CN102850294A - Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant - Google Patents
Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant Download PDFInfo
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- CN102850294A CN102850294A CN2012103623560A CN201210362356A CN102850294A CN 102850294 A CN102850294 A CN 102850294A CN 2012103623560 A CN2012103623560 A CN 2012103623560A CN 201210362356 A CN201210362356 A CN 201210362356A CN 102850294 A CN102850294 A CN 102850294A
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Abstract
The invention relates to a method for synthesizing a rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via a two-step process by using hydrogen peroxide as an oxidant. The method comprises the following steps: step 1: weighing 100g of 98% sulfuric acid to prepare 20% sulfuric acid; adding into a reaction kettle containing 94g of cyclohexylamine; sufficiently reacting the sulfuric acid with the cyclohexylamine under a condition of controlling the temperature at 50 DEG C and the rotation speed at 500r/min; and dropping 130ml of M-Na salt with the density of 1.5g/ml to generate M-cyclohexylamine salt; and step 2: adding 600ml of oxidant hydrogen peroxide with the mass content of 8.0-18.0% at flow rate of 5ml/min; dropwise adding for 2.0 hours; extracting, washing with water, filtering and drying after the reaction to obtain the rubber vulcanizing promoter CZ, wherein the purity of the promoter CZ is higher than 99%. The method is simple in process, the M-Na salt in an M workshop is directly used as a raw material to leave out an acidification process and a dewatering and drying process in the M workshop and leave out a cyclohexylamine recycling process in a traditional technique; and the method provided by the invention is suitable for industrialization.
Description
Technical field
The present invention relates to the novel synthesis of a kind of thiofide N cyclohexyl 2 benzothiazole sulfenamide (CZ), belong to the rubber vulcanization accelerant CZ production technical field.Take the method for hydrogen peroxide as oxygenant two step synthesis rubber vulcanization accelerant CZ
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 very important effect in Vulcanization Process of Rubber, it can accelerate the reaction of rubber and vulcanizing agent greatly, boost productivity, also can improve the physical and mechanical properties of vulcanized rubber simultaneously, CZ is the requisite a kind of primary accelerator of present rubber industry.Accelerant CZ is the active aftereffect of a kind of height half ultra fast accelerator, and scorching quality is good, process safety, and curing time is short.Document (fine chemistry industry, 2006,23:923) reported the method that catalytic oxidation synthesizes CZ.With stirring in captax, hexahydroaniline, catalyzer, the water adding reactor, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with hydrogen peroxide.The hexahydroaniline amount that this method is used is large, and mother liquor is through the Distillation recovery hexahydroaniline, and the yield of accelerant CZ is not high.Document (Guangxi Chemical Industry, 1994,23:58) reported the fast synthesis method of accelerant CZ.With stirring in captax, hexahydroaniline, catalyzer, the water adding reactor, make its salify; React suction filtration, washing, filtration, the dry product that gets as oxygenant with hydrogen peroxide.Mother liquor is through the Distillation recovery hexahydroaniline.This method accelerant CZ yield is low.
Summary of the invention
The object of the present invention is to provide take the method for a kind of hydrogen peroxide as oxygenant two step synthesis rubber vulcanization accelerant CZ; Take hydrogen peroxide as oxygenant, take the method for M-Na salt as the raw material production rubber vulcanization accelerant CZ, the method is simple to operate, and the hexahydroaniline consumption is little, good product quality, yield high, and the hexahydroaniline content in the mother liquor is very low, without Distillation recovery.
For achieving the above object, the present invention is realized by following technical proposals: a kind of take hydrogen peroxide as the oxygen agent, take the method for M-Na salt as the raw material production rubber vulcanization accelerant CZ, it is characterized in that comprising following process:
The first step takes by weighing 98% sulfuric acid 100g, is configured to 20% sulfuric acid, joins in the reactor of existing 94 gram hexahydroaniline, be under 500 rev/mins the condition at 50 ° of C, rotating speed, make the abundant and hexahydroaniline reaction of sulfuric acid, dripping density is 1.5g/ml M-Na salt 130ml again, generates the M-cyclohexylamine salt.
Second step adds the oxidant hydrogen peroxide 600ml of mass content as 8.0 ~ 18.0% take 5ml/ minute flow velocity, time for adding is 2.0 hours, react complete rear suction filtration, washing, filtration, the dry rubber accelerator CZ product that gets, the purity of accelerant CZ reaches more than 99%.
The invention has the advantages that: the method process is simple, directly the M-Na salt with the M workshop is raw material, has saved the acidizing process in M workshop and drying, drying process, has saved the hexahydroaniline recovery process in the old technique, be easy to industrialization, the purity of the accelerant CZ that synthesizes reaches more than 99%.Yield has reached more than 97%.
Embodiment
Embodiment 1:
The first step takes by weighing 98% sulfuric acid 100g, is configured to 20% sulfuric acid, joins in the reactor of existing 94 gram hexahydroaniline, be under 500 rev/mins the condition at 50 ° of C, rotating speed, make the abundant and hexahydroaniline reaction of sulfuric acid, dripping density is 1.5g/ml M-Na salt 130ml again, generates the M-cyclohexylamine salt.
