CN106316981A - Preparation method of N-cyclohexyl-2-benzothiazolesulfenamide - Google Patents
Preparation method of N-cyclohexyl-2-benzothiazolesulfenamide Download PDFInfo
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- CN106316981A CN106316981A CN201510343547.6A CN201510343547A CN106316981A CN 106316981 A CN106316981 A CN 106316981A CN 201510343547 A CN201510343547 A CN 201510343547A CN 106316981 A CN106316981 A CN 106316981A
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- catalyst
- preparation
- cyclohexylamine
- cbs
- benzothiazole disulfide
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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
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
Abstract
The invention belongs to the technical field of fine chemical engineering, and concretely relates to an oxidant-free preparation method of N-cyclohexyl-2-benzothiazolesulfenamide (CBS). The CBS is synthesized from benzothiazole disulfide (a sulfuration promoter DM) and cyclohexylamine by using an inorganic or organic alkaline catalyst, no oxidant is needed in the reaction process, the added catalyst can be repeatedly used, and the addition amount of the catalyst is 5-30% of the weight of benzothiazole disulfide. The yield of the CBS product synthesized through the method stabilizes in a range of 98-99.5, methanol insoluble substances in the product are stable, the lowest content of the methanol insoluble substances is 0.1%, and the highest content of the methanol insoluble substances is 0.22%, and no wastewater is generated in the process, so the method is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of fine, be specifically related to a kind of method that anaerobic agent prepares N cyclohexyl 2 benzothiazole sulfenamide.
Background technology
N cyclohexyl 2 benzothiazole sulfenamide (hereinafter referred to as accelerator CBS) is one of important kind of sulfenamide vulcanization accelerator, have anti-incipient scorch and the big advantage of curingprocess rate fast two concurrently, in natural rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, it is particularly suited for the furnace black sizing material that alkalescence is higher, variable color and pollution are slight, and volume of production and the consumption of the most external CBS account for the 50% of thiazoles sulfuration chemicals total amount.In recent years, along with China's radial development, the demand of accelerator CBS is also presented the longest trend.
The synthetic method of CBS mainly has sodium hypochlorite oxidization, Oxygen Catalytic Oxidation method, electrolytic oxidation, chlorine oxidation process, hydrogen peroxide oxidation method etc. at present, oxidizing process has raw material and is easy to get, the advantages such as equipment requirements is the highest, and product yield is high, and technique is simple and widely used by institute both at home and abroad.This method is to carry out condensation with 2-benzothiazolyl mercaptan (hereinafter referred to as M) in the presence of an oxidizer with cyclohexylamine to generate CBS, but this technique is owing to using extra oxidant or solvent, course of reaction can produce oxidized byproduct, produces substantial amounts of reluctant waste water, seriously polluted.
European patent EP 180169, proposes 1600mL water, the sodium salt of 378g50%M and the sulphuric acid mix and blend of 178.2g cyclohexylamine and 343g20%, it is warming up to 50 DEG C, then adds 457mL15% sodium hypochlorite stirring reaction 30min, obtain 223gCBS, product fusing point 102-103 DEG C, purity 99%.
German patent DE 3021419, propose in aqueous 10%-30%(weight ratio) 2 one butyl cellosolve solvents in, add M, then 20-50 DEG C it is warmed up to, add cyclohexylamine, then aoxidize at 25-60 DEG C with sodium hypochlorite, be then cooled to 5-l5 DEG C of crystallization, sucking filtration drying, the CBS of available purity 99%, yield reaches 90%.
Li Yan etc. (petrochemical technology and application, Vol26(1), 2008,31-33) with captax, cyclohexylamine as raw material, water as solvent, use hydrogen peroxide as oxidant to synthesize N-cyclohexyl-2-benzothiazole sulfonamide (CBS).And by orthogonal experiment, synthesis technique is optimized.CBS yield is 95.28% with optimal conditions, and fusing point is 99.0 DEG C.
Approach described above is to produce the main method used both at home and abroad at present.It is mainly characterized by technical maturity, and condition relaxes, and product quality is preferable, and yield is higher.Shortcoming is to bring solvent to separate, the problems such as recovery, need to neutralize to reclaim the cyclohexylamine of excess with sodium hydroxide after completion of the reaction owing to employing sulphuric acid in the reaction, add product cost, use sulphuric acid, the anticorrosion of equipment is had higher requirement, owing to using oxidant to produce oxidized byproduct, for reaching quality standards, need to wash with substantial amounts of water, produce a large amount of industrial wastewater, to environmentally undesirable.
Summary of the invention
The shortcoming that the present invention is directed to above-mentioned synthetic method, proposes the synthesis technique of a kind of new CBS, can effectively solve the problem that existing synthetic method exists, and makes product yield stable more than 98%, and fusing point reaches 99.5-103 DEG C.Insoluble methyl alcohol meets national standard, and technical process does not produce waste water.
