CN113603621B - Preparation method of mercaptopropionate series compounds - Google Patents
Preparation method of mercaptopropionate series compounds Download PDFInfo
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- CN113603621B CN113603621B CN202110901396.7A CN202110901396A CN113603621B CN 113603621 B CN113603621 B CN 113603621B CN 202110901396 A CN202110901396 A CN 202110901396A CN 113603621 B CN113603621 B CN 113603621B
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- C07—ORGANIC CHEMISTRY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention provides a preparation method of mercaptopropionate series compounds, which comprises the following steps: (a) Fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred raw material ester, wherein the raw material ester is R-S-S-R, R-S-S-S-R or a mixture of the raw material ester in any proportion, and R is-CH 2 CH 2 COOR 1 ，R 1 Is alkyl, stirring and heating, introducing hydrogen sulfide gas for pressurizing after the temperature is raised to 40-80 ℃, keeping the pressure at 0-1Mpa, and reacting for 20-40 min to obtain intermediate ester; (b) And (b) fully mixing the sodium sulfite solid with an ammonia solution to obtain a mixed solution b, adding the mixed solution b into the intermediate ester obtained in the step (a), continuously stirring and heating, introducing hydrogen sulfide gas for pressurizing after the temperature is raised to 40-80 ℃, keeping the pressure at 0-1Mpa, reacting for 20-40 min to obtain a crude mercaptopropionic acid ester product, and purifying to obtain the mercaptopropionic acid ester 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.
Description
Technical Field
The invention relates to a preparation method of mercaptopropionate series compounds, belonging to the field of compound preparation.
Background
The mercapto propionate series compound is one kind of important chemical material and organic solvent. For example, methyl mercaptopropionate is a good organic solvent and also an intermediate for the preparation of isothiazolinones; ethyl mercaptopropionate is used as a raw material of the spice; butyl mercaptopropionate is used as a processing aid for acrylic resin, styrene, neoprene and styrene-acrylic latex; isooctyl mercaptopropionate can be used as a plastic additive and has wide application. At present, the following two methods are mainly used for preparing the mercaptopropionic acid ester compounds:
(1) the synthesis of mercaptopropionic acid esters (CN 1185431A) by addition reaction of hydrogen sulfide and acrylate was carried out in the presence of a solid support functionalized with guanidine basic groups. The method has the disadvantages that the compounds with guanidine basic functional groups are not universal, the price is high, the required reaction conditions are harsh, the whole reaction steps are more, the operation is complex, and the method is not beneficial to industrial production.
(2) Hydrogen sulfide and S 2 R 2 Sodium sulfite is added in the reaction process to obtain mercaptopropionate compounds (CN 102675107A). The method has the disadvantages of long reaction time, low reaction yield and no contribution to large-scale industrial production.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of mercaptopropionic acid ester compounds, which is simple to operate, short in time, high in yield and easy for industrial production.
In order to achieve the purpose, the invention adopts the following technical means:
the invention provides a preparation method of mercaptopropionate series compounds, which comprises the following steps:
(a) Fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred raw material ester, wherein the raw material ester is R-S-S-R, R-S-S-S-R or a mixture of the raw material ester in any proportion, and R is-CH 2 CH 2 COOR 1 ，R 1 Is alkyl, stirring and heating, introducing hydrogen sulfide gas for pressurizing after the temperature is raised to 40-80 ℃, keeping the pressure at 0-1Mpa, and reacting for 20-40 min to obtain intermediate ester; (b) And (2) fully mixing the sodium sulfite solid with an ammonia solution to obtain a mixed solution b, adding the mixed solution b into the intermediate ester obtained in the step (a), continuously stirring and heating, introducing hydrogen sulfide gas to pressurize after the temperature is increased to 40-80 ℃, keeping the pressure at 0-1Mpa, reacting for 20-40 min to obtain a crude mercaptopropionic acid ester product, and purifying to obtain the mercaptopropionic acid ester product.
Further, theR 1 Is an alkyl group containing 1 to 8 carbon atoms, including but not limited to-CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、-C 7 H 15 or-C 8 H 17 。
Further, the concentration of each of the aqueous ammonia solutions is 0.1wt% to 25wt%; preferably, the concentration of each of the aqueous ammonia solutions is 10wt%.
Further, in step (a), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1.31 and 1; in step (b), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1.31 and 1.
Further, the mass ratio of the raw ester to the mixed liquor a is between 1.46 and 1.16, and the mass ratio of the intermediate ester to the mixed liquor b is between 1.46 and 1.16.
Further, the time for each of the reactions was 30min.
Further, the temperature of each of the reactions is 55 ℃ to 60 ℃.
Further, the pressure of each of the reactions was 0.4MPa.
Further, the crude mercaptopropionic acid ester product is distilled and purified to obtain a mercaptopropionic acid ester product and waste liquid, ammonia water in the waste liquid is recovered through distillation, and sodium thiosulfate in the waste liquid is recovered through evaporation and crystallization.
