CN103508977A - Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent - Google Patents
Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent Download PDFInfo
- Publication number
- CN103508977A CN103508977A CN201310467586.8A CN201310467586A CN103508977A CN 103508977 A CN103508977 A CN 103508977A CN 201310467586 A CN201310467586 A CN 201310467586A CN 103508977 A CN103508977 A CN 103508977A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- methanol
- accelerator
- oxidizing agent
- methyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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 method for producing a rubber vulcanization accelerator CZ (N-cyclohexylbenzothiazole-2-sulphenamide) by adopting a double-dripping method using hydrogen peroxide as an oxidizing agent. The method disclosed by the invention comprises the following steps: according to a volume ratio of methanol to cyclohexylamine of (0.5 to 0.8):1, adding mixed solution of methanol and cyclohexylamine into a glass oxidizer, and under the conditions of a temperature of 40 DEG C and a rotating speed of 600 revolutions per minute, adding slurry with a mass ratio of an accelerator M to methanol of 1:1 at a flow rate of 2ml per minute; simultaneously, dropwise adding hydrogen peroxide solution with mass content of 12 percent into the solution at a flow rate of 1ml per minute, stopping dropwise adding the hydrogen peroxide after 90 minutes and carrying out heat preservation for 10 minutes; starting to distill to recover methanol; carrying out suction filtration, washing, filtration and drying on the obtained product to obtain the rubber accelerator CZ product. The method has a simple process, utilizes methanol to replace water and uses the environmental-friendly oxidizing agent hydrogen peroxide as the oxidizing agent so as to reduce wastewater by over 60 percent relative to a conventional process; moreover, the wastewater does not contain salt. The process is easy for industrialization, uses a small quantity of cyclohexylamine and has yield of the accelerator CZ of over 99 percent.
Description
Technical field
The production method that the present invention relates to a kind of thiofide N cyclohexyl 2 benzothiazole sulfenamide (CZ), belongs to rubber vulcanization accelerant CZ production technical field.
Background technology
Along with the development of rubber industry, the research of vulcanization accelerator is more and more subject to people's attention with production.Vulcanization accelerator plays very important effect in Vulcanization Process of Rubber, it can accelerate reacting of rubber and vulcanizing agent greatly, boost productivity, also can improve the physical and mechanical properties of vulcanized rubber, CZ is the requisite a kind of primary accelerator of current rubber industry simultaneously.Accelerant CZ is aftereffect half ultra fast accelerator that a kind of height is active, 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.Captax, hexahydroaniline, catalyzer, water 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.The hexahydroaniline amount that this method is used is large, and the yield of accelerant CZ is not high.Document (Guangxi Chemical Industry, 1994,23:58) reported the fast synthesis method of accelerant CZ.Captax, hexahydroaniline, catalyzer, water are added in reactor and stirred, make its salify; With clorox, as oxygenant, react suction filtration, washing, filtration, the dry product that to obtain.This method accelerant CZ yield is low.
Summary of the invention
Methyl alcohol as solvent, hydrogen peroxide be two methods of oxygenant, produce the method for rubber vulcanization accelerant CZ.The method is simple to operate, and the brine waste amount of generation is few, hexahydroaniline consumption is little, yield is high.
For achieving the above object, the present invention is realized by following technical proposals: a kind ofly take methyl alcohol as solvent, sodium chlorate are the method that two methods of oxygenant are produced rubber vulcanization accelerant CZs, it is characterized in that comprising following process:
By the volume ratio of methyl alcohol and hexahydroaniline, be 0.5～0.8:1, methyl alcohol and hexahydroaniline mixing liquid are joined in stills for air blowing, at 30-60 ℃, rotating speed, be under the condition of 600 revs/min, with the flow velocity of 2ml/ minute, add mass ratio 1:1 captax: the slip of methyl alcohol, simultaneously with the flow velocity of 1ml/ minute, in solution, drip the hydrogen peroxide solution that mass content is 8-16%, after 90 minutes, stop dripping hydrogen peroxide, be incubated 10 minutes.Start Distillation recovery methyl alcohol; Product is through suction filtration, washing, filtration, the dry rubber accelerator CZ product that to obtain, and the yield of accelerant CZ reaches more than 99%.
