CN101676273B - Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide - Google Patents
Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide Download PDFInfo
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Abstract
A method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfonamide belongs to the field of fine chemical engineering. In the method, 2-thiol group benzothiazole crude product is used as raw material, and organic matters are added into the reaction system as a decoking agent to remove tar in the raw material MBT so as to directly produce a qualified product. The invention can reduce the MBT refining step, saves acid, alkali, labor wage and power consumed in the refining process, thus reducing production cost and greatly reducing waste water amount produced in the MBT refining step; the invention is an energy-saving, consumption-reducing and environment-friendly preparation technique, and is suitable for industrial production.
Description
Technical field: the invention belongs to the fine chemical technology field, be specifically related to a kind of environmental protection and energy saving, utilizing 2-benzothiazolyl mercaptan (MBT) crude product is that raw material directly synthesizes the into method of accelerator N-tertiary butyl benzothiazole time acid amides (hereinafter to be referred as accelerator NS).
Background technology: accelerator NS belongs to the sulfenamide aftereffect thiofide of high comprehensive performance, be developed country and the regional main rubber ingredients kinds of using such as the U.S., West Europe, its consumption is about 60% of sulfenamide type accelerators total quantity consumed, variable color and contaminative are slight, have multiple functions such as anti-scorch, promotion, activation, in fields such as styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, polyisoprene rubber, obtained to use widely.Because NS has the primary amine structure,, be described as standard promotor so can not produce carcinogens such as nitrosamine.Its chemical structure is:
Preparation method at present commonly used is that an alkali metal salt and the TERTIARY BUTYL AMINE with 2-benzothiazolyl mercaptan (MBT) or DM or MBT is raw material, reacts to form under the effect of oxygenant.Its chemical equation is:
According to the molecular ratio of raw material, aforesaid method is divided into big matching method and little matching method again.
It is 4 that U.S. Longwote Co (US4258197) adopts the molecular ratio of amine and MBT, and yield is 92%.
Japan artificial silk company of eastern nation (JP74110664, JP74134674) adds tensio-active agent in water, the molecular ratio of TERTIARY BUTYL AMINE and MBT reduces to 1.5, and yield reaches 96%.
The yield of domestic patent (CN1069489A) report is 93%.Selected oxygenant comprises clorox, chlorine and hydrogen peroxide.
The employed raw material MBT of the above the whole bag of tricks is through purified, content greater than 98% product, this product used process for purification usually is an acid-base method: be about to the dissolving of crude product MBT adding diluted alkaline and separate out except that the defocused diluted acid that adds again, produce a large amount of waste water in the treating process, whenever refining 1 ton of MBT finished product produces 30 tons of waste water approximately.The various documents of consulting are not seen the method that MBT crude product synthesis accelerant NS is arranged.And crude product MBT is normally made by the reaction under high temperature, high pressure of aniline, sulphur and dithiocarbonic anhydride, reaction is except that generating desired substance, other has impurity such as intermediate products such as diphenyl thiourea, benzothiazole and tar, and the content of main composition (butt) is about 85-92%.When the crude product MBT that contains impurity was used for synthetic NS, impurity can remain in the finished product, causes the defective of quality.
Summary of the invention: main purpose of the present invention provides a kind of environmental protection and energy saving novel method, is raw material with the MBT crude product promptly, directly synthesis accelerant NS.Thereby make MBT make with extra care and merge into the purpose that a step reaches consumption reduction, energy-saving and environmental protection.
The present invention is achieved like this: mainly be to adopt the MBT crude product, promptly 2-benzothiazolyl mercaptan crude product is the direct synthesis accelerant N of raw material-tertiary butyl benzo thiazolesulfenamide.
Specifically the inventive method is that MBT crude product, TERTIARY BUTYL AMINE, water are added in the reactor, after stirring, add oxygenant and decoking agent to reaction end (when decoking agent is aniline and hexahydroaniline, then after finishing the adding oxygenant, add again), cooling, filter, with filter cake with water washing to pH be neutrality, promptly get accelerant N-tertiary butyl benzo thiazolesulfenamide finished product behind the filtration cakes torrefaction.Reaction conditions: oxidizing temperature: 25-40 ℃; Oxidization time: 1-2 hours; The molecular ratio of TERTIARY BUTYL AMINE and MBT: 3.5-5; Finished product drying temperature: 50-70 ℃.
Usually, the quality index of MBT crude product of the present invention is weight percentage: moisture content≤30%, oven dry back MBT content 〉=90%; Selected organism decoking agent is a kind of in hexalin, isopropylcarbinol, aniline, the hexahydroaniline.
Above-mentioned decoking agent hexalin or isopropylcarbinol can add before oxidizer, also can add after oxidizer.
Above-mentioned decoking agent aniline or hexahydroaniline add after oxidizer.