Further, each reaction is carried out in an autoclave or a pipe-type continuous reactor.
Further, the pressurization of each reaction needs to be completed quickly to ensure the reaction efficiency.
Compared with the prior art, the invention has the following advantages:
(1) the method has the advantages of simple synthetic route, greatly shortened reaction time, improved reaction yield, improved overall efficiency, suitability for high-pressure kettles or pipeline type continuous reactors, simple operation, low cost and easy industrial production.
(2) The waste liquid produced by the invention can be recovered without waste discharge.
Drawings
FIG. 1 is a chromatogram of a methyl mercaptopropionate standard;
FIG. 2 is a chromatogram of the methyl mercaptopropionate product prepared in example 1 of the present invention;
FIG. 3 is a chromatogram of a reference sample of ethyl mercaptopropionate;
FIG. 4 is a chromatogram of the ethyl mercaptopropionate product prepared in example 2 of the present invention;
FIG. 5 is a chromatogram of a butyl mercaptopropionate standard;
FIG. 6 is a chromatogram of butyl mercaptopropionate product prepared in example 3 of the present invention;
FIG. 7 is a chromatogram of isooctyl mercaptopropionate standard sample;
FIG. 8 is a chromatogram of the isooctyl mercaptopropionate 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 substitutions are intended to be within the scope of the invention.
EXAMPLE 1 preparation of methyl mercaptopropionate Compound
(a) A sodium sulfite solid, a 10wt% aqueous ammonia solution and a raw material ester in which the mass of R-S-S-R is 33.7% and the mass of R-S-S-R is 66.3% were prepared in a mass ratio of 1.62 2 CH 2 COOCH 3 (ii) a Fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution a, putting raw material ester into an autoclave with a stirrer and a thermometer, adding the mixed solution a into the stirred raw material ester, sealing, stirring and heating to 55-60 ℃, quickly introducing hydrogen sulfide gas into the autoclave for pressurizing, keeping the pressure at 0.4Mpa, and reactingExhausting and cooling after 30min, and standing and separating liquid in the kettle to obtain intermediate ester; (b) Preparing sodium sulfite solid, 10wt% of ammonia water solution and the intermediate ester obtained in the step (a) according to the mass ratio of 1.62.
The chromatogram of the methyl mercaptopropionate standard sample is shown in figure 1, and the chromatogram of the methyl mercaptopropionate product prepared in this example is shown in figure 2.
EXAMPLE 2 preparation of the Compound Ethyl mercaptopropionate
(a) A sodium sulfite solid, a 10wt% ammonia aqueous solution and a raw material ester in which the mass of R-S-S-R is 60.2% and the mass of R-S-S-R is 39.8% were prepared in a mass ratio of 1.62 2 CH 2 COOC 2 H 5 (ii) a Fully mixing sodium sulfite solid and an ammonia water solution to obtain a mixed solution a, putting raw material ester into a high-pressure kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred raw material ester, sealing, stirring and heating to 55-60 ℃, quickly introducing hydrogen sulfide gas into the kettle to pressurize, keeping the pressure at 0.4MPa, discharging gas and cooling after reacting for 30min, and standing and separating liquid in the kettle to obtain intermediate ester; (b) Preparing a sodium sulfite solid, a 10wt% ammonia water solution and the intermediate ester obtained in the step (a) according to the mass ratio of 1.62% of the crude ethyl mercaptopropionate, purifying the ethyl mercaptopropionate to over 99% by a distillation device, recovering ammonia water in waste liquid by distillation, and recovering sodium thiosulfate in the waste liquid by evaporation crystallization for the next reaction.
The chromatogram of the ethyl mercaptopropionate standard sample is shown in FIG. 3, and the chromatogram of the ethyl mercaptopropionate product prepared in this example is shown in FIG. 4.
EXAMPLE 3 preparation of the Compound butyl mercaptopropionate
(a) Sodium sulfite solid, 10wt% aqueous ammonia solution and a raw material ester in which the mass of R-S-S-R was 75.4% and the mass of R-S-S-R was 24.6% were prepared in a mass ratio of 1:1.62 2 CH 2 COOC 4 H 9 (-C 4 H 9 Is n-butyl); fully mixing sodium sulfite solid and an ammonia water solution to obtain a mixed solution a, placing raw material ester into a high-pressure kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred raw material ester, sealing, stirring and heating to 55-60 ℃, quickly introducing hydrogen sulfide gas into the kettle for pressurizing, keeping the pressure at 0.4Mpa, exhausting and cooling after reacting for 30min, and standing and separating liquid in the kettle to obtain intermediate ester; (b) Preparing a sodium sulfite solid, a 10wt% ammonia water solution and the intermediate ester obtained in the step (a) according to a mass ratio of 1.62.
