CN107814776A - A kind of continuous preparation method of N- tert-butyl groups benzo thiazolesulfenamide - Google Patents
A kind of continuous preparation method of N- tert-butyl groups benzo thiazolesulfenamide Download PDFInfo
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- CN107814776A CN107814776A CN201610823600.7A CN201610823600A CN107814776A CN 107814776 A CN107814776 A CN 107814776A CN 201610823600 A CN201610823600 A CN 201610823600A CN 107814776 A CN107814776 A CN 107814776A
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- 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 technical field of fine, and in particular to a kind of continuous anaerobic agent prepares N- tert-butyl group benzo thiazolesulfenamides（TBBS）Method.With benzothiazole disulfide（Accelerator DM）, organic solvent and tert-butylamine be raw material, from inorganic or organic basic catalyst, TBBS is synthesized in two flow reactors, oxidant is not needed during reaction, the catalyst added may be reused, catalyst charge is the 5-30% of the benzothiazole disulfide weight added, the TBBS products synthesized according to the inventive method, stable yield is in the range of 98 99.5%, and insoluble methyl alcohol is less than 0.1% in product, technical process does not produce waste water, is suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of continuous preparation N- tert-butyl groups benzothiazole time sulphur
The method of acid amides.
Background technology
N tert butyl benzothiazole 2 sulfenamide (hereinafter referred to as accelerator TBBS) is that sulfenamide vulcanization promotees
Enter one of important kind of agent, have fast two big advantage of anti-incipient scorch and curingprocess rate concurrently, for natural rubber, butadiene-styrene rubber, suitable
In buna, isoprene rubber, the higher furnace black sizing material of the alkalescence that is particularly suitable for use in, discoloration and pollution are slight, alternative containing secondary
Amido has the possible NOBS of carcinogenicity（N morpholinyl benzothiaolesulfenamide）, Germany will in l994 law-making stipulations
The NOBS of tire industry is replaced with CBS (CZ) or TBBS.Current external TBBS output and consumption accounts for thiazoles sulphur
Change 40% with chemicals total amount.In recent years, as China's radial develops, the demand of accelerator TBBS is also presented
Quickly long trend.
TBBS synthetic method mainly has sodium hypochlorite oxidization, Oxygen Catalytic Oxidation method, electrolytic oxidation, chlorine at present
Oxidizing process, hydrogen peroxide oxidation method etc., there is oxidizing process raw material to be easy to get, and equipment requirement is not high, and product yield is high, and it is excellent that technique is simple etc.
Point and it is widely used by domestic and international institute.The method is with 2- benzothiazolyl mercaptans（Hereinafter referred to as M）Deposited with tert-butylamine in oxidant
In lower progress batch condensation reaction generation TBBS, but the technique is due to the product using intermittent reaction, generated in course of reaction
It may proceed to participate in oxidation reaction, produce oxidized byproduct, while produce substantial amounts of reluctant waste water, seriously polluted, production
Efficiency is low, and labor intensity is high.
DE3021419 patents, propose in aqueous 10%-30%（Weight ratio）2 one butyl cellosolve solvents in, add
M, 20-50 DEG C is then warming up to, adds tert-butylamine, then aoxidized with sodium hypochlorite at 25-60 DEG C, is then cooled to
5-l5 DEG C of crystallization, drying is filtered, can obtain the TBBS of purity 99.7%, yield is up to 92%.
DE3440801 patents, propose 160mL water, 378g 50%M sodium salt and 292g tert-butylamines and 588g's 20%
Sulfuric acid mixes, and is warming up to 60 DEG C, then adds 472mL15% sodium hypochlorite stirring reaction 30min, obtains 202gTBBS, product
109 DEG C of fusing point, purity 99%.
Raw material M sodium salt is changed to M by domestic CN1069489 etc., and is properly added surfactant and can then be obtained average receipts
The product of rate more than 93%, fusing point are 105 DEG C.