Usually, decoking agent aniline or isopropylcarbinol or hexalin content are greater than 99%, and add-on is 1-2 a times of MBT weight; The concentration expressed in percentage by weight of decoking agent hexahydroaniline is 40%-100%, and all the other components are water, and the 1-2 that the pure product add-on of hexahydroaniline is a MBT weight doubly.
Compared with prior art, the present invention only need add the purpose that certain amount of organic solvent can reach decoking in building-up process, raw material MBT is made with extra care with the accelerator NS synthesis step unite two into one, and has reduced the consumption of MBT, reduce the quantity of waste water, reduced production cost.Present method is specially adapted to the enterprise that MBT and accelerator NS are promptly produced in the promotor coproduction simultaneously.Below respectively from accelerator NS raw material consumption and " three wastes " amount comparative descriptions positively effect of the present invention.
Raw material consumption relatively
Last table data presentation: with the MBT crude product is raw material synthesis accelerant NS, and one ton of finished product raw materials cost of every production can descend 1251 yuan.
NS finished product per ton " three wastes " generation relatively
Last table data declaration: the three wastes generation of MBT crude product technology is significantly smaller than the three wastes generation of MBT elaboration technology.
Embodiment: further specify this patent below by embodiment.
Comparative Examples: with the MBT crude product is raw material, does not add decoking agent
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (water content: 23.57%, dry product purity 90.69%), under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, TERTIARY BUTYL AMINE adds aqueous sodium hypochlorite solution (volume 100ml, available chlorine content 173.88g/L) after feeding in raw material and finishing again, 45～55 ℃ of reinforced process temperature span of control, after adding, uniform temp is kept reaction 1 hour, be cooled to 25 ℃, filter 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 101.9 ℃ of finished product fusing points, yield 95.8% (in MBT).The fusing point index of accelerator NS salable product is 103 ℃, and test-results shows, can not obtain qualified finished product with crude product MBT synthesis accelerant.
Embodiment 1: add the decoking agent hexalin before oxygenant drips
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (component concentration is with embodiment 1), hexalin 72.3 grams, under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, after adding amine and finishing, add aqueous sodium hypochlorite solution (volume 100ml, available chlorine content 173.88g/L), 45～55 ℃ of reinforced process temperature span of control, after adding, uniform temp is kept reaction 1 hour, be cooled to 25 ℃, filter 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 103.2 ℃ of finished product fusing points, yield 72.4% (in MBT) reaches salable product fusing point index.
Embodiment 2: add the decoking agent isopropylcarbinol before oxygenant drips
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (component concentration is with embodiment 1), isopropylcarbinol 72.3 grams, under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, behind reinforced the finishing, add aqueous sodium hypochlorite solution (volume 100ml, available chlorine content 173.88g/L), drip 45～55 ℃ of process temperature span of control, after dropwising, uniform temp is kept reaction 1 hour, be cooled to 25 ℃, filter 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 103.6 ℃ of finished product fusing points, yield 55.0% (in MBT) reaches salable product fusing point index.
Embodiment 3: add the decoking agent isopropylcarbinol behind the oxygenant material
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (component concentration is with embodiment 1) are under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, after adding amine and finishing, add aqueous sodium hypochlorite solution (volume 100ml, available chlorine content 173.88g/L) again, drip 45～55 ℃ of process temperature span of control, after dropwising, uniform temp is kept reaction 1 hour, adds isopropylcarbinol 72.3 grams, stirring was kept 30 minutes, was cooled to 25 ℃, filtered, 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 104.1 ℃ of finished product fusing points, yield 84.7% (in MBT) reaches first grade fusing point index (first grade fusing point index is 104 ℃).
Embodiment 4: the reinforced back of oxygenant adds decoking agent aniline
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (component concentration is with embodiment 1) are under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, after adding amine and finishing, drip chlorine bleach liquor (volume 100ml, available chlorine content 173.88g/L), 45～55 ℃ of reinforced process temperature span of control, after adding, uniform temp is kept reaction 1 hour, adds aniline 72.3 grams, stirring was kept 30 minutes, was cooled to 25 ℃, filtered, 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 104.3 ℃ of finished product fusing points, yield 81.3% (in MBT) reaches first grade fusing point index.
Embodiment 5: the reinforced back of oxygenant adds the decoking agent hexahydroaniline
Add entry 60ml in the four-hole boiling flask, MBT crude product 48.2 grams (component concentration is with embodiment 1) are under the agitation condition, add TERTIARY BUTYL AMINE, temperature is controlled at below 40 ℃, behind reinforced the finishing, drip chlorine bleach liquor (volume 100ml, available chlorine content 173.88g/L), 45～55 ℃ of reinforced process temperature span of control, after adding, uniform temp is kept reaction 1 hour, adds hexahydroaniline 72.3 grams, stirring was kept 30 minutes, was cooled to 25 ℃, filtered, 40ml cold water washing filter cake 3 times, 50 ℃ of oven dry.
