CN104327012A - Catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfenamide - Google Patents
Catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfenamide Download PDFInfo
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- CN104327012A CN104327012A CN201410508794.2A CN201410508794A CN104327012A CN 104327012 A CN104327012 A CN 104327012A CN 201410508794 A CN201410508794 A CN 201410508794A CN 104327012 A CN104327012 A CN 104327012A
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- cyclohexyl
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- tetrasulphated phthalcyanine
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- benzothiazole sulfenamide
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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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Abstract
A catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfonamide includes following steps: (1) preparation of M slurry: filling a reaction kettle with a promoter M and water according to n(M):n(H2O)=1:80 with normal-temperature stirring for 10 min; (2) adding dropwisely cyclohexylamine according to n(M):n(cyclohexylamine)=1:1.5 with normal-temperature stirring for 20 min to salification; (3) adding a catalyst accounting for 1%-2% of the amount of substance of the M with temperature being increased to 30-45 DEG C; (4) adding dropwisely hydrogen peroxide according to n(M):n(H2O2)=1:1.2-1.8 with continuously stirring for 20 min after dropwise addition being finished; and (5) performing a reaction, decreasing the temperature, performing filtration with a filter cake being washed with dilute Na2CO3 and performing a drying process to obtain a finished product. The invention is advantaged in that with addition of the catalyst in a certain proportion, a reaction time is reduced and a reaction temperature is reduced. The catalytically synthetic method is convenient to carry out and is suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of rubber accelerator, particularly relate to a kind of process for catalytic synthesis of N cyclohexyl 2 benzothiazole sulfenamide.
Background technology
N-cyclohexyl-2-benzothiazole sulfonamide, commodity are called accelerator CBS, are one of a kind of conventional vulcanized rubber promotor, have the excellent and large advantage of curing time short two of scorching quality.Tensile modulus and the tensile strength of cross-linked rubber can be improved with accelerant MBT, TMTD, MBTS used time.This product is specially adapted to natural gum and the synthetical glue of the stronger Audit For Process reinforcement carbon black of alkalescence, and variable color is slight, no blooming, cross-linked rubber ageing-resistant performance are excellent, are mainly applicable to manufacture the mechanicals such as tire, rubber overshoes, sebific duct, adhesive plaster, cable, general consumption be 0.5-2 part not etc.At present, the main production of rubber vulcanizing accelerator CBS adopts captax to be starting raw material, through oxidizing obtained, the oxygenant of main use has clorox, hydrogen peroxide, oxygen etc., sodium hypochlorite oxidization produces waste gas and water pollutions in building-up process, dioxygen oxidation needs to carry out under a certain pressure, higher to the sealing requirements of equipment, comparatively safe hidden danger is larger, hydrogen peroxide relatively with above two kinds of not only environmental protection but also do not need the equipment of high requirement, be better oxygenant.Hydrogen peroxide is easily decomposed into high reactivity intermediate under high temperature, illumination, catalyst action, plays oxygenizement.Protoxydic temperature can fall in the use of catalyzer, shortens oxidization time, obtains good quality product.
Summary of the invention
The object of this invention is to provide a kind of process for catalytic synthesis of N cyclohexyl 2 benzothiazole sulfenamide.。
Technical scheme of the present invention comprises the following steps:
(1) configuration of M slurry: captax and water are pressed n (M): n (H
2o)=1:80 adds reactor, stirring at normal temperature 10min;
(2) hexahydroaniline is dripped by n (M): n (hexahydroaniline)=1:1.5, stirring at room temperature 20mim salify;
(3) add catalyzer by the amount of substance of M than 1% ~ 2%, be warming up to 30 ~ 45 degree;
(4) by n (M): n (H
2o
2)=1:1.2 ~ 1.8 drip hydrogen peroxide, dropwise rear continuation and stir 20min;
(5) reaction cooling, filters, the rare Na of filter cake
2cO
3wash, washing, dry, obtain product;
Described catalyzer is any one in Tetrasulphated phthalcyanine manganese, Tetrasulphated phthalcyanine iron, tetrasulfonated zinc phthalocyanine, Tetrasulphated phthalcyanine cobalt, Tetrasulphated phthalcyanine nickel, Tetrasulphated phthalcyanine copper.