Batch process described above is main method used by production both at home and abroad at present.It is mainly characterized by technique
Maturation, condition relax, and product quality is preferable, and yield is higher.Shortcoming is due to have used sulfuric acid to need reacting in the reaction
Cheng Houyong sodium hydroxides are neutralized to reclaim excessive tert-butylamine, add product cost, and using sulfuric acid, the anti-corrosion of equipment is proposed
Higher requirement, due to producing oxidized byproduct using oxidant, to reach quality standards, it is necessary to use substantial amounts of water washing,
A large amount of industrial wastewaters are produced, it is unfavorable to environment.Due to completing reaction in same reactor, and the dosage of oxidant is in reacting
Excessive, oxidant can continue to react with product, generate oxidized byproduct, in order to remove oxidant, it is necessary to use substantial amounts of washing
Wash, wastewater flow rate is big, and is not easy to remove, and is thermally decomposed in the oxidant that follow-up drying process remains, decomposes TBBS, Yi Zao
Insoluble methyl alcohol content into finished product TBBS is unstable, or even does not reach quality index requirement, while causes the outward appearance of product to be in
Existing red.
The content of the invention
The shortcomings that present invention is directed to above-mentioned intermittent oxidation synthetic method, propose that a kind of new TBBS continuous anaerobic agent is closed
Into technique, in the presence of a catalyst, reaction is continuously finished in two different reactors, can effectively solve existing synthesis
The problem of method is present, make product yield stable more than 98%, fusing point is up to more than 107 DEG C.Insoluble methyl alcohol is low, and technique mistake
Journey does not produce waste water.
The present invention is with benzothiazole disulfide（Accelerator DM）, organic solvent and tert-butylamine be raw material, from suitable
Catalyst continuously synthesize TBBS, do not need oxidizer during reaction, the catalyst added may be reused, and urge
Agent addition is the 5-30% of the benzothiazole disulfide weight added, the TBBS products synthesized according to the inventive method, is received
Rate is stable in the range of 98-99.5%, and insoluble methyl alcohol is less than 0.1% in product.
The present invention main technical schemes be：Using benzothiazole disulfide, organic solvent and tert-butylamine as raw material, in alkalescence
In the presence of catalyst agent, carry out as follows：
1) organic solvent, benzothiazole disulfide are sequentially added in batching kettle under stirring condition；30-60 points are stirred after adding
Clock, obtain homogeneous solution；
2) under stirring condition, at 20-50 DEG C by measuring pump, tert-butylamine, curing benzo are continuously added into first reactor
The mol ratio of the solution of thiazole and organic solvent, benzothiazole disulfide and tert-butylamine is 1：1.5-1.8；
3) residence time of the reaction solution in first reactor be 1-3 hours after overflow to second reactor；
4) while continuously addition catalyst solution, catalyst charge are the benzothiazole disulfide added into second reactor
The 5-30% materials of weight keep 50-100 DEG C of temperature of charge in second reactor, continue to react 0.5-2 hours；
5) by reaction solution through distilling desolventizing, cooling to less than 20 DEG C, filtering, wash, dry required product；
6) filtrate is passed through to the concentration reuse being concentrated under reduced pressure to 30%.
Usually, the inventive method is that organic solvent, benzothiazole disulfide are sequentially added into dispensing under agitation
In kettle；30-60 minutes are stirred after adding, obtain homogeneous solution；Under stirring condition, at 20-50 DEG C by measuring pump, to
The solution and catalyst solution of tert-butylamine, benzothiazole disulfide and organic solvent, curing are continuously added in one reactor
The mol ratio 1 of benzothiazole and tert-butylamine：1-3.0 preferably 1：1.5-1.8, stop of the reaction solution in first reactor
Time is 1-3 hours, preferably 1.5 hours, then overflows to second reactor；Into second reactor, continuous addition is urged simultaneously
Agent solution, the dosage of catalyst are the 5%-30% of benzothiazole disulfide weight, preferably 10%.；In second reactor
Material, which is warming up to 50-100 DEG C, to be continued to react 0.5-2 hours, preferably 1 hour；Reaction solution is cooled to less than 20 DEG C, through steaming
Evaporate desolventizing, filtering, washing, dry required product；Filtrate is passed through to the concentration reuse being concentrated under reduced pressure to 30%.
