CN102367238A - Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide - Google Patents
Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide Download PDFInfo
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- CN102367238A CN102367238A CN201110280208XA CN201110280208A CN102367238A CN 102367238 A CN102367238 A CN 102367238A CN 201110280208X A CN201110280208X A CN 201110280208XA CN 201110280208 A CN201110280208 A CN 201110280208A CN 102367238 A CN102367238 A CN 102367238A
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Abstract
The invention discloses a method for synthesizing an accelerator N,N-dicyclohexyl-2-benzothiazole sulfonamide. The method comprises the following steps: adding 200-1000ml 10-30% sulfuric acids into a reaction kettle containing 200-1000g dicyclohexyl amines; fully reacting the sulfuric acids with the dicyclohexyl amines at 20-80 DEG C under a condition of a rotating speed about 200-1500rpm; filtering and then adding into an oxidation pot; and then adding 200-1000ml isopropyl alcohol; adding an oxidizing agent sodium hypochlorite of which a mass content is 8.0-18.0%, under the condition of a flowing speed about 20-100 milliliters per minute, wherein a dropwise adding time is 1.0-3.0 hours; after finishing the reaction, extracting, washing with water, filtering and drying, thereby acquiring a product of rubber accelerator DZ. The purity of the accelerator DZ is above 99% and the yield reaches 95%. The method has the advantages that the process is simple and is easily industrialized, few dicyclohexyl amines are adopted, the yield of product DZ is high and the quality is excellent.
Description
Technical field
The present invention relates to a kind of thiofide N, the working method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ) belongs to the rubber vulcanization accelerator DZ production technical field.
Background technology
Along with the development of rubber industry, the research of vulcanization accelerator more and more comes into one's own with production.DZ is a delayed action accelerator, is the requisite a kind of primary accelerator of present rubber industry.It can accelerate the reaction of rubber and vulcanizing agent greatly, boosts productivity, and also can improve the physical and mechanical properties of vulcanized rubber simultaneously.This procedure of patent (patent No. 200810053774.5) of delivering on July 8th, 2008 comprises: Virahol and dicyclohexyl amine are joined in the stills for air blowing, under stirring condition, make dicyclohexyl amine fully be dissolved in the Virahol; With certain flow velocity, add sulfuric acid, control pH value simultaneously; Add M-Na salt with certain flow velocity then; The dropping oxidizing agent Youxiaolin is controlled the pH value in the reaction process simultaneously, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.Though the DZ quality that the method for this patent obtains has reached 99%, the not concrete numeral of yield, and operation goes up and need three kinds of raw materials to drip simultaneously, also need control the PH of reaction solution, so in operation more complicated.Document (scientific and technical information, 2005,7:23) reported the method for the synthetic DZ of big proportioning oxidation style.With stirring in captax, dicyclohexyl amine, the Virahol adding reactor drum, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with Youxiaolin.The dicyclohexyl amine amount that this method is used is big, and the yield of accelerator DZ is not high.Document (China Synthetic Rubber Industry, 1996,19:317) reported the fast synthesis method of accelerator DZ.With stirring in captax, dicyclohexyl amine, the Virahol adding reactor drum, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with ydrogen peroxide 50.This method accelerator DZ yield is low.
Summary of the invention
To the object of the present invention is to provide a kind of hypochlorous sodium be oxygenant, be the method for raw material production rubber vulcanization accelerator DZ with M-Na salt; This method is simple to operate; Do not need to drip simultaneously three kinds of raw materials; Need not control the pH value of reaction solution, the dicyclohexyl amine consumption is an amount of, and the DZ that synthesizes is at yield, qualitatively than higher.
For achieving the above object, the present invention realizes through following technical proposals:
A kind of accelerant N; The compound method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide joins 10～30% sulfuric acid, 200～1000ml in the reaction kettle of existing 200～1000 gram dicyclohexyl amines, is under 200～1500 rev/mins the condition at 20～80 ℃, rotating speed; Make the abundant and dicyclohexyl amine reaction of sulfuric acid; Join after the filtration in the stills for air blowing, add 200～1000ml Virahol again, adding mass content with 20～100ml/ minute flow velocity then is 8.0～18.0% oxygenant Youxiaolin; The dropping time is 1.0～3.0 hours, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.
The invention has the advantages that: this procedure is simple, does not need to drip simultaneously three kinds of raw materials, need not control the pH value of reaction solution, is easy to industriallization, and the dicyclohexyl amine of use is an amount of, and the purity of the accelerator DZ that synthesizes reaches more than 99%.Yield has reached more than 95%.
Embodiment
Embodiment 1:
1000ml30% sulfuric acid is joined in the reaction kettle of existing 1000 gram dicyclohexyl amines; Be under 1500 rev/mins the condition, sulfuric acid fully to be reacted with dicyclohexyl amine at 20 ℃, rotating speed, join in the stills for air blowing after the filtration; Add the 1000ml Virahol again; Adding mass content with 100ml/ minute flow velocity then is 18.0% oxygenant Youxiaolin, and the dropping time is 3.0 hours, reaction finish back suction filtration, washing, filtration, dry rubber accelerator DZ product; The purity of accelerator DZ reaches more than 99%, and yield has reached 96%.