The preferred Tetrasulphated phthalcyanine iron of described catalyzer.
Beneficial effect of the present invention is: after adding a certain proportion of catalyzer, and the temperature needed for oxidation is reduced to 30 degree from 65 degree, and does not affect reaction yield.The time for adding of hydrogen peroxide is reduced to 50min from 80min, shortens the reaction times.This process for catalytic synthesis is convenient and swift, reduces reaction times and temperature, is applicable to large-scale industrial production.
Embodiment
Of the present inventionly to comprise the following steps:
(1) configuration of M slurry: captax and water are pressed n (M): n (H
2o)=1:80 adds reactor, stirring at normal temperature 10min;
(2) hexahydroaniline is dripped by n (M): n (hexahydroaniline)=1:1.5, stirring at room temperature 20mim salify;
(3) add catalyzer by the amount of substance of M than 1% ~ 2%, be warming up to 30 ~ 45 degree;
(4) by n (M): n (H
2o
2)=1:1.3 ~ 1.5 drip hydrogen peroxide, and reaction end neutralized verdigris solution and starch KI test paper measure, and dropwise rear continuation and stir 20min;
(5) reaction cooling, filters, the rare Na of filter cake
2cO
3wash, washing, dry, obtain product;
Described catalyzer is any one in Tetrasulphated phthalcyanine manganese, Tetrasulphated phthalcyanine iron, tetrasulfonated zinc phthalocyanine, Tetrasulphated phthalcyanine cobalt, Tetrasulphated phthalcyanine nickel, Tetrasulphated phthalcyanine copper.。
Embodiment one:
Take 10g captax, add 90g water, making beating 10min, add hexahydroaniline salify in n (M): n (hexahydroaniline)=1:1.5 ratio, add catalyzer by M amount of substance 1%, be warming up to 30 degree, drip the hydrogen peroxide of 14%, time for adding is 50min, and reaction end neutralized verdigris solution and starch KI test paper measure, and through filtering, washing, the aftertreatment such as dry obtains product.
Embodiment two:
Take 10g captax, add 90g water, making beating 10min, in n (M): n (hexahydroaniline) :=1:1.5 ratio adds hexahydroaniline salify, add Tetrasulphated phthalcyanine iron by M amount of substance 1%, be warming up to 35 degree, by n (M): n (H
2o
2)=1:1.3 drips the hydrogen peroxide of 14%, and time for adding is 40min, and reaction end neutralized verdigris solution and starch KI test paper measure, and through filtering, washing, the aftertreatment such as dry obtains product, yield 92.2%.
Embodiment three:
Take 10g captax, add 90g water, making beating 10min, in n (M): n (hexahydroaniline) :=1:1.5 ratio adds hexahydroaniline salify, add Tetrasulphated phthalcyanine iron by M amount of substance 2%, be warming up to 40 degree, by n (M): n (H
2o
2)=1:1.4 drips the hydrogen peroxide of 14%, and time for adding is 40min, and reaction end neutralized verdigris solution and starch KI test paper measure, and through filtering, washing, the aftertreatment such as dry obtains product, yield 95.4%.
Embodiment four:
Take 10g captax, add 90g water, making beating 10min, in n (M): n (hexahydroaniline) :=1:1.5 ratio adds hexahydroaniline salify, add Tetrasulphated phthalcyanine iron by M amount of substance 2%, be warming up to 45 degree, by n (M): n (H
2o
2)=1:1.5 drips the hydrogen peroxide of 14%, and time for adding is 40min, and reaction end neutralized verdigris solution and starch KI test paper measure, and through filtering, washing, the aftertreatment such as dry obtains product, yield 94.2%.