Synthesize TBBS according to the process conditions of the present invention, product appearance is white powder, product yield it is stable 98% with
On, for fusing point up to more than 107 DEG C, insoluble methyl alcohol stable content meets standard GB/T/T21840-2008 less than 0.1%.
Embodiment
The present invention is further described with reference to embodiment.
Embodiment 1
With agitator, thermometer, reflux condenser container in add 16 kilograms of solvent methanol, open stirring, at room temperature
6.8kg is added portionwise（0.2kmol）Benzothiazole disulfide, stirring 30 minutes is added, solid is all dissolved.Stirring condition
Under, at 40-45 DEG C respectively by respective measuring pump, the continuous addition tert-butylamine into first reactor, benzothiazole disulfide with
The mixed solution of organic solvent, charging rate are respectively 240g/ hours, 2280 g/ hours, and control reaction solution is in first reactor
In residence time be 90 minutes time, then overflow to second reactor, while continuous with measuring pump into second reactor
30% sodium hydroxide solution is added, charging rate is 224g/ hours, and it is 80-85 DEG C to control second reactor reaction temperature,
Residence time is 1 hour, completes reacted reaction solution and overflows in distillation still, solvent and unreacted tertiary fourth are boiled off under decompression
Amine, 15-20 DEG C is then cooled to, filtered, water washing, filtrate liquid concentration set is used as the catalyst of next batch, solid product
In 50 DEG C of dryings, 474.3 grams of finished products, 108.6 DEG C of fusing point, TBBS yields 99.5%, insoluble methyl alcohol 0.07% are obtained per hour.
Embodiment 2
Operating condition replaces sodium hydroxide with embodiment 1, but using potassium hydroxide, obtains 468 Grams Per Hour finished products, 107 DEG C of fusing point,
TBBS yields 98.5%.Insoluble methyl alcohol 0.09%.
Embodiment 3
Operating condition replaces sodium hydroxide with embodiment 1, but using TMAH, obtains 468 grams of finished products per hour,
106.8 DEG C of fusing point, TBBS yields 98.5%, insoluble methyl alcohol 0.1%.
Embodiment 4
Operating condition replaces sodium hydroxide with embodiment 1, but with TBAH, obtains 467.2 grams of finished products per hour,
107.1 DEG C of fusing point, TBBS yields 98%, insoluble methyl alcohol 0.05%.
Embodiment 5
Operating condition is with embodiment 1, but the mol ratio of benzothiazole disulfide and tert-butylamine is by 1：1.5 increase to 1：1.8, per small
When obtain 470 grams of finished products, 107.5 DEG C of fusing point, TBBS yields 98.6%, insoluble methyl alcohol 0.08%.
Embodiment 6
Operating condition replaces fresh sodium hydroxide with embodiment 1, but using recovery sodium hydroxide, obtain per hour 468 grams into
Product, 107.3 DEG C of fusing point, TBBS yields 98.5%, insoluble methyl alcohol 0.08%.
Embodiment 7
Operating condition replaces methanol with embodiment 1, but with ethanol, obtains 468 grams of finished products, 108.3 DEG C of fusing point, TBBS per hour
Yield 98.5%, insoluble methyl alcohol 0.06%.
Embodiment 8
Operating condition replaces methanol with embodiment 1, but with toluene or dimethylbenzene, obtains 467.2 grams of finished products, fusing point per hour
107.4 DEG C, TBBS yields 98%, insoluble methyl alcohol 0.05%.
Claims (10)
- A kind of 1. continuous preparation method of N- tert-butyl groups benzo thiazolesulfenamide, it is characterised in that with benzothiazole disulfide, Organic solvent and tert-butylamine are raw material, in the presence of a catalyst continuous synthesis, it is characterised in that are carried out as follows：1) organic solvent, benzothiazole disulfide are added in batching kettle under stirring condition；30-60 minutes are stirred after adding, are obtained To homogeneous solution；2）Under stirring condition, at 20-50 DEG C, tert-butylamine is continuously added into first reactor, benzothiazole disulfide is with having The mol ratio of the solution of solvent, benzothiazole disulfide and tert-butylamine is 1：1.0-3.0；3）Step 2）Middle reaction solution enters second reactor after stopping 1-3 hours in first reactor；Into second reactor, continuously addition catalyst solution, catalyst charge are the benzothiazole disulfide weight added simultaneously The 5-30% of amount, material keep 50-100 DEG C of temperature of charge in second reactor, continue to react 0.5-2 hours；4) by step 3）Middle reaction solution filtering, washs, dry required product through distilling desolventizing, cooling to less than 20 DEG C；5）Filtrate is passed through to the concentration reuse being concentrated under reduced pressure to 30%.
