CN111620836A - Method for refining 2-mercaptobenzothiazole - Google Patents
Method for refining 2-mercaptobenzothiazole Download PDFInfo
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- CN111620836A CN111620836A CN202010579092.9A CN202010579092A CN111620836A CN 111620836 A CN111620836 A CN 111620836A CN 202010579092 A CN202010579092 A CN 202010579092A CN 111620836 A CN111620836 A CN 111620836A
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- mercaptobenzothiazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
A method for refining 2-mercaptobenzothiazole relates to the technical field of refining of an accelerant M, and comprises the steps of reducing crude 2-mercaptobenzothiazole synthesized by an aniline method under high pressure to 100-200 ℃, mixing with toluene, cooling for crystallization under stirring, and separating to obtain a semi-finished product of the 2-mercaptobenzothiazole; and (3) mixing the semi-finished product of the 2-mercaptobenzothiazole with a sodium sulfite solution, heating, stirring, refluxing for 1-2 hours, cooling to room temperature, and filtering to obtain the finished product of the 2-mercaptobenzothiazole. The invention has the beneficial effects that: the method combines solvent crystallization and deep impurity removal, has high product yield and purity, solves the problem of purification and refining of the current 2-mercaptobenzothiazole, makes up for the shortage of the market, develops a new technological route for producing the high-purity 2-mercaptobenzothiazole, and solves the shortage of the high-purity 2-mercaptobenzothiazole in the current market.
Description
Technical Field
The invention relates to the technical field of refining of an accelerator M, and particularly relates to a method for refining 2-mercaptobenzothiazole.
Background
The 2-mercaptobenzothiazole is called as an accelerator M, is one of the largest varieties of rubber vulcanization accelerators at home and abroad in production and sale quantity, is also a parent for producing and synthesizing other post-effect accelerators (such as CBS, NS, DM, DZ, DS, NOBS, DIBS and the like), has wide application and maximum consumption, and also has special application in electrochemistry and the like, wherein the chemical plasticizer, the metal corrosion inhibitor, the mineral flotation agent, the resin modifier, the polymer initiator, the precious metal extractant, the lubricant and the adsorbent. In addition, it is also useful for the synthesis of pharmaceutical intermediates, such as 2-methylthiobenzothiazole, 2-ethylthiobenzothiazole, mefenacet, and the like.
The purity of the 2-mercaptobenzothiazole directly influences the application effect of the 2-mercaptobenzothiazole, and particularly, the 2-mercaptobenzothiazole with low purity is used as a raw material for synthesizing other vulcanization accelerators and medical intermediates, so that the yield of the product is reduced, and unnecessary troubles are brought to the subsequent process due to the increase of side reactions. It is worth mentioning that the price of the high-purity 2-mercaptobenzothiazole is about 10 times of the common price.
At present, the synthesis of the accelerator M basically adopts an aniline route, but the purity of the 2-mercaptobenzothiazole crude product produced by the method is low, about 15-20 percent of components are not the accelerator M, and the tar content is large; impurities in the product include: benzothiazole, anilinobenzothiazole, phenylisothiocyanate, diphenylthiourea, and the like, and aniline, sulfur, and resins having an unknown structure, which are not completely reacted, are collectively referred to as waste resins.
Therefore, 2-mercaptobenzothiazole produced by the aniline method needs to be separated and purified for use, and the most used methods at present are an alkali-dissolution acid-precipitation method and an organic solvent method. It has also been reported that 2-mercaptobenzothiazole is further purified by a method combining an improved alkali dissolution and acid precipitation method and an organic solvent, or by methods of adding activated carbon for decolorization, macroporous resin adsorption, hydrogen peroxide oxidation and the like. Although many reports exist on the purification of 2-mercaptobenzothiazole, the process is usually complicated, the operation is complex and the implementation is difficult.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for refining 2-mercaptobenzothiazole, which takes crude 2-mercaptobenzothiazole synthesized by an aniline method under high pressure as a raw material, adopts a method combining solvent crystallization and deep impurity removal, can obtain high-purity 2-mercaptobenzothiazole, and is simple and easy to implement.
The invention provides a method for refining 2-mercaptobenzothiazole, which comprises the following procedures; step one, a solvent crystallization preliminary impurity removal process, namely reducing the temperature of crude 2-mercaptobenzothiazole synthesized by an aniline method under high pressure to 100-200 ℃, mixing the crude 2-mercaptobenzothiazole with toluene, cooling and crystallizing under stirring, and separating to obtain a semi-finished 2-mercaptobenzothiazole product;
and secondly, a deep impurity removal process, namely mixing the semi-finished product of the 2-mercaptobenzothiazole with a sodium sulfite solution, heating, stirring, refluxing for 1-2 hours, cooling to room temperature, and filtering to obtain the finished product of the 2-mercaptobenzothiazole.
