CN106632141A - Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method - Google Patents
Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method Download PDFInfo
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- CN106632141A CN106632141A CN201611195692.5A CN201611195692A CN106632141A CN 106632141 A CN106632141 A CN 106632141A CN 201611195692 A CN201611195692 A CN 201611195692A CN 106632141 A CN106632141 A CN 106632141A
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- Prior art keywords
- cyclohexylamine
- hydrogen peroxide
- methyl alcohol
- peroxide solution
- sodium hypochlorite
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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)
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Abstract
The invention discloses a method for producing a rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide) by a two-drop method. The method comprises the following steps of, according to a volume ratio, which is 2 to 1, of methanol to cyclohexylamine, adding the mixed liquid of the methanol and the cyclohexylamine into an oxidation device, in an agitation condition, adding a fused coarse M at a temperature of 170 to 180 DEG C, making the M and the cyclohexylamine generate an M-cyclohexylamine salt, afterwards, dropwise adding a hydrogen peroxide solution into a solution, then, after 80 to 120 minutes, replacing the hydrogen peroxide solution with sodium hypochlorite, dropwise adding the sodium hypochlorite to find an endpoint, carrying out a judgment by using starch-potassium iodide test paper, when the test paper becomes black, stopping dropwise adding the sodium hypochlorite, and starting distillation to recover the methanol; carrying out suction filtration, water scrubbing, filtration and drying on a product, so as to obtain the rubber vulcanization accelerator CZ. The yield of the accelerator CZ reaches 99 percent or above; the use level of the cyclohexylamine in the method is low; an M purification process as well as a pulping procedure and a cyclohexylamine distillation procedure in an old process is reduced; the link of producing the CZ is reduced; produced wastewater is decreased by 70 percent or above compared with that in the old process; the method is easy for industrialized production.
Description
Technical field
The present invention relates to a kind of producer of thiofide N cyclohexyl 2 benzothiazole sulfenamide (CZ)
Method, belongs to rubber vulcanization accelerant CZ production technical field.
Background technology
With the development of rubber industry, research and the production of vulcanization accelerator are increasingly subject to people's attention.Sulfuration promotees
Enter agent and very important effect is played in Vulcanization Process of Rubber, it can greatly speed up the reaction of rubber and vulcanizing agent, improve life
Yield, while can also improve the physical and mechanical properties of vulcanized rubber, CZ is a kind of requisite main rush of current rubber industry
Enter agent.Accelerant CZ is a kind of active ultra fast accelerator of aftereffect half of height, and scorching quality is excellent, process safety, sulfuration
Time is short.Document (fine chemistry industry, 2006,23:923) method that catalytic oxidation synthesizes CZ is reported.By captax, (2- is dredged
Alcohol radical benzothiazole), cyclohexylamine, catalyst, water add reactor in stir so as into salt；Entered as oxidant with hydrogen peroxide
Row reaction, cooling, suction filtration, washing, filtration, dry product.The cyclohexylamine amount that the method is used is big, and the yield of accelerant CZ
It is not high, can only achieve 90% or so, reason be M and cyclohexylamine due to carrying out at normal temperatures into salt temperature, into being solid (M) during salt
Liquid (cyclohexylamine), thus it is not high into salt rate, more than 98% is not reached, it is the main cause for causing this method yield not high.Document
(Guangxi Chemical Industry, 1994,23：58) fast synthesis method of accelerant CZ is reported.By captax, cyclohexylamine, catalyst, water
Add in reactor and stir so as into salt；Reacted as oxidant with sodium hypochlorite, it is suction filtration, washing, filtration, dry
Product.The method accelerant CZ yield is also only 90% or so, and reason is also that M is caused with cyclohexylamine into salt rate is not high.
The content of the invention
In order to solve problem of the prior art, present invention proposition one kind is with methyl alcohol as solvent, (2- not purified is dredged thick M
Alcohol radical benzothiazole) for raw material, hydrogen peroxide for oxidant production rubber vulcanization accelerant CZ method.The method is simple to operate,
Production link is few, wastewater flow rate that is producing is few, cyclohexylamine consumption is little, high income.
The present invention is realized by the following technical scheme：
A kind of method that two drops method produces rubber vulcanization accelerant CZ, is 2 by the volume ratio of methyl alcohol and cyclohexylamine：1, by first
Alcohol is added in oxidator with cyclohexylamine mixing liquid, under agitation, adds the temperature of melting thick at 170 DEG C to 180 DEG C
M, makes M and cyclohexylamine generate M- cyclohexylamine salts, and quality hydrogen peroxide solution is then added dropwise in solution, after 80-120 minutes, then changes
Sodium hypochlorite is added dropwise and looks for terminal, is judged with starch potassium iodide paper, when test paper blackening, stops that sodium hypochlorite is added dropwise, and starts to steam
Evaporate recovery methyl alcohol；Product Jing suction filtrations, washing, filtration, dry rubber accelerator CZ products.
It is preferred that when methyl alcohol is with cyclohexylamine mixing liquid 160-240ml, adding the temperature of melting in 170 DEG C to 180 DEG C M100-
140g。
It is preferred that speed of agitator is 400-800 rev/min.
It is preferred that hydrogen peroxide solution mass content is 8-12%；It is 1-5ml/ minutes that digit rate is added dropwise.