Test-results: 104.0 ℃ of finished product fusing points, yield 89.9% (in MBT) reaches first grade fusing point index.
Claims (2)
1. the method for a direct synthesis accelerant N-tertiary butyl benzo thiazolesulfenamide, it is characterized in that adopting 2-benzothiazolyl mercaptan crude product is that raw material is directly synthetic, adds decoking agent in reaction system; Soon 2-benzothiazolyl mercaptan crude product, TERTIARY BUTYL AMINE, water add in the reactor, after stirring, add oxygenant and decoking agent, to the reaction end postcooling, filter, with filter cake with water washing to pH be neutrality, promptly get accelerator N-tertiary butyl benzothiazole sulphenamide finished product behind the filtration cakes torrefaction, reaction conditions: oxidizing temperature: 25-40 ℃; Oxidization time: 1-2 hour; The molecular ratio of TERTIARY BUTYL AMINE and 2-benzothiazolyl mercaptan: 3.5-5; Finished product drying temperature: 50-70 ℃; Described decoking agent is a kind of in hexalin, isopropylcarbinol, aniline, the hexahydroaniline; Decoking agent aniline or isopropylcarbinol or hexalin content are greater than 99%, and add-on is 1-2 a times of 2-benzothiazolyl mercaptan weight; The concentration expressed in percentage by weight of decoking agent hexahydroaniline is 40%-100%, and all the other components are water, and the pure product add-on of hexahydroaniline is 1-2 a times of 2-benzothiazolyl mercaptan weight; Decoking agent hexalin or isopropylcarbinol add before oxygenant adds or after adding; Decoking agent aniline or hexahydroaniline add the back at oxygenant and add; Described 2-benzothiazolyl mercaptan crude product is to be reacted down in high temperature, high pressure by aniline, sulphur and dithiocarbonic anhydride to make, and reaction is except that generating desired substance, and other has diphenyl thiourea, benzothiazole and tar impurity, the contents on dry basis 85-92% of main composition.
2. method according to claim 1 is characterized in that the quality index of the 2-benzothiazolyl mercaptan crude product that adopts is weight percentage: moisture content≤30%, oven dry back 2-benzothiazolyl mercaptan content 〉=90%.
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| CN2008101560715A CN101676273B (en) | 2008-09-19 | 2008-09-19 | Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide |
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| CN2008101560715A CN101676273B (en) | 2008-09-19 | 2008-09-19 | Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide |
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| CN101676273B true CN101676273B (en) | 2011-05-18 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838563A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Synthesis method of rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) |
| CN102838561A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Production method of rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) |
| CN103524453A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Synthetic method for rubber vulcanization accelerator NS by solvent method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258197A (en) * | 1979-06-08 | 1981-03-24 | Pennwalt Corporation | Manufacture of sulfenamides |
| CN1069489A (en) * | 1992-08-28 | 1993-03-03 | 沈阳化工学院 | A kind of reparation technology of thiofide |
| US5436346A (en) * | 1991-12-21 | 1995-07-25 | Akzo Nobel N.V. | Process for the preparation of benzothiazolyl-2-sulphenamides |
-
2008
- 2008-09-19 CN CN2008101560715A patent/CN101676273B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258197A (en) * | 1979-06-08 | 1981-03-24 | Pennwalt Corporation | Manufacture of sulfenamides |
| US5436346A (en) * | 1991-12-21 | 1995-07-25 | Akzo Nobel N.V. | Process for the preparation of benzothiazolyl-2-sulphenamides |
| CN1069489A (en) * | 1992-08-28 | 1993-03-03 | 沈阳化工学院 | A kind of reparation technology of thiofide |
Non-Patent Citations (2)
| Title |
|---|
| 张越等.橡胶硫化促进剂NS的合成.《河北师范大学学报(自然科学版)》.1998,第22卷(第2期),226-228，238. * |
| 徐万平等.硫化促进剂NS的合成研究.《精细化工》.2000,第17卷(第5期),277-279. * |
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Address after: Baoying County, Jiangsu province 225824 Yangzhou City Xia Ji Zhen Guo Xia Road No. 18 Patentee after: Nanhua Group Corp. Address before: 210048 Jiangsu Province, Nanjing city Liuhe District Dachang geguan Road No. 699 Patentee before: Nanhua Group Corp. |
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Address after: Baoying County, Jiangsu province 225824 Yangzhou City Xia Ji Zhen Guo Xia Road No. 18 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Baoying County, Jiangsu province 225824 Yangzhou City Xia Ji Zhen Guo Xia Road No. 18 Patentee before: Nanhua Group Research Institute |