CN101402615B - Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) - Google Patents
Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) Download PDFInfo
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- CN101402615B CN101402615B CN2008101598356A CN200810159835A CN101402615B CN 101402615 B CN101402615 B CN 101402615B CN 2008101598356 A CN2008101598356 A CN 2008101598356A CN 200810159835 A CN200810159835 A CN 200810159835A CN 101402615 B CN101402615 B CN 101402615B
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- mercaptobenzothiazole
- toluene
- mbt
- thiofide
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Abstract
The invention relates to a method for refining a thiofide 2-mercaptobenzothiazole (M). The method is characterized in that an extraction method and an alkali dissolving and acid isolation method are creatively combined. The method comprises the following steps: crude thiofide M is extracted by using toluene for three times to remove resin impurities so as to obtain high-purity thiofide M; the thiofide M in the resin is purified by the alkali dissolving and acid isolation method; and the thiofideoluene is reclaimed by a distillation method. By adopting the processing, the thiofide M with high purity, high melting point and short melting period can be obtained.
Description
Technical field
The present invention relates to the process for purification of a kind of thiofide 2-mercaptobenzothiazole (M), belong to field of fine chemical.
Background technology
Along with the development of rubber industry, the research of vulcanization accelerator more and more is subject to people's attention with production.Vulcanization accelerator plays important effect in vulcanization of rubber process, it can accelerate the reaction of rubber and vulcanizing agent greatly, boost productivity, also can improve simultaneously the physical and mechanical properties of vulcanized rubber, 2 Mercaptobenzothiazole (MBT) is a kind of important promotor in the present rubber industry, generally, impurity is mainly resin and intermediate product (as benzothiazole) in this promotor, and the existence of impurity makes the of low quality of product.
China mostly adopts traditional alkali-soluble acid analysis method to the refining of 2 Mercaptobenzothiazole (MBT) at present, and this technology alkali charge is big, and the cost height has obvious defects in addition aspect environmental protection, not only produce the black tarry materials of a lot of intractable, and produces a large amount of waste water.
Also having the aniline extractive crystallization process to come the treated rubber accelerator M in the document, be to utilize 2 Mercaptobenzothiazole (MBT) to be insoluble to aniline to remove the resin that wherein is dissolved in aniline, but this method operation is long, and operation is also complicated.
The molten extraction process of another kind of toluene alkali, be that the crude product 2 Mercaptobenzothiazole (MBT) is joined in the excessive alkaline solution, repeatedly extract filtrate to remove soluble impurity and part insoluble impurities with toluene, add acid out again and go out 2 Mercaptobenzothiazole (MBT), though this method combines the high and high advantage of alkali solution technique productive rate of solvent extration purity, but has produced a large amount of waste water.
Summary of the invention
The object of the present invention is to provide the process for purification of 2 Mercaptobenzothiazole (MBT), this method is simple to operate, and waste water produces few, makes 2 Mercaptobenzothiazole (MBT) purity height, fusing point height, melting range weak point.The present invention is realized by following technical proposals:
1. in extraction kettle, add 200～400ml toluene, add 100～150g massfraction again and be 85～90% crude product 2 Mercaptobenzothiazole (MBT), keep 25～55 ℃ of temperature, stir after 0.5～4 hour, emit upper toluene solution.And then in extraction kettle, add 120～250ml toluene, and keep 25～55 ℃ of temperature, stirred 0.5～3 hour, emit toluene solution.In extraction kettle, add 100～200ml toluene, suction filtration while stirring at last again.After suction filtration is intact, obtains purity and can reach 98.5% 2 Mercaptobenzothiazole (MBT).
2. the toluene solution that will be dissolved with 2 Mercaptobenzothiazole (MBT) and resin is poured in the reactor, in reactor, add content 3～20% with respect to the alkali of 2 Mercaptobenzothiazole (MBT) excessive 10～12% (as NaOH, KOH), stirred 0.5～1 hour down at 40～50 ℃, behind the standing demix, emit supernatant liquid and distill the toluene recycling that obtains, lower floor's solution is through the air blast oxidation, and sedimentation goes out a part of impurity, after its elimination, add non-oxidizable mineral acid (as HCI, H
2SO
4) acidifying, after dehydrating, sediment can get the 2 Mercaptobenzothiazole (MBT) of purity 95～98%.
The invention has the advantages that: operational condition is simple and easy, is easy to industrialization, creationary extraction process and alkali-soluble acid analysis method is joined to together, reduced the consumption of alkali, reduced cost, wherein the first step extraction does not produce waste water, make 2 Mercaptobenzothiazole (MBT) purity height at last, the fusing point height, melting range is short.
Description of drawings
Accompanying drawing 1 is a process flow sheet of the present invention.
Embodiment
In conjunction with the accompanying drawings this invention is elaborated:
With aniline, dithiocarbonic anhydride and sulphur at 250 ℃, reaction is two hours under 9.0～10.0MPa condition, generates mass content and is about 85.0% crude product 2 Mercaptobenzothiazole (MBT), all the other impurity comprise: resin is about 12.5%, intermediate product is about 2.5%.With 100g crude product 2 Mercaptobenzothiazole (MBT), add and contain in the extraction kettle of 200ml toluene, keep 35 ± 2 ℃ of temperature, stir speed (S.S.) 170r/min after 2 hours, opens extraction kettle and emits toluene solution.And then in extraction kettle, add 130ml toluene, and keeping 35 ± 2 ℃ of temperature, stir speed (S.S.) 170r/min after 1 hour, emits toluene solution.Add 100ml toluene at last again in extraction kettle, carry out suction filtration, obtain the 79.24g 2 Mercaptobenzothiazole (MBT) after the drying, purity is 98.5%, melting range is 171～176 ℃.