The invention has the advantages that: the method process is simple, with methyl alcohol, replaces water, is oxygenant by environment-friendly type oxidant hydrogen peroxide, and the older technique of waste water reduces more than 60%, and salt concentration not.This technique is easy to industrialization, and the hexahydroaniline of use is few, and the yield of accelerant CZ reaches more than 99%.
Embodiment
Embodiment 1:
By the volume ratio of methyl alcohol and hexahydroaniline, be 0.5:1, methyl alcohol and hexahydroaniline mixing liquid are joined in glass oxidizer, at 30 ℃, rotating speed, be under the condition of 600 revs/min, with the flow velocity of 2ml/ minute, add mass ratio 1:1 captax: the slip of methyl alcohol, simultaneously with the flow velocity of 1ml/ minute, to dripping mass content in solution, it is 16% hydrogen peroxide solution, after 90 minutes, stop dripping hydrogen peroxide, be incubated 10 minutes.Start Distillation recovery methyl alcohol; Product is through suction filtration, washing, filtration, the dry rubber accelerator CZ product that to obtain, and the yield of accelerant CZ reaches more than 99%.
Embodiment 2:
By the volume ratio of methyl alcohol and hexahydroaniline, be 0.65:1, methyl alcohol and hexahydroaniline mixing liquid are joined in glass oxidizer, at 45 ℃, rotating speed, be under the condition of 600 revs/min, with the flow velocity of 2ml/ minute, add mass ratio 1:1 captax: the slip of methyl alcohol, simultaneously with the flow velocity of 1ml/ minute, to dripping mass content in solution, be 12% chlorine bleach liquor, after 90 minutes, stop dripping hydrogen peroxide, be incubated 10 minutes.Start Distillation recovery methyl alcohol; Product is through suction filtration, washing, filtration, the dry rubber accelerator CZ product that to obtain, and the yield of accelerant CZ reaches more than 99%.
Embodiment 3:
By the volume ratio of methyl alcohol and hexahydroaniline, be 0.8:1, methyl alcohol and hexahydroaniline mixing liquid are joined in glass oxidizer, at 60 ℃, rotating speed, be under the condition of 600 revs/min, with the flow velocity of 2ml/ minute, add mass ratio 1:1 captax: the slip of methyl alcohol, simultaneously with the flow velocity of 1ml/ minute, to dripping mass content in solution, be 8% chlorine bleach liquor, after 90 minutes, stop dripping hydrogen peroxide, be incubated 10 minutes.Start Distillation recovery methyl alcohol; Product is through suction filtration, washing, filtration, the dry rubber accelerator CZ product that to obtain, and the yield of accelerant CZ reaches more than 99%.
Claims (1)
1. a hydrogen peroxide is the method that two methods of oxygenant are produced rubber vulcanization accelerant CZ; It is characterized in that: by the volume ratio of methyl alcohol and hexahydroaniline, be 0.5～0.8:1, methyl alcohol and hexahydroaniline mixing liquid are joined in glass oxidizer, at 40 ℃, rotating speed, be under the condition of 600 revs/min, with the flow velocity of 2ml/ minute, add mass ratio 1:1 captax: the slip of methyl alcohol, simultaneously with the flow velocity of 1ml/ minute, to dripping mass content in solution, it is 12% hydrogen peroxide solution, after 90 minutes, stop dripping hydrogen peroxide, be incubated 10 minutes.Start Distillation recovery methyl alcohol; Product is through suction filtration, washing, filtration, the dry rubber accelerator CZ product that to obtain, and the yield of accelerant CZ reaches more than 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467586.8A CN103508977A (en) | 2013-09-30 | 2013-09-30 | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467586.8A CN103508977A (en) | 2013-09-30 | 2013-09-30 | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103508977A true CN103508977A (en) | 2014-01-15 |
Family
ID=49892459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310467586.8A Pending CN103508977A (en) | 2013-09-30 | 2013-09-30 | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508977A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632141A (en) * | 2016-12-21 | 2017-05-10 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method |
| CN110627740A (en) * | 2019-09-30 | 2019-12-31 | 山东尚舜化工有限公司 | Novel environment-friendly production method of accelerator CBS without waste salt and wastewater |