- 2. preparation method according to claim 1, it is characterized in that organic solvent is alcohols or aromatic hydrocarbon substance, organic solvent Dosage is 1-10 times of benzothiazole disulfide weight.
- 3. preparation method according to claim 2, it is characterized in that consumption of organic solvent is benzothiazole disulfide weight 2-3 times.
- 4. the preparation method according to Claims 2 or 3, it is characterized in that alcohols solvent be methanol, ethanol, isopropanol,（It is different） Butanol, cyclohexanol, methyl isobutyl alcohol or one or more, aromatic hydrocarbon solvent be toluene, ethylbenzene, one kind in dimethylbenzene or It is a variety of.
- 5. preparation method according to claim 1, it is characterised in that catalyst used is inorganic or organic basic material, Inorganic base is the one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, and organic base is TMAH, four fourths One or both of base ammonium hydroxide, the dosage of catalyst agent are the 5%-30% of benzothiazole disulfide weight.
- 6. preparation method according to claim 5, it is characterized in that the dosage of catalyst agent is benzothiazole disulfide weight 10%.
- 7. preparation method according to claim 1, it is characterised in that the mol ratio of benzothiazole disulfide and tert-butylamine is 1：1.0-10.
- 8. preparation method according to claim 7, it is characterised in that the mol ratio of benzothiazole disulfide and tert-butylamine is 1：1.5-1.8.
- 9. preparation method according to claim 1, its feature is 1-3 hours for fear of the reaction time of first reactor, the The time in reaction time of two reactors is 0.5-2 hours；First reactor temperature is 20-50 DEG C, the reaction temperature of second reactor Spend for 50-100 DEG C.
- 10. preparation method according to claim 9, the reaction time of first reactor is 1.5 hours, second reactor Time in reaction time is 1 hour；First reactor temperature is 40-45 DEG C, and the reaction temperature of second reactor is 80-85 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116993A (en) * | 2019-12-06 | 2020-05-08 | 科迈化工股份有限公司 | TBBS granulation adhesive, preparation method and application |
Citations (3)
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|---|---|---|---|---|
| US4751301A (en) * | 1985-05-11 | 1988-06-14 | Bayer Aktiengesellschaft | Process for preparing benzothiazolesulphenamides |
| CN104557772A (en) * | 2014-12-16 | 2015-04-29 | 科迈化工股份有限公司 | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking methanol as solvent |
| CN105503772A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method for N-tert-butyl benzothiazole sulfenamide |
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2016
- 2016-09-14 CN CN201610823600.7A patent/CN107814776A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751301A (en) * | 1985-05-11 | 1988-06-14 | Bayer Aktiengesellschaft | Process for preparing benzothiazolesulphenamides |
| CN105503772A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method for N-tert-butyl benzothiazole sulfenamide |
| CN104557772A (en) * | 2014-12-16 | 2015-04-29 | 科迈化工股份有限公司 | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking methanol as solvent |
Non-Patent Citations (2)
| Title |
|---|
| 徐万平 等: "硫化促进剂N-叔丁基-苯并噻唑(TBBS)的合成工艺综述", 《化工时刊》 * |
| 贾太轩 等: "Ｎ-叔丁基-２-苯骈噻唑次磺酰胺制备及其光谱分析", 《光谱学与光谱分析》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116993A (en) * | 2019-12-06 | 2020-05-08 | 科迈化工股份有限公司 | TBBS granulation adhesive, preparation method and application |
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Application publication date: 20180320 |