2. the toluene solution that will be dissolved with 2 Mercaptobenzothiazole (MBT) and resin is poured in the reactor, adding concentration is 10% sodium hydroxide solution 15g in reactor, perhaps add concentration and be 10% potassium hydroxide solution 21g, add 17g water then, be heated to 50 ℃, stirred 1 hour, leave standstill separatory after, oil reservoir distills and obtains toluene, is resin at the bottom of the still; Water layer is through the air blast oxidation, small-particle resin formation precipitation, with adding the HCI solution of 6% (w/v) after its filtering, stir, keep 35 ℃ of temperature, the pH value of acidifying mixture is about 1 in adition process, acidifying continues 15min, and washing is to neutral, behind the filtration drying then, the 5.20g 2 Mercaptobenzothiazole (MBT), purity is 97.0%, melting range is 170～175 ℃.
Claims (1)
1. the process for refining of thiofide 2-mercaptobenzothiazole (M), it is characterized in that: thick M is earlier through three toluene extractions, extracting toluene consumption for the first time: the crude product 2 Mercaptobenzothiazole (MBT) is 1.5～3: 1, extracting toluene consumption for the second time: the crude product 2 Mercaptobenzothiazole (MBT) is 1.0～2: 1, wash the toluene consumption for the third time: the crude product 2 Mercaptobenzothiazole (MBT) is 0.75～1.5: 1, the unit of toluene and crude product 2 Mercaptobenzothiazole (MBT) is mass unit kg, temperature is 25～55 ℃ in the extracting and washing process, most of M is purified, again the M that is dissolved in the toluene is extracted with alkali solution technique, the alkali of adding excessive 10～12% in the toluene solution after filtration, then the M sodium salt is neutralized, separate out M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101598356A CN101402615B (en) | 2008-11-12 | 2008-11-12 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101598356A CN101402615B (en) | 2008-11-12 | 2008-11-12 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
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| Publication Number | Publication Date |
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| CN101402615A CN101402615A (en) | 2009-04-08 |
| CN101402615B true CN101402615B (en) | 2011-02-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021234497A1 (en) * | 2020-05-16 | 2021-11-25 | Nitrex Chemicals India Limited | Process for the purification of 2 mercaptobenzothiazole |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693701B (en) * | 2009-10-21 | 2011-05-04 | 山东阳谷华泰化工股份有限公司 | Purification process for vulcanization accelerator 2-mercaptobenzothiazole |
| CN102070562B (en) * | 2010-12-21 | 2012-07-25 | 天津大学 | Method for preparing 2-mercaptobenzothiazole |
| CN102302916B (en) * | 2011-06-28 | 2014-06-25 | 山东阳谷华泰化工股份有限公司 | Device for synthesizing accelerating agent NS by oxygen oxidation method |
| CN102603668B (en) * | 2012-02-21 | 2013-11-27 | 刘炤 | Method for treating 2-mercaptobenzothiazole production waste |
| 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 |
| CN102718728B (en) * | 2012-07-01 | 2015-06-17 | 山东尚舜化工有限公司 | Refining process of rubber vulcanization accelerator MBT |
| CN102718729B (en) * | 2012-07-01 | 2014-09-03 | 山东尚舜化工有限公司 | Method for producing refining M by calcium salt method |
| CN102827103A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Production method of medical intermediate MBT (2-mercaptobenzthiazole) |
| CN104415571A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Device and method for continuously purifying vulcanization accelerator-2-mercaptobenzothiazole |
| CN103739569B (en) * | 2014-01-09 | 2016-03-23 | 山东尚舜化工有限公司 | A kind of method of purification of rubber vulcanization accelerant MBT |
| CN104190232A (en) * | 2014-09-05 | 2014-12-10 | 淄博高汇化工有限公司 | Vulcanization accelerator M tail gas treatment device |
| CN109535099A (en) * | 2018-10-24 | 2019-03-29 | 科迈化工股份有限公司 | Method by recycling MBT in resin |
| CN109608417B (en) * | 2018-10-24 | 2023-04-07 | 科迈化工股份有限公司 | Method for directly synthesizing accelerator MBTS by recovering crude MBT from resin |
| 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 |
| CN116283826B (en) * | 2023-01-29 | 2024-06-18 | 山东尚舜化工有限公司 | Process method for efficiently recovering MBT from liquid resin |
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|---|---|---|---|---|
| US3770759A (en) * | 1969-08-14 | 1973-11-06 | Bayer Ag | Production of 2-mercaptobenzthiazole |
| CN1687040A (en) * | 2005-04-11 | 2005-10-26 | 苏秋利 | Method for extracting 2-mercapto benzothiazole |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770759A (en) * | 1969-08-14 | 1973-11-06 | Bayer Ag | Production of 2-mercaptobenzthiazole |
| CN1687040A (en) * | 2005-04-11 | 2005-10-26 | 苏秋利 | Method for extracting 2-mercapto benzothiazole |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021234497A1 (en) * | 2020-05-16 | 2021-11-25 | Nitrex Chemicals India Limited | Process for the purification of 2 mercaptobenzothiazole |
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| CN101402615A (en) | 2009-04-08 |
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Effective date of registration: 20100108 Address after: 217, Qinghe West Road, Yanggu County, Shandong, 217, South Ring Road, Liaocheng, China: 252300 Applicant after: Shandong Yanggu Huatai chemical industry Limited by Share Ltd Co-applicant after: National Engineering Technology Research Center for Rubber Chemicals Address before: Zip code 217, South Ring Road, Yanggu County, Liaocheng, Shandong: 252300 Applicant before: Shandong Yanggu Huatai Chemical Co., Ltd. Co-applicant before: National Engineering Technology Research Center for Rubber Chemicals |
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