| CN112745278A (en) * | 2019-10-31 | 2021-05-04 | 北京彤程创展科技有限公司 | Method for preparing rubber accelerator CZ and rubber composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872845A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气集团公司 | Method and equipment for preparing 2 - benzothiazole sulphenamide |
| 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 |
| CN101367777A (en) * | 2008-01-16 | 2009-02-18 | 天津市科迈化工有限公司 | Novel production method of rubber vulcanization accelerant CZ |
-
2013
- 2013-09-30 CN CN201310467586.8A patent/CN103508977A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872845A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气集团公司 | Method and equipment for preparing 2 - benzothiazole sulphenamide |
| 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 |
| CN101367777A (en) * | 2008-01-16 | 2009-02-18 | 天津市科迈化工有限公司 | Novel production method of rubber vulcanization accelerant CZ |
Non-Patent Citations (4)
| Title |
|---|
| 倪立宠 等: "硫化促进剂CBS的合成", 《化工生产与技术》, vol. 16, no. 4, 30 April 2009 (2009-04-30) * |
| 刘秀兰 等: "双氧水氧化法合成橡胶硫化促进剂CBS的中试研究", 《精细化工》, vol. 24, no. 10, 31 October 2007 (2007-10-31) * |
| 李艳: "橡胶硫化促进剂CBS的双氧水氧化法合成", 《石化技术与应用》, vol. 26, no. 1, 31 January 2008 (2008-01-31) * |
| 高研 等: "混合氧化法合成硫化促进剂CBS的新工艺研究", 《现代化工》, vol. 29, no. 1, 30 September 2009 (2009-09-30) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632141A (en) * | 2016-12-21 | 2017-05-10 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method |
| CN110627740A (en) * | 2019-09-30 | 2019-12-31 | 山东尚舜化工有限公司 | Novel environment-friendly production method of accelerator CBS without waste salt and wastewater |
| CN112745278A (en) * | 2019-10-31 | 2021-05-04 | 北京彤程创展科技有限公司 | Method for preparing rubber accelerator CZ and rubber composition |
| CN112745278B (en) * | 2019-10-31 | 2022-06-14 | 北京彤程创展科技有限公司 | Method for preparing rubber accelerator CZ and rubber composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101157664A (en) | New method for synthesizing rubber vulcanization accelerator CZ | |
| CN101318942A (en) | Novel method for preparing vulcanized rubber accelerant DZ with cooling-down circulating water system | |
| CN102838560A (en) | Method for synthesizing rubber vulcanization accelerator NS by using sodium hypochlorite as oxidizer | |
| CN105037295B (en) | A kind of method for producing sulfenamide thiofide | |
| CN103524453A (en) | Synthetic method for rubber vulcanization accelerator NS by solvent method | |
| CN101215272A (en) | Method of producing rubber vulcanization accelerator DM | |
| CN102850294A (en) | Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant | |
| CN103508977A (en) | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent | |
| CN102827104A (en) | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer | |
| CN101367777A (en) | Novel production method of rubber vulcanization accelerant CZ | |
| CN101134748A (en) | Method for producing rubber vulcanization accelerator DM | |
| CN102838562A (en) | Method for synthesizing rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) through two-step method by taking hydrogen peroxide as oxidant | |
| CN101134749A (en) | New method for synthesizing rubber vulcanization accelerator CZ | |
| CN102367238A (en) | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide | |
| CN101735171A (en) | Method for synthesizing thiofide NS by oxygen oxidation method | |
| CN103508978A (en) | Method for producing rubber vulcanization accelerator CZ with two-dropping method | |
| CN103524450A (en) | Synthetic method for accelerator DZ by using methanol as solvent | |
| CN101717381A (en) | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant | |
| CN103508976A (en) | Method for producing rubber vulcanization accelerator NS | |
| CN102838565A (en) | Production method of rubber vulcanization accelerator DZ | |
| CN106632141A (en) | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method | |
| CN101157663A (en) | Method for producing rubber vulcanization accelerator NS | |
| CN104370746B (en) | A kind of cost-effective preparation method to nitrobenzyl alcohol | |
| CN103539757A (en) | Method for synthesizing rubber vulcanization accelerator CZ | |
| CN101143856A (en) | Method of producing rubber vulcanization accelerator DZ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140115 |