The present invention with benzothiazole disulfide (accelerator DM) and cyclohexylamine as raw material, suitable catalyst is selected to synthesize CBS, oxidizer is need not during reaction, the catalyst added can be reused, and catalyst charge is the 5-30% of the benzothiazole disulfide weight added, according to the CBS product of the inventive method synthesis, stable yield is in the range of 98.0-99.5%, in product, insoluble methyl alcohol is stable, and insoluble methyl alcohol minimum 0.1% is the highest by 0.22%.
The main technical schemes of the present invention is: with benzothiazole disulfide and cyclohexylamine as raw material, in the presence of base catalyst, carry out as follows:
1) under stirring condition, water, benzothiazole disulfide are sequentially added in reactor；Stir 30-60 minute after adding, obtain suspension；
2) under stirring condition, at 20-40 DEG C of continuous interpolation cyclohexylamine, benzothiazole disulfide is 1:1.5-1.8 with the mol ratio of cyclohexylamine, and the control interpolation time is 15-60 minute, continues to stir 0.5-2 hour at 20-40 DEG C after adding cyclohexylamine；
3) under stirring condition, being added continuously in reactor by catalyst in the range of 35-85 DEG C, catalyst charge is the 5-30% of the benzothiazole disulfide weight added, the interpolation time controlled at 10-60 minute；
4) it is warmed up to 80-85 DEG C after having added catalyst and continues to 0.5-2 hour；
5) reactant liquor is cooled to less than 20 DEG C, through filtering, washing, be dried to obtain required product；
Usually, above-mentioned steps 5) catalyst in filtrate reuses through concentrating under reduced pressure, the concentration reaching 30%.
The inventive method is water, benzothiazole disulfide to be sequentially added in reactor under agitation；Stir 30-60 minute after adding, obtain a suspension；Under stirring condition, at 20-40 DEG C of continuous interpolation cyclohexylamine, benzothiazole disulfide is 1:1.5-3.0 with the mol ratio of cyclohexylamine, the control interpolation time is 15-60 minute, optimum is 30-40 minute, continues to stir 0.5-2 hour at 20-40 DEG C, optimum 1-2 hour after adding cyclohexylamine；Then being added continuously in the range of 35-85 DEG C in reactor by catalyst, the consumption of catalyst is the 5%-30% of benzothiazole disulfide weight, and optimum is 10%.The interpolation time controls at 10-60 minute, and optimum is 20-30 minute；Being warmed up to 80-85 DEG C after having added catalyst continue to 0.5-2 hour, optimum is 1 hour；Maintaining complete, reactant liquor cools to less than 20 DEG C, through filtering, washing, is dried to obtain required product.
Catalyst used by the present invention is inorganic or organic basic material, inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, organic base Tetramethylammonium hydroxide, TBAH, the consumption of catalyst is the 5%-30% of benzothiazole disulfide weight, and optimum is 10%.
Synthesizing CBS according to the process conditions of the present invention, product appearance is white powder, and product yield is stable more than 98%, and fusing point reaches more than 99.5 DEG C, and insoluble methyl alcohol stable content is in the range of 0.1%-0.22%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment
1
nullWith agitator、Thermometer、The 500ml four-hole boiling flask of reflux condenser adds 160 milliliters of water，Open stirring，At room temperature it is dividedly in some parts 68g(0.2mol) benzothiazole disulfide，Add stirring half an hour，Then 30g(0.3mol is added) cyclohexylamine，Add temperature to control at 30-35 DEG C，30 minutes interpolation time，Maintain 2 hours at 30-35 DEG C after adding cyclohexylamine，Maintain complete，At 35-40 DEG C，30% sodium hydroxide 20 milliliters is added in 30 minutes，It is warmed up to 80-85 DEG C after having added and continues to 1 hour，Stirring borehole cooling to 15-20 DEG C，Filter，Wash four times with 40 milliliters of water，Secondary washings merge Distillation recovery cyclohexylamine with mother solution，Remaining liquid concentrates set and is used as catalyst and the reaction water of next batch，Solid product is dried at 50 DEG C，Sample analysis，Weigh，Obtain 52.8g finished product，Fusing point 103 DEG C，CBS yield 99.5%，Insoluble methyl alcohol 0.1%.
Embodiment
2
Operating condition is with embodiment 1, but uses potassium hydroxide to replace sodium hydroxide, obtains 52g finished product, fusing point 100 DEG C, CBS productivity 98.5%.Insoluble methyl alcohol 0.12%.
Embodiment
3
Operating condition is with embodiment 1, but uses tetramethyl oxyammonia to replace sodium hydroxide, obtains 51.8g finished product, fusing point 99.5 DEG C, CBS productivity 98.0%, insoluble methyl alcohol 0.2%.
Embodiment
4
Operating condition is with embodiment 1, but replaces sodium hydroxide with tetrabutylammonium hydroxide amine, obtains 51.8g finished product, fusing point 100 DEG C, CBS productivity 98%, insoluble methyl alcohol 0.22%.
Embodiment
5
Operating condition is with embodiment 1, but the mol ratio of benzothiazole disulfide and cyclohexylamine is increased to 1:1.8 by 1:1.5, obtains 51.9g finished product, fusing point 102 DEG C, CBS productivity 98.1%, insoluble methyl alcohol 0.12%.