Above one embodiment of the present of invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (3)
1. the process for catalytic synthesis of a N cyclohexyl 2 benzothiazole sulfenamide comprises the following steps:
(1) configuration of M slurry: captax and water are pressed n (M): n (H
2o)=1:80 adds reactor, stirring at normal temperature 10min;
(2) hexahydroaniline is dripped by n (M): n (hexahydroaniline)=1:1.5, stirring at room temperature 20mim salify;
(3) add catalyzer by the amount of substance of M than 1% ~ 2%, be warming up to 30 ~ 45 degree;
(4) by n (M): n (H
2o
2)=1:1.2 ~ 1.8 drip hydrogen peroxide, dropwise rear continuation and stir 20min;
(5) reaction cooling, filters, the rare Na of filter cake
2cO
3wash, washing, dry, obtain product.
2. the process for catalytic synthesis of a kind of N cyclohexyl 2 benzothiazole sulfenamide according to claim 1, is characterized in that: described catalyzer is any one in Tetrasulphated phthalcyanine manganese, Tetrasulphated phthalcyanine iron, tetrasulfonated zinc phthalocyanine, Tetrasulphated phthalcyanine cobalt, Tetrasulphated phthalcyanine nickel, Tetrasulphated phthalcyanine copper.
3. the process for catalytic synthesis of a kind of N cyclohexyl 2 benzothiazole sulfenamide according to claim 1, is characterized in that: the preferred Tetrasulphated phthalcyanine iron of described catalyzer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410508794.2A CN104327012A (en) | 2014-09-28 | 2014-09-28 | Catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfenamide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410508794.2A CN104327012A (en) | 2014-09-28 | 2014-09-28 | Catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfenamide |
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| CN104327012A true CN104327012A (en) | 2015-02-04 |
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| CN201410508794.2A Pending CN104327012A (en) | 2014-09-28 | 2014-09-28 | Catalytically synthetic method of N-cyclohexyl-2-benzothiazole sulfenamide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831750A (en) * | 2017-01-24 | 2017-06-13 | 郑州大学 | The method of catalytic molecular oxygen oxidation sulfenamide compound of the generation with S N keys in water phase |
| CN110156717A (en) * | 2019-06-20 | 2019-08-23 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of rubber vulcanization accelerator NS |
| CN110305075A (en) * | 2019-07-11 | 2019-10-08 | 聊城大学 | A kind of method of Co catalysts oxygen method synthesis N cyclohexyl 2 benzothiazole sulfenamide |
| 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 |
| CN114768882A (en) * | 2022-06-20 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Heterogeneous catalyst for producing vulcanization accelerator TBBS by oxygen method and preparation method and application thereof |
-
2014
- 2014-09-28 CN CN201410508794.2A patent/CN104327012A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831750A (en) * | 2017-01-24 | 2017-06-13 | 郑州大学 | The method of catalytic molecular oxygen oxidation sulfenamide compound of the generation with S N keys in water phase |
| CN106831750B (en) * | 2017-01-24 | 2019-09-06 | 郑州大学 | The oxidation of catalytic molecular oxygen generates the method with the sulfenamide compound of S-N key in water phase |
| CN110156717A (en) * | 2019-06-20 | 2019-08-23 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of rubber vulcanization accelerator NS |
| CN110156717B (en) * | 2019-06-20 | 2023-06-13 | 山东阳谷华泰化工股份有限公司 | Synthesis method of rubber vulcanization accelerator NS |
| CN110305075A (en) * | 2019-07-11 | 2019-10-08 | 聊城大学 | A kind of method of Co catalysts oxygen method synthesis N cyclohexyl 2 benzothiazole sulfenamide |
| 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 |
| CN114768882A (en) * | 2022-06-20 | 2022-07-22 | 科迈(天津)建设工程股份有限公司 | Heterogeneous catalyst for producing vulcanization accelerator TBBS by oxygen method and preparation method and application thereof |
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Application publication date: 20150204 |