In the first step, the dosage of the toluene is as follows: adding 1.5-3L of toluene into each kilogram of crude product 2-mercaptobenzothiazole;
in the first step, the temperature is reduced to 20-60 ℃ under stirring, the mixture is divided into a solid phase and a liquid phase, the liquid phase is toluene and impurities dissolved in the toluene, the solid phase is 2-mercaptobenzothiazole, the solid phase is sent to a scraper type centrifuge to remove a solvent, and then the toluene solvent is added for washing, so that the 2-mercaptobenzothiazole is further purified; vacuum drying for 1.5h to obtain 2-mercaptobenzothiazole semi-finished product, and distilling the mother liquor to recover toluene for recycling.
In the second step, the mass concentration of the sodium sulfite solution is 5-8%, and the using amount of the sodium sulfite is 12-16% of the mass of the 2-mercaptobenzothiazole semi-finished product; and cooling to room temperature, filtering, preparing sodium thiosulfate from the filtered mother liquor, and washing the filter cake with water to obtain the finished product of 2-mercaptobenzothiazole.
The sodium sulfite can also be replaced by sodium metabisulfite or potassium metabisulfite, sodium sulfite potassium double salt (NaKSO)3) Potassium ammonium sulfite double salt (KNH)4SO3) Sodium ammonium sulfite double salt (NaNH)4SO3）。
The invention has the beneficial effects that: the high-purity 2-mercaptobenzothiazole is obtained by adopting a method combining solvent crystallization and deep impurity removal. The product obtained by the method has high yield, high purity, good safety and environment-friendly crystallization solvent; the factors of yield, purity, environmental safety, production safety, toxicity and the like are fully considered.
The process meets the quality standard requirements of developing downstream products, solves the problem of purification and refining of the current 2-mercaptobenzothiazole, makes up for the shortage of the market, and develops a new process technical route for producing high-purity 2-mercaptobenzothiazole. Solving the shortage of high-purity 2-mercaptobenzothiazole in the current market.
Detailed Description
Example 1, the present invention provides a method for purifying 2-mercaptobenzothiazole, comprising the steps of,
firstly, primarily removing impurities by solvent crystallization, cooling crude 2-mercaptobenzothiazole synthesized by aniline high-pressure reaction to 200 ℃, conveying the crude 2-mercaptobenzothiazole to a pretreatment solvent crystallization kettle through a pipeline, fully mixing and dissolving the crude 2-mercaptobenzothiazole with toluene, adding 3L of toluene into 1Kg of crude 2-mercaptobenzothiazole, stirring, cooling to 60 ℃, dividing the mixture into a solid phase and a liquid phase, wherein the liquid phase is toluene and dissolved impurities thereof, the solid phase is 2-mercaptobenzothiazole, conveying the solid phase to a scraper type centrifuge to remove the solvent, adding a toluene solvent for washing, and further purifying the 2-mercaptobenzothiazole; vacuum drying for 1.5h to obtain a semi-finished product of the 2-mercaptobenzothiazole, wherein the yield is 70.24 percent and the purity is 98.86 percent; and distilling the mother liquor to recover the toluene.
And secondly, deeply removing impurities, mixing the 2-mercaptobenzothiazole semi-finished product with a sodium sulfite solution with the mass concentration of 8%, wherein the amount of the sodium sulfite is 0.16 times of that of the 2-mercaptobenzothiazole semi-finished product, heating, stirring, refluxing and reacting for 2 hours, cooling to room temperature, filtering, preparing sodium thiosulfate from mother liquor, washing a filter cake to obtain the finished product of 2-mercaptobenzothiazole, wherein the yield is 97.20%, and the purity is 99.89%.