Embodiment
6
Operating condition is with embodiment 1, but the mol ratio of benzothiazole disulfide and cyclohexylamine is increased to 1:3.0 by 1:1.5, obtains 51.8g finished product, fusing point 103 DEG C, CBS productivity 98%, insoluble methyl alcohol 0.1%.
Embodiment
7
Operating condition is with embodiment 1, but uses and reclaim sodium hydroxide replacement fresh sodium hydroxide, obtains 52.4g finished product, fusing point 101.3 DEG C, CBS productivity 99%, insoluble methyl alcohol 0.12%.
Claims (8)
1. a N cyclohexyl 2 benzothiazole sulfenamide preparation method, with benzothiazole disulfide and cyclohexylamine as raw material, synthesizes, it is characterised in that carry out as follows in the presence of a catalyst:
1) under stirring condition, water, benzothiazole disulfide are sequentially added in reactor；Stir 30-60 minute after adding, obtain suspension；
2) under stirring condition, at 20-40 DEG C of continuous interpolation cyclohexylamine, benzothiazole disulfide is 1:1.5-3.0 with the mol ratio of cyclohexylamine, and the control interpolation time is 15-60 minute, continues to stir 0.5-2 hour at 20-40 DEG C after adding cyclohexylamine；
3) under stirring condition, being added continuously in reactor by catalyst in the range of 35-85 DEG C, the consumption of catalyst is the 5%-30% of benzothiazole disulfide weight, and the interpolation time controlled at 10-60 minute；
4) it is warmed up to 80-85 DEG C after having added catalyst and continues to 0.5-2 hour；
5) reactant liquor is cooled to less than 20 DEG C, through filtering, washing, be dried to obtain required product.
Preparation method the most according to claim 1, is characterized in that catalyst used is inorganic or organic basic material, and inorganic base is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and organic base is selected from Tetramethylammonium hydroxide, TBAH.
Preparation method the most according to claim 1, it is characterised in that the consumption of catalyst is 10%.
Preparation method the most according to claim 1, it is characterised in that the cyclohexylamine interpolation time is 30 minutes.
Preparation method the most according to claim 1, it is characterised in that the interpolation time of catalyst is 30 minutes.
Preparation method the most according to claim 1, it is characterised in that the interpolation temperature of catalyst is 35-40 DEG C.
Preparation method the most according to claim 1, it is characterised in that be warmed up to 80-85 DEG C after having added catalyst and continue to 1 hour.
Preparation method the most according to claim 1, it is characterised in that the catalyst in step 5) filtrate is reused through concentrating under reduced pressure, the concentration reaching 30%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054598A (en) * | 2019-04-04 | 2019-07-26 | 上海倍裕实业有限公司 | A kind of novel processing step of rubber vulcanization accelerant CZ |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
| CN112625003A (en) * | 2020-12-30 | 2021-04-09 | 蔚林新材料科技股份有限公司 | N-cyclohexyl-2-benzothiazole sulfonamide and synthesis process thereof |
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| US4127454A (en) * | 1976-10-05 | 1978-11-28 | Ouchi Shinko Kagaku Kogyo Kabushiki Kaisha | Preparation of benzothiazolylsulfenamides |
| US4751301A (en) * | 1985-05-11 | 1988-06-14 | Bayer Aktiengesellschaft | Process for preparing benzothiazolesulphenamides |
| US4801707A (en) * | 1984-08-18 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the production of benzothiazole sulphene amides |
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2015
- 2015-06-19 CN CN201510343547.6A patent/CN106316981A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127454A (en) * | 1976-10-05 | 1978-11-28 | Ouchi Shinko Kagaku Kogyo Kabushiki Kaisha | Preparation of benzothiazolylsulfenamides |
| US4801707A (en) * | 1984-08-18 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the production of benzothiazole sulphene amides |
| US4751301A (en) * | 1985-05-11 | 1988-06-14 | Bayer Aktiengesellschaft | Process for preparing benzothiazolesulphenamides |
Non-Patent Citations (3)
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| 上海市橡胶工业制品研究所: "《橡胶译丛 第9辑》", 30 April 1965 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054598A (en) * | 2019-04-04 | 2019-07-26 | 上海倍裕实业有限公司 | A kind of novel processing step of rubber vulcanization accelerant CZ |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
| CN110523332B (en) * | 2019-09-16 | 2021-07-02 | 山东尚舜化工有限公司 | Equipment and method for continuously producing vulcanization accelerator CBS |
| CN112625003A (en) * | 2020-12-30 | 2021-04-09 | 蔚林新材料科技股份有限公司 | N-cyclohexyl-2-benzothiazole sulfonamide and synthesis process thereof |
| CN112625003B (en) * | 2020-12-30 | 2023-11-28 | 蔚林新材料科技股份有限公司 | N-cyclohexyl-2-benzothiazole sulfenamide and synthesis process thereof |
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Application publication date: 20170111 |