water entrainer is toluene;
C) reactant crude product is placed in enamel still, washs three times with alkaline solution, each alkaline solution consumption is 25% of reactant crude product amount, and collect organic phase, then with distilled water, organic phase is washed three times, each distilled water consumption is 17% of organic phasor, obtains clean organic phase;
Wherein alkaline solution is saturated sodium bicarbonate solution;
D) clean organic phase underpressure distillation is removed the water of water entrainer and trace, obtain 3-mercaptopropionic acid ester.
2. the preparation method of a kind of 3-mercaptopropionic acid ester according to claim 1, is characterized in that: described alcohol compound is CH
3oH, C
6h
14o
3, C
5h
12o
4in one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200699A (en) * | 2017-06-30 | 2017-09-26 | 重庆天原化工有限公司 | A kind of esterification process and its application |
| CN110256311A (en) * | 2019-05-24 | 2019-09-20 | 潍坊加华化工有限公司 | A kind of methyl thioglycolate process for refining |
| CN110845376A (en) * | 2019-11-25 | 2020-02-28 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol mercaptocarboxylic ester |
| CN112521319A (en) * | 2020-12-15 | 2021-03-19 | 山东理工大学 | Method for preparing methyl thioglycolate in molten salt hydrate |
Citations (1)
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| CN104053646A (en) * | 2012-01-27 | 2014-09-17 | 可奥熙搜路司有限公司 | Method for producing 3-mercaptopropionic acid, and carbonic acid ester composition having mercapto group using same, and method for producing thiourethane-based optical materials |
-
2015
- 2015-09-10 CN CN201510569558.6A patent/CN105085335A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104053646A (en) * | 2012-01-27 | 2014-09-17 | 可奥熙搜路司有限公司 | Method for producing 3-mercaptopropionic acid, and carbonic acid ester composition having mercapto group using same, and method for producing thiourethane-based optical materials |
Non-Patent Citations (3)
| Title |
|---|
| 周艳阳，等: "一种巯基酯类光敏胶单体的合成及其性能研究", 《中国胶粘剂》 * |
| 康富春，等: "硫醇固化剂的合成和应用", 《热固性树脂》 * |
| 彭东明，等: "巯基化合物的合成及应用于环氧甲基丙烯酸酯的紫外光固化研究", 《中南大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200699A (en) * | 2017-06-30 | 2017-09-26 | 重庆天原化工有限公司 | A kind of esterification process and its application |
| CN110256311A (en) * | 2019-05-24 | 2019-09-20 | 潍坊加华化工有限公司 | A kind of methyl thioglycolate process for refining |
| CN110845376A (en) * | 2019-11-25 | 2020-02-28 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol mercaptocarboxylic ester |
| CN110845376B (en) * | 2019-11-25 | 2022-01-04 | 益丰新材料股份有限公司 | Preparation method of pentaerythritol mercaptocarboxylic ester |
| CN112521319A (en) * | 2020-12-15 | 2021-03-19 | 山东理工大学 | Method for preparing methyl thioglycolate in molten salt hydrate |
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Application publication date: 20151125 |