Second step adds the oxidant hydrogen peroxide 600ml of mass content as 8.0% take 5ml/ minute flow velocity, time for adding is 2.0 hours, react complete rear suction filtration, washing, filtration, the dry rubber accelerator CZ product that gets, the purity of accelerant CZ reaches more than 99%, and yield has reached 97%.
Embodiment 2:
The first step takes by weighing 98% sulfuric acid 100g, is configured to 20% sulfuric acid, joins in the reactor of existing 94 gram hexahydroaniline, be under 500 rev/mins the condition at 50 ° of C, rotating speed, make the abundant and hexahydroaniline reaction of sulfuric acid, dripping density is 1.5g/ml M-Na salt 130ml again, generates the M-cyclohexylamine salt.
Second step adds the oxidant hydrogen peroxide 600ml of mass content as 14.0% take 5ml/ minute flow velocity, time for adding is 2.0 hours, react complete rear suction filtration, washing, filtration, the dry rubber accelerator CZ product that gets, the purity of accelerant CZ reaches more than 99%, and yield has reached 97.4%.
Embodiment 3:
The first step takes by weighing 98% sulfuric acid 100g, is configured to 20% sulfuric acid, joins in the reactor of existing 94 gram hexahydroaniline, be under 500 rev/mins the condition at 50 ° of C, rotating speed, make the abundant and hexahydroaniline reaction of sulfuric acid, dripping density is 1.5g/ml M-Na salt 130ml again, generates the M-cyclohexylamine salt.
Second step adds the oxidant hydrogen peroxide 600ml of mass content as 18.0% take 5ml/ minute flow velocity, time for adding is 2.0 hours, react complete rear suction filtration, washing, filtration, the dry rubber accelerator CZ product that gets, the purity of accelerant CZ reaches more than 99%, and yield has reached 97.1%.
Claims (1)
1. one kind take the method for hydrogen peroxide as oxygenant two step synthesis rubber vulcanization accelerant CZ; It is characterized in that step is as follows:
The first step takes by weighing 98% sulfuric acid 100g, is configured to 20% sulfuric acid, joins in the reactor of existing 94 gram hexahydroaniline, be under 500 rev/mins the condition at 50 ° of C, rotating speed, make the abundant and hexahydroaniline reaction of sulfuric acid, dripping density is 1.5g/ml M-Na salt 130ml again, generates the M-cyclohexylamine salt;
Second step adds the oxidant hydrogen peroxide 600ml of mass content as 8.0 ~ 18.0% take 5ml/ minute flow velocity, and time for adding is 2.0 hours, reacts complete rear suction filtration, washing, filtration, dry rubber accelerator CZ product.
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| CN2012103623560A CN102850294A (en) | 2012-09-25 | 2012-09-25 | Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant |
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| CN2012103623560A CN102850294A (en) | 2012-09-25 | 2012-09-25 | Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508978A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ with two-dropping method |
| CN103524454A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerant DZ by solvent method |
| CN103804319A (en) * | 2014-03-06 | 2014-05-21 | 东营万通橡胶助剂有限公司 | Process for recycling accelerator M from residual liquid of rubber accelerator CZ distillation still |
| CN104119293A (en) * | 2013-04-24 | 2014-10-29 | 陈尔凡 | Method for synthesizing rubber accelerator CBS through plasma oxidation process |
| CN107445918A (en) * | 2017-08-14 | 2017-12-08 | 青岛奥克凯姆化学助剂有限公司 | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method |
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| CN101157664A (en) * | 2007-09-10 | 2008-04-09 | 天津市科迈化工有限公司 | New method for synthesizing rubber vulcanization accelerator CZ |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
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2012
- 2012-09-25 CN CN2012103623560A patent/CN102850294A/en active Pending
Patent Citations (2)
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| CN101157664A (en) * | 2007-09-10 | 2008-04-09 | 天津市科迈化工有限公司 | New method for synthesizing rubber vulcanization accelerator CZ |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
Non-Patent Citations (1)
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| 胡生泳 等: "硫化促进剂CZ合成方法进展", 《精细石油化工》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119293A (en) * | 2013-04-24 | 2014-10-29 | 陈尔凡 | Method for synthesizing rubber accelerator CBS through plasma oxidation process |
| CN104119293B (en) * | 2013-04-24 | 2016-03-23 | 陈尔凡 | Plasma oxidation method synthetic rubber accelerator CBS |
| CN103508978A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ with two-dropping method |
| CN103524454A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerant DZ by solvent method |
| CN103804319A (en) * | 2014-03-06 | 2014-05-21 | 东营万通橡胶助剂有限公司 | Process for recycling accelerator M from residual liquid of rubber accelerator CZ distillation still |
| CN107445918A (en) * | 2017-08-14 | 2017-12-08 | 青岛奥克凯姆化学助剂有限公司 | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method |
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Application publication date: 20130102 |