It is good organic solvent that the reason for yield of accelerant CZ reaches more than 99%, high income is methyl alcohol, and M is dissolved in
In methyl alcohol, and add the temperature of melting in 170 DEG C to 180 DEG C thick M, into salt be liquid (M methyl alcohol) liquid (cyclohexylamine) into salt,
It is higher into salt rate than prior art solid (M) liquid (cyclohexylamine), into also 50 DEG C higher than prior art or so of temperature during salt, into salt
Rate has reached more than 98%.This method cyclohexylamine consumption is few, reduces pulping process and distillation ring in M purification process, old technique
Hexylamine operation, reduces the link of production CZ, and the older technique of waste water for making production reduces more than 70%, it is easy to industrialized production.
Specific embodiment
Embodiment 1：
By methyl alcohol and cyclohexylamine volume ratio 2:1 mixing liquid 160ml is added in oxidator, speed of agitator be 400 turns/
Under conditions of minute, 170 DEG C to 180 DEG C thick M140g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generate M- cyclohexylamine
Salt, then with the flow velocity of 1ml/ minutes, the hydrogen peroxide solution that mass content is 8% is added dropwise in solution, after 80 minutes, changes time chlorine
Sour sodium looks for terminal, and with starch potassium iodide paper reaction end is judged, when test paper blackening, stops that sodium chlorate is added dropwise, and starts distillation
Reclaim methyl alcohol；Product Jing suction filtrations, washing, filtration, dry rubber accelerator CZ products.The yield of accelerant CZ reach 99% with
On.
Embodiment 2：
By methyl alcohol and cyclohexylamine volume ratio 2:1 mixing liquid 200ml is added in oxidator, speed of agitator be 600 turns/
Under conditions of minute, 170 DEG C to 180 DEG C thick M120g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generate M- cyclohexylamine
Salt, then with the flow velocity of 3ml/ minutes, the hydrogen peroxide solution that mass content is 10% is added dropwise in solution, after 100 minutes, changes secondary
Sodium chlorate looks for terminal, and with starch potassium iodide paper reaction end is judged, when test paper blackening, stops that sodium chlorate is added dropwise, and starts to steam
Evaporate recovery methyl alcohol；Product Jing suction filtrations, washing, filtration, dry rubber accelerator CZ products.The yield of accelerant CZ reaches 99%
More than.
Embodiment 3：
By methyl alcohol and cyclohexylamine volume ratio 2:1 mixing liquid 240ml is added in oxidator, speed of agitator be 800 turns/
Under conditions of minute, 170 DEG C to 180 DEG C thick M100g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generate M- cyclohexylamine
Salt, then with the flow velocity of 5ml/ minutes, the hydrogen peroxide solution that mass content is 12% is added dropwise in solution, after 120 minutes, changes secondary
Sodium chlorate looks for terminal, and with starch potassium iodide paper reaction end is judged, when test paper blackening, stops that sodium hypochlorite is added dropwise, and starts
Distillation recovery methyl alcohol；Product Jing suction filtrations, washing, filtration, dry rubber accelerator CZ products.The yield of accelerant CZ reaches
More than 99%.
Claims (5)
1. a kind of method that two drops method produces rubber vulcanization accelerant CZ, is characterized in that：It is with the volume ratio of cyclohexylamine by methyl alcohol
2：1, methyl alcohol and cyclohexylamine mixing liquid are added in oxidator, under agitation, the temperature for adding melting is arrived at 170 DEG C
180 DEG C of thick M, make thick M and cyclohexylamine generate M- cyclohexylamine salts, and quality hydrogen peroxide solution is then added dropwise in solution, and 80-120 divides
Zhong Hou, then change sodium hypochlorite be added dropwise look for terminal, judged with starch potassium iodide paper, when test paper blackening, stop dropwise addition hypochlorous acid
Sodium, starts Distillation recovery methyl alcohol；Product Jing suction filtrations, washing, filtration, dry rubber accelerator CZ products.
2. the method for claim 1, when it is characterized in that methyl alcohol with cyclohexylamine mixing liquid 160-240ml, adds melting
170 DEG C to 180 DEG C thick M100-140g.
3. the method for claim 1, is characterized in that speed of agitator is 400-800 rev/min.
4. the method for claim 1, is characterized in that hydrogen peroxide solution mass content is 8-12%.
5. the method for claim 1, is characterized in that hydrogen peroxide solution dropwise addition digit rate is 1-5ml/ minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611195692.5A CN106632141A (en) | 2016-12-21 | 2016-12-21 | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611195692.5A CN106632141A (en) | 2016-12-21 | 2016-12-21 | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445918A (en) * | 2017-08-14 | 2017-12-08 | 青岛奥克凯姆化学助剂有限公司 | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method |
| 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 |
| CN112409291A (en) * | 2020-12-03 | 2021-02-26 | 鹤壁市恒力橡塑股份有限公司 | Preparation method of rubber accelerator CBS |
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| CN101717379A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Production method of rubber vulcanizing accelerator CBS |
| 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 |
| CN103508977A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent |
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2016
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| CN101717379A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Production method of rubber vulcanizing accelerator CBS |
| 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 |
| CN103508977A (en) * | 2013-09-30 | 2014-01-15 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ by adopting double-dripping method using hydrogen peroxide as oxidizing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445918A (en) * | 2017-08-14 | 2017-12-08 | 青岛奥克凯姆化学助剂有限公司 | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method |
| 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 |
| CN112409291A (en) * | 2020-12-03 | 2021-02-26 | 鹤壁市恒力橡塑股份有限公司 | Preparation method of rubber accelerator CBS |
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