The chromatogram of the butyl mercaptopropionate standard sample is shown in FIG. 5, and the chromatogram of the butyl mercaptopropionate product prepared in this example is shown in FIG. 6.
EXAMPLE 4 preparation of isooctyl mercaptopropionate
(a) A sodium sulfite solid, a 10wt% aqueous ammonia solution and a starting ester in which the mass of R-S-S-R was 54.6% and the mass of R-S-S-R was 45.4% were prepared in a mass ratio of 1.62 2 CH 2 COOC 8 H 17 (-C 8 H 17 Is isooctyl); fully mixing sodium sulfite solid and an ammonia water solution to obtain a mixed solution a, putting raw material ester into a high-pressure kettle with a stirrer and a thermometer, adding the mixed solution a into the stirred raw material ester, sealing, stirring and heating to 55-60 ℃, quickly introducing hydrogen sulfide gas into the kettle to pressurize, keeping the pressure at 0.4MPa, discharging gas and cooling after reacting for 30min, and standing and separating liquid in the kettle to obtain intermediate ester; (b) Preparing sodium sulfite solid, 10wt% of ammonia water solution and the intermediate ester obtained in the step (a) according to the mass ratio of 1.62.
The chromatogram of the isooctyl mercaptopropionate standard sample is shown in FIG. 7, and the chromatogram of the isooctyl mercaptopropionate product prepared in this example is shown in FIG. 8.
Claims (11)
1. A preparation method of mercaptopropionate series compounds is characterized by comprising the following steps:
(a) Fully mixing the sodium sulfite solid with an ammonia water solution to obtain a mixed solution a, adding the mixed solution a into stirred raw material ester, wherein the raw material ester is R-S-S-R, R-S-S-S-R or a mixture of the raw material ester in any proportion, and R is-CH 2 CH 2 COOR 1 ，R 1 Is alkyl, is stirred and heated up, and is heated to 40-80 DEG CIntroducing hydrogen sulfide gas to pressurize, keeping the pressure at 0-1Mpa, reacting for 20-40 min to obtain intermediate ester; (b) And (2) fully mixing the sodium sulfite solid with an ammonia solution to obtain a mixed solution b, adding the mixed solution b into the intermediate ester obtained in the step (a), continuously stirring and heating, introducing hydrogen sulfide gas to pressurize after the temperature is increased to 40-80 ℃, keeping the pressure at 0-1Mpa, reacting for 20-40 min to obtain a crude mercaptopropionic acid ester product, and purifying to obtain the mercaptopropionic acid ester product.
2. The method of claim 1, wherein R is 1 Is an alkyl group having 1 to 8 carbon atoms.
3. The method according to claim 1, wherein the concentration of each of the aqueous ammonia solutions is 0.1wt% to 25wt%.
4. The production method according to claim 3, wherein the concentration of each of the aqueous ammonia solutions is 10wt%.
5. The process according to claim 1, characterized in that in step (a), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1; in step (b), the mass ratio of the sodium sulfite to the aqueous ammonia solution is between 1.31 and 1.
6. The preparation method according to claim 1, wherein the mass ratio of the raw ester to the mixed solution a is 1.46 to 1.16, and the mass ratio of the intermediate ester to the mixed solution b is 1.
7. The production method according to claim 1, wherein the time for each reaction is 30min.
8. The method of claim 1, wherein the temperature of each reaction is 55 ℃ to 60 ℃.
9. The method of claim 1, wherein the pressure of each reaction is 0.4Mpa.
10. The preparation method according to claim 1, wherein the crude mercaptopropionic acid ester product is distilled and purified to obtain a mercaptopropionic acid ester product and a waste liquid, ammonia water in the waste liquid is recovered by distillation, and sodium thiosulfate in the waste liquid is recovered by evaporation and crystallization.
11. The method according to claim 1, wherein each reaction is carried out in an autoclave or a pipe-type continuous reactor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675170A (en) * | 2011-03-08 | 2012-09-19 | 北京天擎化工有限公司 | Preparation of 3-mercaptopropionate |
| CN113004177A (en) * | 2021-03-16 | 2021-06-22 | 靳浩田 | Continuous production method of 3-mercaptopropionic acid alkyl ester and 3, 3' -trithiodipropionic acid dialkyl ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675170A (en) * | 2011-03-08 | 2012-09-19 | 北京天擎化工有限公司 | Preparation of 3-mercaptopropionate |
| CN113004177A (en) * | 2021-03-16 | 2021-06-22 | 靳浩田 | Continuous production method of 3-mercaptopropionic acid alkyl ester and 3, 3' -trithiodipropionic acid dialkyl ester |
Non-Patent Citations (1)
| Title |
|---|
| Hyperbranched Polymers with High Degrees of Branching and Low Dispersity Values: Pushing the Limits of Thiol−Yne Chemistry;Alexander B. Cook,等;《Macromolecules》;20160202;第49卷;1296-1304 * |
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