CN105503772A - Preparation method for N-tert-butyl benzothiazole sulfenamide - Google Patents
Preparation method for N-tert-butyl benzothiazole sulfenamide Download PDFInfo
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- CN105503772A CN105503772A CN201410496405.9A CN201410496405A CN105503772A CN 105503772 A CN105503772 A CN 105503772A CN 201410496405 A CN201410496405 A CN 201410496405A CN 105503772 A CN105503772 A CN 105503772A
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Abstract
The invention belongs to the technical field of fine chemical engineering and particularly relates to a method of preparing N-tert-butyl benzothiazole sulfonamide (TBBS) without an oxidant. In the invention, benzothiazole disulfide (vulcanization accelerator DM) and tert-butyl amine as raw materials are used for synthesizing the TBBS with an inorganic or an organic alkaline catalyst, wherein the reaction process is free of any oxidant and the added catalyst can be reused. The addition amount of the catalyst is 5-30% of the weight of the disulfide benzothiazole. By means of the method, the yield of the TBBS is 96-98.5%, is stable in insoluble-in-methane substances being 0.13-0.32%, is free of generation of waste water and 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-tertiary butyl benzo thiazolesulfenamide.
Background technology
N tert butyl benzothiazole 2 sulfenamide (hereinafter referred to as accelerator TBBS) is one of important kind of sulfenamide vulcanization accelerator, have anti-incipient scorch and the large advantage of vulcanization rate fast two concurrently, for natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, in polyisoprene rubber, be particularly useful for the furnace treated black sizing material that alkalescence is higher, variable color and pollution are slightly, the alternative NOBS(N-morpholinyl benzothiaolesulfenamide having carinogenicity possible containing secondary amine), the NOBS of tire industry is replaced with CBS (CZ) or TBBS in l994 law-making stipulation by Germany.Turnout and the consumption of current external TBBS account for 40% of thiazoles sulfuration chemical total amount.In recent years, along with China's radial development, trend long fast is also presented to the demand of accelerator TBBS.
The synthetic method of current TBBS mainly contains sodium hypochlorite oxidization, Oxygen Catalytic Oxidation method, electrolytic oxidation, chlorine oxidation process, hydrogen peroxide oxidation method etc., oxidation style has raw material and is easy to get, advantages such as equipment requirements is not high, and product yield is high, and technique is simple and extensively being adopted both at home and abroad.This method carries out condensation in the presence of an oxidizer with 2-benzothiazolyl mercaptan (hereinafter referred to as M) and TERTIARY BUTYL AMINE to generate TBBS, but this technique is owing to using extra oxygenant or solvent, reaction process can produce oxidized byproduct, produces a large amount of reluctant waste water, seriously polluted.
DE3021419 patent, propose in moisture 10%-30%(weight ratio) 2 one butyl cellosolve solvents in, add M, then 20-50 DEG C is warmed up to, add TERTIARY BUTYL AMINE, then be oxidized at 25-60 DEG C with clorox, be then cooled to 5-l5 DEG C of crystallization, suction filtration oven dry, can obtain the TBBS of purity 99.7%, yield reaches 92%.
DE3440801 patent, proposes 160mL water, the sodium salt of 378g50%M and the sulfuric acid mix and blend of 292g TERTIARY BUTYL AMINE and 588g20%, be warming up to 60 DEG C, then add 472mL15% clorox stirring reaction 30min, obtain 202gTBBS, product fusing point 109 DEG C, purity 99%.
Domestic CN1069489 etc. change the sodium salt of raw material M into M, and suitably add the product that tensio-active agent then can obtain average yield more than 93%, and fusing point is 105 DEG C.
The above method produces the main method adopted both at home and abroad at present.Its principal feature is technical maturity, and condition relaxes, and quality product is better, and yield is higher.Shortcoming brings separated from solvent, the problems such as recovery, need to neutralize to reclaim excessive TERTIARY BUTYL AMINE with sodium hydroxide after completion of the reaction owing to employing sulfuric acid in the reaction, add product cost, use sulfuric acid, the anticorrosion of equipment is had higher requirement, owing to using oxygenant to produce oxidized byproduct, for reaching quality standards, need with a large amount of water washings, produce a large amount of trade effluent, unfavorable to environment.Because the consumption of oxygenant is in the reaction excessive, be not easy to wash away, in the oxygenant decomposes that follow-up drying process is residual, TBBS is decomposed, easily cause the insoluble methyl alcohol content of finished product TBBS unstable, even do not reach quality index requirement, cause the outward appearance of product to present redness simultaneously.
