CN104557774A - Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent - Google Patents
Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent Download PDFInfo
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- CN104557774A CN104557774A CN201410784541.8A CN201410784541A CN104557774A CN 104557774 A CN104557774 A CN 104557774A CN 201410784541 A CN201410784541 A CN 201410784541A CN 104557774 A CN104557774 A CN 104557774A
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- accelerator
- dicyclohexyl
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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
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- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method for producing an accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as a solvent. The synthesis method comprises the following steps: adding 50-80g of molten crude M into a reactor containing 45-72g of dicyclohexylamine and 600ml of isopropanol, fully reacting the crude M with dicyclohexylamine in the temperature range of 60-100 DEG C at the rotational speed of 800 revolutions/minute, then adding an oxidant, namely sodium hypochlorite with 12-18mg/100ml of available chlorine at the flow rate of 5ml/min, simultaneously controlling the pH value of a reaction solution to 8-11, dropping for 2h, and performing suction filtration, water washing, filtration and drying after the reaction to obtain a rubber accelerator DZ product. The purity of the accelerator DZ is above 99%. The method has the advantages of simple process, low production cost, easiness in industrialization, high yield of product DZ and good quality.
Description
Technical field
The present invention relates to the production method of a kind of thiofide N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ), belong to rubber vulcanization accelerator DZ production technical field.
Background technology
Along with the development of rubber industry, the R & D and manufacture of vulcanization accelerator more and more comes into one's own.DZ is delayed action accelerator, is the requisite a kind of primary accelerator of current 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.Patent (patent No. 200810053774.5) the method process delivered on July 8th, 2008 comprises: join in stills for air blowing by Virahol and dicyclohexyl amine, under the condition stirred, dicyclohexyl amine is fully dissolved in Virahol, with certain flow velocity, add sulfuric acid, control pH value simultaneously, then M-Na salt is added with certain flow velocity, drip oxidizing agent sodium hypochlorite simultaneously, pH value is controlled, after completion of the reaction suction filtration, washing, filtration, dry rubber accelerator DZ product in reaction process.Although the DZ quality that the method for this patent obtains reaches 99%, the not concrete numeral of yield, and operation needs three kinds of raw materials to drip simultaneously, also needs the PH controlling reaction solution, so operationally more complicated.Document (scientific and technical information, 2005,7:23) reports the method for large proportioning oxidation style synthesis DZ.Captax, dicyclohexyl amine, Virahol are added in reactor and stirs, make its salify; React as oxygenant with clorox, cooling, suction filtration, washing, filtration, dry product.The dicyclohexyl amine amount that this method uses is large, and the yield of accelerator DZ is not high.Document (China Synthetic Rubber Industry, 1996,19:317) reports the fast synthesis method of accelerator DZ.Captax, dicyclohexyl amine, Virahol are added in reactor and stirs, make its salify; React as oxygenant with hydrogen peroxide, cooling, suction filtration, washing, filtration, dry product.This method salify rate is low, causes DZ yield low.
Summary of the invention
The object of the present invention is to provide a kind of with clorox be oxygenant, with thick M be raw material, Virahol is that the method for rubber vulcanization accelerator DZ produced by solvent, the method is simple to operate, do not need to drip three kinds of raw materials simultaneously, do not need the pH value controlling reaction solution, dicyclohexyl amine consumption is appropriate, and the DZ synthesized is at yield, higher qualitatively.
For achieving the above object, the present invention is realized by following technical proposals: a kind of with clorox be oxygenant, with thick M be raw material, Virahol produces the method for rubber vulcanization accelerator DZ for solvent, it is characterized in that comprising following process:
The thick M50-80g of melting is joined in the reactor of existing 45-72 gram dicyclohexyl amine and 600ml Virahol, under 60-100 DEG C of scope, rotating speed are the condition of 800 revs/min, make thick M fully and dicyclohexyl amine react, then add with the flow velocity of 5ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 12-18mg/100ml, control the pH8-11 of reaction soln simultaneously, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, dry rubber accelerator DZ product.