Example 2, the present invention provides a method for purifying 2-mercaptobenzothiazole, comprising the steps of,
firstly, primarily removing impurities by solvent crystallization, cooling crude 2-mercaptobenzothiazole synthesized by aniline high-pressure reaction to 150 ℃, conveying the crude 2-mercaptobenzothiazole to a pretreatment solvent crystallization kettle through a pipeline, fully mixing and dissolving the crude 2-mercaptobenzothiazole with toluene, adding 2L of toluene into 1Kg of crude product, stirring, reducing the temperature for crystallization, cooling to 40 ℃, dividing the crude product into a solid phase and a liquid phase, wherein the liquid phase is toluene and dissolved impurities thereof, the solid phase is 2-mercaptobenzothiazole, conveying the solid phase to a scraper type centrifuge for removing the solvent, adding a toluene solvent for washing, and further purifying the 2-mercaptobenzothiazole; vacuum drying for 1.5h to obtain a semi-finished product of the 2-mercaptobenzothiazole, wherein the yield is 84.49 percent, and the purity is 98.12 percent; and distilling the mother liquor to recover the toluene.
And secondly, deeply removing impurities, mixing the 2-mercaptobenzothiazole semi-finished product with a sodium sulfite solution with the mass concentration of 6.5%, wherein the amount of the sodium sulfite is 0.14 times of that of the 2-mercaptobenzothiazole semi-finished product, heating, stirring, refluxing and reacting for 1.5 hours, cooling to room temperature, filtering, preparing sodium thiosulfate from mother liquor, washing a filter cake to obtain the finished product 2-mercaptobenzothiazole, wherein the yield is 97.35%, and the purity is 99.88%.
Example 3, the present invention provides a method for purifying 2-mercaptobenzothiazole, comprising the steps of,
firstly, primarily removing impurities by solvent crystallization, cooling crude 2-mercaptobenzothiazole synthesized by aniline high-pressure reaction to 100 ℃, conveying the crude 2-mercaptobenzothiazole to a pretreatment solvent crystallization kettle through a pipeline, fully mixing and dissolving the crude 2-mercaptobenzothiazole with toluene, adding 1.5L of toluene into 1Kg of crude 2-mercaptobenzothiazole, stirring, cooling to 20 ℃, separating into a solid phase and a liquid phase, wherein the liquid phase is toluene and dissolved impurities thereof, the solid phase is 2-mercaptobenzothiazole, conveying the solid phase to a scraper type centrifuge to remove the solvent, adding a toluene solvent for washing, and further purifying the 2-mercaptobenzothiazole; vacuum drying for 1.5h to obtain a semi-finished product of the 2-mercaptobenzothiazole, wherein the yield is 89.77 percent, and the purity is 97.95 percent; and distilling the mother liquor to recover the toluene.
And secondly, deeply removing impurities, mixing the 2-mercaptobenzothiazole semi-finished product with a sodium sulfite solution with the mass concentration of 5-8%, wherein the amount of the sodium sulfite is 0.12 times of that of the 2-mercaptobenzothiazole semi-finished product, heating, stirring, refluxing and reacting for 1 hour, cooling to room temperature, filtering, preparing sodium thiosulfate from mother liquor, washing a filter cake to obtain the finished product of 2-mercaptobenzothiazole, wherein the yield is 97.34%, and the purity is 99.98%.
Claims (5)
1. A method for purifying 2-mercaptobenzothiazole, which is characterized by comprising the following steps:
step one, a solvent crystallization preliminary impurity removal process, namely reducing the temperature of crude 2-mercaptobenzothiazole synthesized by an aniline method under high pressure to 100-200 ℃, mixing the crude 2-mercaptobenzothiazole with toluene, cooling and crystallizing under stirring, and separating to obtain a semi-finished 2-mercaptobenzothiazole product;
and secondly, a deep impurity removal process, namely mixing the semi-finished product of the 2-mercaptobenzothiazole with a sodium sulfite solution, heating, stirring, refluxing for 1-2 hours, cooling to room temperature, and filtering to obtain the finished product of the 2-mercaptobenzothiazole.
2. The method according to claim 1, wherein the amount of toluene used in the first step is: 1.5-3L of toluene was added per kg of crude 2-mercaptobenzothiazole.
3. The method for refining 2-mercaptobenzothiazole according to claim 1, wherein in the first step, the temperature is reduced to 20-60 ℃ under stirring, the mixture is divided into a solid phase and a liquid phase, the liquid phase is toluene and dissolved impurities thereof, the solid phase is 2-mercaptobenzothiazole, the solid phase is sent to a scraper centrifuge to remove the solvent, and then the toluene solvent is added for washing, so as to further purify the 2-mercaptobenzothiazole; vacuum drying for 1.5h to obtain 2-mercaptobenzothiazole semi-finished product, and distilling the mother liquor to recover toluene for recycling.