Embodiment 2:
500ml15% sulfuric acid is joined in the reaction kettle of existing 200 gram dicyclohexyl amines; Be under 600 rev/mins the condition, sulfuric acid fully to be reacted with dicyclohexyl amine at 50 ℃, rotating speed, join in the stills for air blowing after the filtration; Add the 300ml Virahol again; Adding mass content with 60ml/ minute flow velocity then is 13.0% oxygenant Youxiaolin, and the dropping time is 2.0 hours, reaction finish back suction filtration, washing, filtration, dry rubber accelerator DZ product; The purity of accelerator DZ reaches more than 99%, and yield has reached 95.6%.
Embodiment 3:
Enforcement joins 200ml10% sulfuric acid in the reaction kettle of existing 500 gram dicyclohexyl amines; Be under 200 rev/mins the condition, sulfuric acid fully to be reacted with dicyclohexyl amine at 80 ℃, rotating speed, join in the stills for air blowing after the filtration; Add the 200ml Virahol again; Adding mass content with 20ml/ minute flow velocity then is 8.0% oxygenant Youxiaolin, and the dropping time is 1 hour, reaction finish back suction filtration, washing, filtration, dry rubber accelerator DZ product; The purity of accelerator DZ reaches more than 99%, and yield has reached 95%.
Claims (1)
1. accelerant N; The compound method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide is characterized in that 10～30% sulfuric acid, 200～1000ml is joined in the reaction kettle of existing 200～1000 gram dicyclohexyl amines, is under 200～1500 rev/mins the condition at 20～80 ℃, rotating speed; Make the abundant and dicyclohexyl amine reaction of sulfuric acid; Join after the filtration in the stills for air blowing, add 200～1000ml Virahol again, adding mass content with 20～100ml/ minute flow velocity then is 8.0～18.0% oxygenant Youxiaolin; The dropping time is 1.0～3.0 hours, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110280208XA CN102367238A (en) | 2011-09-20 | 2011-09-20 | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110280208XA CN102367238A (en) | 2011-09-20 | 2011-09-20 | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide |
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| CN102367238A true CN102367238A (en) | 2012-03-07 |
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| CN201110280208XA Pending CN102367238A (en) | 2011-09-20 | 2011-09-20 | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| CN102838565A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Production method of rubber vulcanization accelerator DZ |
| CN103102327A (en) * | 2012-11-16 | 2013-05-15 | 江苏国立化工科技有限公司 | Preparation method of rubber accelerator DZ (N,N-Dicyclohexyl-2-benzothiazolsulfene amide) |
| 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 |
| CN103524450A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Synthetic method for accelerator DZ by using methanol as solvent |
| 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 |
Citations (5)
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| US3549650A (en) * | 1966-12-22 | 1970-12-22 | Monsanto Co | Process for preparing n-branched-chain alkyl and cycloalkyl 2-benzothiazole sulfenamides |
| RO110337B1 (en) * | 1995-03-23 | 1995-12-29 | Inst Cercetari Chim | Preparation process of 2-benztyazolesulphenamides with possibility of dispersion and increased stability |
| CN101318942A (en) * | 2008-07-18 | 2008-12-10 | 天津市科迈化工有限公司 | Novel method for preparing vulcanized rubber accelerant DZ with cooling-down circulating water system |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
| CN101899020A (en) * | 2010-03-22 | 2010-12-01 | 天津市科迈化工有限公司 | DZ synthesized by mixing mother solution |
-
2011
- 2011-09-20 CN CN201110280208XA patent/CN102367238A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549650A (en) * | 1966-12-22 | 1970-12-22 | Monsanto Co | Process for preparing n-branched-chain alkyl and cycloalkyl 2-benzothiazole sulfenamides |
| RO110337B1 (en) * | 1995-03-23 | 1995-12-29 | Inst Cercetari Chim | Preparation process of 2-benztyazolesulphenamides with possibility of dispersion and increased stability |
| CN101318942A (en) * | 2008-07-18 | 2008-12-10 | 天津市科迈化工有限公司 | Novel method for preparing vulcanized rubber accelerant DZ with cooling-down circulating water system |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
| CN101899020A (en) * | 2010-03-22 | 2010-12-01 | 天津市科迈化工有限公司 | DZ synthesized by mixing mother solution |
Non-Patent Citations (1)
| Title |
|---|
| 张越，等: "用粗M合成橡胶硫化促进剂DZ", 《化学推进剂与高分子材料》, no. 4, 31 December 1999 (1999-12-31) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| CN102838565A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Production method of rubber vulcanization accelerator DZ |
| CN103102327A (en) * | 2012-11-16 | 2013-05-15 | 江苏国立化工科技有限公司 | Preparation method of rubber accelerator DZ (N,N-Dicyclohexyl-2-benzothiazolsulfene amide) |
| 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 |
| CN103524450A (en) * | 2013-09-30 | 2014-01-22 | 科迈化工股份有限公司 | Synthetic method for accelerator DZ by using methanol as solvent |
| 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 |
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Application publication date: 20120307 |