The invention has the advantages that: the method process is simple, do not need to drip three kinds of raw materials simultaneously, do not need the pH value controlling reaction solution, do not use sulfuric acid, sodium hydroxide, do not produce the waste water of contains sodium sulfate, production cost is low, is easy to industrialization, the dicyclohexyl amine used is appropriate, and the purity of the accelerator DZ synthesized reaches more than 95%.Yield reaches more than 95%.
Embodiment
Embodiment 1:
The thick M50g of melting is joined in the reactor of existing 45 grams of dicyclohexyl amines and 600ml Virahol, under 60 DEG C of rotating speeds are the condition of 800 revs/min, make thick M fully and dicyclohexyl amine react, then add with the flow velocity of 5ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 12mg/100ml, control the pH8-11 of reaction soln simultaneously, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, dry rubber accelerator DZ product.The purity of accelerator DZ reaches more than 95%.
Embodiment 2:
The thick M65g of melting is joined in the reactor of existing 58.5 grams of dicyclohexyl amines and 600ml Virahol, under 80 DEG C of rotating speeds are the condition of 800 revs/min, make thick M fully and dicyclohexyl amine react, then add with the flow velocity of 5ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 16mg/100ml, control the pH8-11 of reaction soln simultaneously, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, dry rubber accelerator DZ product.The purity of accelerator DZ reaches more than 95%.
Embodiment 3:
The thick M80g of melting is joined in the reactor of existing 72 grams of dicyclohexyl amines and 600ml Virahol, under 100 DEG C of rotating speeds are the condition of 800 revs/min, make thick M fully and dicyclohexyl amine react, then add with the flow velocity of 5ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 18mg/100ml, control the pH8-11 of reaction soln simultaneously, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, dry rubber accelerator DZ product.The purity of accelerator DZ reaches more than 95%.
Claims (1)
1. one kind is that accelerant N produced by solvent with Virahol, the synthetic method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, the thick M50-80g of melting is joined in the reactor of existing 45-72 gram dicyclohexyl amine and 600ml Virahol, 60-100 DEG C of scope, rotating speed is under the condition of 800 revs/min, make thick M fully and dicyclohexyl amine react, then add with the flow velocity of 5ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 12-18mg/100ml, control the pH8-11 of reaction soln simultaneously, time for adding is 2 hours, suction filtration after completion of the reaction, washing, filter, dry rubber accelerator DZ product.The purity of accelerator DZ reaches more than 99%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410784541.8A CN104557774A (en) | 2014-12-16 | 2014-12-16 | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent |
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| CN201410784541.8A CN104557774A (en) | 2014-12-16 | 2014-12-16 | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent |
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| CN104557774A true CN104557774A (en) | 2015-04-29 |
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| CN201410784541.8A Pending CN104557774A (en) | 2014-12-16 | 2014-12-16 | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658894A (en) * | 2018-06-12 | 2018-10-16 | 山东尚舜化工有限公司 | A kind of synthetic method of thiofide DCBS |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314663A1 (en) * | 1987-10-29 | 1989-05-03 | Monsanto Europe S.A./N.V. | Process for the preparation of benzothiazole-2-sulphenamides |
| CN102391206A (en) * | 2011-09-20 | 2012-03-28 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator DZ |
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2014
- 2014-12-16 CN CN201410784541.8A patent/CN104557774A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314663A1 (en) * | 1987-10-29 | 1989-05-03 | Monsanto Europe S.A./N.V. | Process for the preparation of benzothiazole-2-sulphenamides |
| CN102391206A (en) * | 2011-09-20 | 2012-03-28 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator DZ |
Non-Patent Citations (2)
| 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, 30 April 1999 (1999-04-30), pages 25 - 26 * |
| 殷树梅等: "一步法合成高品质N,N-二环己基-2-苯并噻唑次磺酰胺新工艺", 《精细石油化工》, vol. 23, no. 6, 30 November 2006 (2006-11-30), pages 7 - 9 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658894A (en) * | 2018-06-12 | 2018-10-16 | 山东尚舜化工有限公司 | A kind of synthetic method of thiofide DCBS |
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Application publication date: 20150429 |