CN103524450A - Synthetic method for accelerator DZ by using methanol as solvent - Google Patents
Synthetic method for accelerator DZ by using methanol as solvent Download PDFInfo
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- CN103524450A CN103524450A CN201310466164.9A CN201310466164A CN103524450A CN 103524450 A CN103524450 A CN 103524450A CN 201310466164 A CN201310466164 A CN 201310466164A CN 103524450 A CN103524450 A CN 103524450A
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- accelerator
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- sulfuric acid
- methanol
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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 discloses a synthetic method for an accelerator DZ by using methanol as a solvent. According to the method, the methanol is used as the solvent, sodium hypochlorite is used as an oxidizing agent, and an M-Na salt is used as a raw material. The synthetic method is characterized by adding 50 g of sulfuric acid having a concentration of 24% into a reactor already having 43g of dicyclohexylamine and 200-800 mL of the methanol, reacting the sulfuric acid and the dicyclohexylamine completely at 30-60 DEG C and at a rotate speed of 800 r/min, and then adding dropwise 98 g of the M-Na salt; adding the oxidizing agent sodium hypochlorite having effective chlorine of 12-18.0/100 mL at a flow rate of 5 mL/min with an addition time of 2 h and the pH being controlled to be 8-11 at the same time; and after the reaction is finished, performing suction filtration, washing with water, filtering and drying to obtain a rubber vulcanization accelerator DZ product. The purity of the accelerator DZ reaches over 99%. The method has simple processes, low production cost, easy industrialization, high yield for the product DZ, and good quality of the product DZ.
Description
Technical field
The present invention relates to a kind of thiofide N, the production method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ), belongs to 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 delayed action accelerator, is the requisite a kind of primary accelerator of current rubber industry.It can accelerate reacting 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 of delivering on July 8th, 2008 comprises: Virahol and dicyclohexyl amine are joined in stills for air blowing, under the condition stirring, make dicyclohexyl amine fully be dissolved in Virahol, flow velocity with certain, adds sulfuric acid, controls pH value simultaneously, then with certain flow velocity, add M-Na salt, drip oxygenant clorox simultaneously, in reaction process, control pH value, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.Although the DZ quality that the method for this patent obtains has reached 99%, the not concrete numeral of yield, and need three kinds of raw materials simultaneously to drip in operation, also needs to control the PH of reaction solution, thus in operation more complicated.Document (scientific and technical information, 2005,7:23) reported the method for the synthetic DZ of large proportioning oxidation style.Captax, dicyclohexyl amine, Virahol are added in reactor and stirred, make its salify; With clorox, as oxygenant, react cooling, suction filtration, washing, filtration, the dry product that to obtain.The dicyclohexyl amine amount that this method is used is large, 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.Captax, dicyclohexyl amine, Virahol are added in reactor and stirred, make its salify; With hydrogen peroxide, as oxygenant, react cooling, suction filtration, washing, filtration, the dry product that to obtain.This method accelerator DZ yield is low.
Summary of the invention
The object of the present invention is to provide a kind of take methyl alcohol as solvent, clorox be oxygenant, the method for M-Na salt as raw material production rubber vulcanization accelerator DZ of take, the method is simple to operate, do not need to drip three kinds of raw materials simultaneously, do not need to control the pH value of reaction solution, the methyl alcohol lower with unit price is solvent, and the DZ synthesizing is at yield, higher qualitatively.
For achieving the above object, the present invention is realized by following technical proposals: a kind of take methyl alcohol as solvent clorox as oxygenant, the M-Na salt of the take method that is raw material production rubber vulcanization accelerator DZ, it is characterized in that comprising following process:
24% sulfuric acid 50g joins in the reactor of existing 43 grams of dicyclohexyl amines and 200～800ml methyl alcohol, is, under the condition of 800 revs/min, to make sulfuric acid fully and dicyclohexyl amine reaction, at dropping 98g M-Na salt at 30-60 ℃, rotating speed; The flow velocity of then take 5ml/ minute adds the oxygenant clorox that available chlorine is 12-18.0/100ml, controls the pH8-11 of reaction soln simultaneously, and time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.
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 to control the pH value of reaction solution, using unit price is solvent than the methyl alcohol of low one times of Virahol, be easy to industrialization, the dicyclohexyl amine of use is appropriate, and the purity of the accelerator DZ synthesizing reaches more than 99%.Yield has reached more than 95%.
Embodiment
Embodiment 1:
24% sulfuric acid 50g joins in the reactor of existing 43 grams of dicyclohexyl amines and 200ml methyl alcohol, at 30 ° of C, rotating speed, be under the condition of 800 revs/min, make sulfuric acid fully and dicyclohexyl amine react, dripping 98g M-Na salt, the flow velocity of then take 5ml/ minute adds the oxygenant clorox that available chlorine is 18.0/100ml, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.
Embodiment 2:
24% sulfuric acid 50g joins in the reactor of existing 43 grams of dicyclohexyl amines and 500ml methyl alcohol, at 45 ℃, rotating speed, be under the condition of 800 revs/min, make sulfuric acid fully and dicyclohexyl amine react, dripping 98g M-Na salt, the flow velocity of then take 5ml/ minute adds the oxygenant clorox that available chlorine is 15.0/100ml, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.
Embodiment 3:
24% sulfuric acid 50g joins in the reactor of existing 43 grams of dicyclohexyl amines and 800ml methyl alcohol, at 60 ℃, rotating speed, be under the condition of 800 revs/min, make sulfuric acid fully and dicyclohexyl amine react, dripping 98g M-Na salt, the flow velocity of then take 5ml/ minute adds the oxygenant clorox that available chlorine is 12.0/100ml, time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.
Claims (1)
1. take the synthetic method that methyl alcohol produces accelerator DZ as solvent for one kind, take methyl alcohol as solvent, clorox as oxygenant, take M-Na salt as raw material, it is characterized in that: 24% sulfuric acid 50g is joined in the reactor of existing 43 grams of dicyclohexyl amines and 200～800ml methyl alcohol, at 30-60 ℃, rotating speed, be under the condition of 800 revs/min, make sulfuric acid fully and dicyclohexyl amine react, then drip 98g M-Na salt; The flow velocity of then take 5ml/ minute adds the oxygenant clorox that available chlorine is 12-18.0/100ml, controls the pH8-11 of reaction soln simultaneously, and time for adding is 2 hours, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310466164.9A CN103524450A (en) | 2013-09-30 | 2013-09-30 | Synthetic method for accelerator DZ by using methanol as solvent |
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| CN201310466164.9A CN103524450A (en) | 2013-09-30 | 2013-09-30 | Synthetic method for accelerator DZ by using methanol as solvent |
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| CN103524450A true CN103524450A (en) | 2014-01-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108586383A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D CBS |
| CN108727300A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of technique of sodium hypochlorite synthesis vulcanization accelerator N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102367238A (en) * | 2011-09-20 | 2012-03-07 | 科迈化工股份有限公司 | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide |
| 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 |
| 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) |
-
2013
- 2013-09-30 CN CN201310466164.9A patent/CN103524450A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102367238A (en) * | 2011-09-20 | 2012-03-07 | 科迈化工股份有限公司 | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide |
| 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 |
| 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) |
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》, 31 December 1999 (1999-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108727300A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of technique of sodium hypochlorite synthesis vulcanization accelerator N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide |
| CN108586383A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D CBS |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
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Application publication date: 20140122 |