Summary of the invention
The present invention is directed to the shortcoming of above-mentioned synthetic method, propose the synthesis technique of a kind of new TBBS, effectively can solve existing synthetic method Problems existing, make product yield be stabilized in more than 96%, fusing point reaches 106-107 DEG C.Insoluble methyl alcohol meets national standard, and technological process does not produce waste water.
The present invention with benzothiazyl disulfide (accelerator DM) and TERTIARY BUTYL AMINE for raw material, select suitable catalyzer synthesis TBBS, oxidizer is not needed in the process of reaction, the catalyzer added can be reused, and catalyst charge is the 5-30% of the benzothiazyl disulfide weight added, according to the TBBS product of the inventive method synthesis, stable yield is within the scope of 96.0-98.5%, in product, insoluble methyl alcohol is stablized, and insoluble methyl alcohol is minimum is 0.13%, the highest by 0.32%.
Main technical schemes of the present invention is: with benzothiazyl disulfide and TERTIARY BUTYL AMINE for raw material, under the existence of basic catalyst agent, carry out as follows:
1) under agitation condition, water, benzothiazyl disulfide are added in reactor successively; Add rear stirring 30-60 minute, obtain suspension;
2) under agitation condition, add TERTIARY BUTYL AMINE continuously at 20-40 DEG C, the mol ratio of benzothiazyl disulfide and TERTIARY BUTYL AMINE is 1:1.5-1.8, and controlling the interpolation time is 15-60 minute, continues to stir 0.5-2 hour at 20-40 DEG C after adding TERTIARY BUTYL AMINE;
3) under agitation condition, be added continuously in reactor by catalyzer within the scope of 35-85 DEG C, catalyst charge is the 5-30% of the benzothiazyl disulfide weight added, add time controling at 10-60 minute;
4) be warmed up to 80-85 DEG C after having added catalyzer to continue to maintain 0.5-2 hour;
5) reaction solution is cooled to less than 20 DEG C, after filtration, washing, dry desired product.
Usually, the inventive method water, benzothiazyl disulfide is added successively in reactor under agitation; Add rear stirring 30-60 minute, obtain a suspension; Under agitation condition, add TERTIARY BUTYL AMINE continuously at 20-40 DEG C, the mol ratio of benzothiazyl disulfide and TERTIARY BUTYL AMINE is 1:1.5-1.8, controlling the interpolation time is 15-60 minute, be preferably 30-40 minute, continue after adding TERTIARY BUTYL AMINE to stir 0.5-2 hour, best 1-2 hour at 20-40 DEG C; Then be added continuously in reactor by catalyzer within the scope of 35-85 DEG C, the consumption of catalyzer agent is the 5%-30% of benzothiazyl disulfide weight, is preferably 10%.Add time controling at 10-60 minute, be preferably 20-30 minute; Be warmed up to 80-85 DEG C after having added catalyzer to continue to maintain 0.5-2 hour, be preferably 1 hour; Maintain complete, reaction solution cools to less than 20 DEG C, after filtration, washing, dry desired product.
The present invention's catalyzer used is inorganic or organic basic material, mineral alkali is as sodium hydroxide, potassium hydroxide, calcium hydroxide, organic bases Tetramethylammonium hydroxide, TBAH, the consumption of catalyzer agent is the 5%-30% of benzothiazyl disulfide weight, is preferably 10%.
Catalyzer in the last filtrate of the present invention through concentrating under reduced pressure, reach 30% concentration reusable.
According to processing condition synthesis TBBS of the present invention, product appearance is white powder, and product yield is stabilized in more than 96%, and fusing point reaches more than 106 DEG C, and insoluble methyl alcohol stable content within the scope of 0.1%-0.4%, and meets standard GB/T/T21840-2008.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
embodiment 1
With agitator, thermometer, 160 milliliters, water is added in the 500ml four-hole boiling flask of reflux exchanger, open stirring, at room temperature add 68g(0.2mol in batches) gram benzothiazyl disulfide, add and stir half hour, then 24 grams of (0.3mol) TERTIARY BUTYL AMINE are added, adding temperature controls at 30-35 DEG C, 30 minutes interpolation time, 2 hours are maintained at 30-35 DEG C after adding TERTIARY BUTYL AMINE, maintain complete, at 40-50 DEG C, 20 milliliters, 30% sodium hydroxide is added in 30 minutes, be warmed up to 80-85 DEG C after having added and continue maintenance 1 hour, stir borehole cooling to 15-20 DEG C, filter, four times are washed with 40 ml waters, secondary washing water and mother liquor merge Distillation recovery TERTIARY BUTYL AMINE, remaining liquid concentrates catalyzer and the reaction water that cover is used as next batch, solid phase prod is 50 DEG C of dryings, sampling analysis, weigh, obtain 46.8 grams of finished products, fusing point 107.4 DEG C, TBBS yield 98.5%, insoluble methyl alcohol 0.13%.