4. The method for refining 2-mercaptobenzothiazole according to claim 1, wherein in the second step, the mass concentration of the sodium sulfite solution is 5-8%, and the amount of sodium sulfite is 12-16% of the mass of the semi-finished product of 2-mercaptobenzothiazole; and cooling to room temperature, filtering, preparing sodium thiosulfate from the filtered mother liquor, and washing the filter cake with water to obtain the finished product of 2-mercaptobenzothiazole.
5. The method of claim 1, wherein the sodium sulfite is further replaced by sodium or potassium metabisulfite, sodium or potassium sulfite double salt, potassium ammonium sulfite double salt, or sodium ammonium sulfite double salt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675676A (en) * | 2020-07-08 | 2020-09-18 | 河南省化工研究所有限责任公司 | Preparation method of vulcanization accelerator high-purity 2-mercaptobenzothiazole |
| CN112661722A (en) * | 2021-01-30 | 2021-04-16 | 蔚林新材料科技股份有限公司 | Novel green and clean process for refining 2-mercaptobenzothiazole |
| CN115286593A (en) * | 2022-08-24 | 2022-11-04 | 鹤壁中昊新材料科技有限公司 | Preparation method of rubber vulcanization accelerator dibenzothiazyl disulfide |
| CN115772138A (en) * | 2022-11-23 | 2023-03-10 | 山东尚舜化工有限公司 | Purification and refining method of rubber accelerator MBT |
Citations (4)
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| US5198550A (en) * | 1991-06-11 | 1993-03-30 | Bayer Aktiengesellschaft | Process for the purification of crude 2-mercaptobenzothiazole |
| CN102675242A (en) * | 2012-05-08 | 2012-09-19 | 中国石油化工股份有限公司 | Refining method of vulkacit M |
| CN106674152A (en) * | 2017-02-17 | 2017-05-17 | 李梦琦 | Method for extracting accelerator M from waste resin |
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Patent Citations (4)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675676A (en) * | 2020-07-08 | 2020-09-18 | 河南省化工研究所有限责任公司 | Preparation method of vulcanization accelerator high-purity 2-mercaptobenzothiazole |
| CN111675676B (en) * | 2020-07-08 | 2023-11-10 | 河南省化工研究所有限责任公司 | Preparation method of vulcanization accelerator 2-mercaptobenzothiazole |
| CN112661722A (en) * | 2021-01-30 | 2021-04-16 | 蔚林新材料科技股份有限公司 | Novel green and clean process for refining 2-mercaptobenzothiazole |
| CN112661722B (en) * | 2021-01-30 | 2024-04-02 | 蔚林新材料科技股份有限公司 | Novel green cleaning process for refining 2-mercaptobenzothiazole |
| CN115286593A (en) * | 2022-08-24 | 2022-11-04 | 鹤壁中昊新材料科技有限公司 | Preparation method of rubber vulcanization accelerator dibenzothiazyl disulfide |
| CN115286593B (en) * | 2022-08-24 | 2024-01-12 | 鹤壁中昊新材料科技有限公司 | Preparation method of dibenzothiazyl disulfide serving as rubber vulcanization accelerator |
| CN115772138A (en) * | 2022-11-23 | 2023-03-10 | 山东尚舜化工有限公司 | Purification and refining method of rubber accelerator MBT |
| CN115772138B (en) * | 2022-11-23 | 2024-06-04 | 山东尚舜化工有限公司 | Method for purifying and refining rubber accelerator MBT |
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Inventor after: Zhao Zengbing Inventor after: Wu Zexin Inventor after: Yuan Zhuqing Inventor after: Zhang Xuehua Inventor after: Yue Yanrong Inventor after: Qiao Guifang Inventor after: Liu Chen Inventor after: Du Junwei Inventor after: Zhang Xian Inventor after: Cheng Lanxing Inventor after: Chen Bo Inventor after: Yang Shucheng Inventor after: Zhang Qianhua Inventor after: Wang Jianfeng Inventor after: Kong Weigang Inventor after: Sun Shoufeng Inventor after: Cheng Xinhe Inventor before: Zhao Zengbing Inventor before: Wu Zexin Inventor before: Yuan Zhuqing Inventor before: Zhang Xuehua Inventor before: Yue Yanrong Inventor before: Qiao Guifang Inventor before: Liu Chen Inventor before: Du Junwei Inventor before: Zhang Xian Inventor before: Cheng Lanxing Inventor before: Chen Bo Inventor before: Yang Shucheng Inventor before: Zhang Qianhua Inventor before: Wang Jianfeng Inventor before: Kong Weigang Inventor before: Sun Shoufeng Inventor before: Cheng Xinhe |
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