embodiment 2
Operational condition with embodiment 1, but uses potassium hydroxide to replace sodium hydroxide, obtains 46.4 grams of finished products, fusing point 107 DEG C, TBBS productive rate 97.5%.Insoluble methyl alcohol 0.12%.
embodiment 3
Operational condition with embodiment 1, but uses tetramethyl-oxyammonia to replace sodium hydroxide, obtains 46.2 grams of finished products, fusing point 106.1 DEG C, TBBS productive rate 97.0%, insoluble methyl alcohol 0.23%.
embodiment 4
Operational condition with embodiment 1, but replaces sodium hydroxide with tetrabutylammonium hydroxide amine, obtains 46.4 grams of finished products, fusing point 107.1 DEG C, TBBS productive rate 97.5%, insoluble methyl alcohol 0.32%.
embodiment 5
Operational condition is with embodiment 1, but the mol ratio of benzothiazyl disulfide and TERTIARY BUTYL AMINE is increased to 1:1.8 by 1:1.5, obtains 46 grams of finished products, fusing point 107.5 DEG C, TBBS productive rate 96.6%, insoluble methyl alcohol 0.28%.
embodiment 6
Operational condition with embodiment 1, but uses recovery sodium hydroxide to replace fresh sodium hydroxide, obtains 46.7 grams of finished products, fusing point 107.3 DEG C, TBBS productive rate 96.9%, insoluble methyl alcohol 0.12%.
Claims (8)
1. a N-tertiary butyl benzo thiazolesulfenamide preparation method, with benzothiazyl disulfide and TERTIARY BUTYL AMINE for raw material, synthesizes in the presence of a catalyst, it is characterized in that carrying out as follows:
1) under agitation condition, water, benzothiazyl disulfide are added in reactor successively; Add rear stirring 30-60 minute, obtain suspension;
2) under agitation condition, add TERTIARY BUTYL AMINE continuously at 20-40 DEG C, the mol ratio of benzothiazyl disulfide and TERTIARY BUTYL AMINE is 1:1.5-1.8, and controlling the interpolation time is 15-60 minute, continues to stir 0.5-2 hour at 20-40 DEG C after adding TERTIARY BUTYL AMINE;
3) under agitation condition, be added continuously in reactor by catalyzer within the scope of 35-85 DEG C, the consumption of catalyzer agent is the 5%-30% of benzothiazyl disulfide weight, adds time controling at 10-60 minute;
4) be warmed up to 80-85 DEG C after having added catalyzer to continue to maintain 0.5-2 hour;
5) reaction solution is cooled to less than 20 DEG C, after filtration, washing, dry desired product.
2. preparation method according to claim 1, it is characterized in that catalyzer used is inorganic or organic basic material, mineral alkali is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and organic bases is Tetramethylammonium hydroxide, TBAH.
3. preparation method according to claim 1, is characterized in that the consumption of catalyzer agent is 10% of benzothiazyl disulfide weight.
4. preparation method according to claim 1, it is characterized in that catalyzer in last filtrate is through concentrating under reduced pressure, the concentration reaching 30% is reused.
5. preparation method according to claim 1, it is characterized in that TERTIARY BUTYL AMINE adds the time is 30 minutes.
6. preparation method according to claim 1, is characterized in that the interpolation time of catalyzer is 30 minutes.
7. preparation method according to claim 1, is characterized in that the interpolation temperature of catalyzer is 40-50 DEG C.
8. preparation method according to claim 1, is warmed up to 80-85 DEG C and continues maintenance 1 hour after it is characterized in that having added catalyzer.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107814776A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of continuous preparation method of N- tert-butyl groups benzo thiazolesulfenamide |
Citations (3)
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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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Patent Citations (3)
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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)
Title |
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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 * |
樊云峰等: "硫化促进剂CZ合成工艺与应用", 《精细化工》 * |
胡生泳等: "硫化促进剂CZ合成方法进展", 《精细石油化工》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107814776A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of continuous preparation method of N- tert-butyl groups benzo thiazolesulfenamide |
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Application publication date: 20160420 |