CN106699684A - Method for producing rubber vulcanization accelerator CZ - Google Patents
Method for producing rubber vulcanization accelerator CZ Download PDFInfo
- Publication number
- CN106699684A CN106699684A CN201611193305.4A CN201611193305A CN106699684A CN 106699684 A CN106699684 A CN 106699684A CN 201611193305 A CN201611193305 A CN 201611193305A CN 106699684 A CN106699684 A CN 106699684A
- Authority
- CN
- China
- Prior art keywords
- cyclohexylamine
- cyclohexane
- methyl alcohol
- rubber vulcanization
- vulcanization accelerator
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for producing a rubber vulcanization accelerator CZ. The method comprises the following steps: adding a mixed liquid of methanol and cyclohexane in a volume ratio of 2:1 into an oxidizer, under a stirring condition, adding molten crude M of 170-180 DEG C to generate M-cyclohexylamine from crude M and cyclohexane, dropping a sodium hypochlorite solution into the solution, after 80-120 minutes, sampling and observing, judging a reaction final point by using potassium iodide-starch test paper, stopping dropping sodium chlorate when the test paper is black, and starting distillation to recycle methanol; performing suction filtration, water washing, filtration and drying, thereby obtaining a rubber vulcanization accelerator CZ product. The yield of the rubber vulcanization accelerator CZ is up to 99% or greater; by adopting the method, a small amount of cyclohexane is used, an M purification procedure and a pulping procedure and a cyclohexane distillation procedure in a conventional process can be reduced, procedures for producing CZ can be reduced, wastewater of the production can be reduced by 70% or greater when being compared with that of the conventional process, and industrial production can be easily achieved.
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 valued by people.Vulcanization 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 that the essential one kind of current rubber industry is main to be promoted
Enter agent.Accelerant CZ is a kind of active ultra fast accelerator of aftereffect half of height, and scorching quality is excellent, process safety, vulcanization
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, make it into salt；Entered as oxidant with hydrogen peroxide
Row reaction, cooling, suction filtration, washing, filtering, dry product.Cyclohexylamine amount that the method is used is big, and accelerant CZ yield
It is not high, can only achieve 90% or so, reason be M and cyclohexylamine due to being carried 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
Stirring in reactor is added, makes it into salt；Reacted as oxidant with sodium hypochlorite, it is suction filtration, washing, filtering, 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) it is raw material, the method that sodium hypochlorite is oxidant production rubber vulcanization accelerant CZ.The method operation letter
Single, production link is few, wastewater flow rate that is producing is few, cyclohexylamine consumption is small, M is high into salt rate with cyclohexylamine, CZ is obtained yield and reaches
99%.
The present invention is realized by the following technical scheme：
A kind of method for producing rubber vulcanization accelerant CZ, is 2 by the volume ratio of methyl alcohol and cyclohexylamine：1 mixing liquid adds
Enter in oxidator, under conditions of stirring, add the temperature of melting in 170 DEG C to 180 DEG C thick M, generate thick M and cyclohexylamine
M- cyclohexylamine salts, then to liquor natrii hypochloritis is added dropwise in solution, after 80-120 minutes, sampling observation is tried with starch potassium iodide
Paper judges reaction end, when test paper blackening, stops that sodium chlorate is added dropwise, and starts Distillation recovery methyl alcohol；Product through suction filtration, washing,
Filtering, dry rubber accelerator CZ products.
It is preferred that when methyl alcohol is with cyclohexylamine 160-240ml, adding 170 DEG C to 180 DEG C thick M100-140g of melting.
It is preferred that speed of agitator is 400-800 revs/min.
It is preferred that sodium hypochlorite mass content is 12-18% solution.
It is preferred that sodium hypochlorite was added dropwise with the flow velocity of 1-5ml/ minutes.
The reason for yield of accelerant CZ reaches more than 99%, high income is that methyl alcohol is good organic solvent, 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, the older technique of waste water of production is reduced more than 70%, it is easy to industrialized production.
Specific embodiment
Embodiment 1：
It is 2 by the volume ratio of methyl alcohol and cyclohexylamine：1 mixing liquid 160ml is added in oxidator, is in speed of agitator
Under conditions of 800 revs/min, 170 DEG C to 180 DEG C thick M120g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generation M-
Cyclohexylamine salt, then with the flow velocity of 1ml/ minutes, to the liquor natrii hypochloritis that dropwise addition mass content in solution is 12%, 80 minutes
Afterwards, sampling observation, reaction end is judged with starch potassium iodide paper, when test paper blackening, stops that sodium chlorate is added dropwise, and starts distillation
Reclaim methyl alcohol；Product is through suction filtration, washing, filtering, dry rubber accelerator CZ products.The yield of accelerant CZ reach 99% with
On.
Embodiment 2：
It is 2 by the volume ratio of methyl alcohol and cyclohexylamine：1 mixing liquid 200ml is added in oxidator, is in speed of agitator
Under conditions of 600 revs/min, 170 DEG C to 180 DEG C thick M100g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generation M-
Cyclohexylamine salt, then with the flow velocity of 3ml/ minutes, to the liquor natrii hypochloritis that dropwise addition mass content in solution is 15%, 100 points
Zhong Hou, sampling observation, reaction end is judged with starch potassium iodide paper, when test paper blackening, stops that sodium chlorate is added dropwise, and starts to steam
Evaporate recovery methyl alcohol；Product is through suction filtration, washing, filtering, dry rubber accelerator CZ products.The yield of accelerant CZ reaches 99%
More than.
Embodiment 3：
It is 2 by the volume ratio of methyl alcohol and cyclohexylamine：1 mixing liquid 240ml is added in oxidator, is in speed of agitator
Under conditions of 400 revs/min, 170 DEG C to 180 DEG C thick M140g of melting are added, be sufficiently stirred for, make thick M and cyclohexylamine generation M-
Cyclohexylamine salt, then with the flow velocity of 5ml/ minutes, to the liquor natrii hypochloritis that dropwise addition mass content in solution is 18%, 120 points
Zhong Hou, sampling observation, reaction end is judged with starch potassium iodide paper, when test paper blackening, stops that sodium chlorate is added dropwise, and starts to steam
Evaporate recovery methyl alcohol；Product is through suction filtration, washing, filtering, dry rubber accelerator CZ products.The yield of accelerant CZ reaches 99%
More than.
Claims (5)
1. a kind of method for producing rubber vulcanization accelerant CZ, it is characterized in that being 2 by the volume ratio of methyl alcohol and cyclohexylamine：1 mixing
Liquid is added in oxidator, under conditions of stirring, adds the temperature of melting in 170 DEG C to 180 DEG C thick M, makes thick M and hexamethylene
Amine generates M- cyclohexylamine salts, and then to liquor natrii hypochloritis is added dropwise in solution, after 80-120 minutes, starch iodine is used in sampling observation
Change potassium test paper and judge reaction end, when test paper blackening, stop that sodium chlorate is added dropwise, start Distillation recovery methyl alcohol；Product through suction filtration,
Washing, filtering, dry rubber accelerator CZ products.
2. the method for claim 1, it is characterized in that when methyl alcohol is with cyclohexylamine 160-240ml, adding 170 DEG C of melting to arrive
180 DEG C of thick M100-140g.
3. the method for claim 1, it is characterized in that speed of agitator is 400-800 revs/min.
4. the method for claim 1, it is characterized in that sodium hypochlorite mass content is 12-18% solution.
5. the method for claim 1, it is characterized in that sodium hypochlorite was added dropwise with the flow velocity of 1-5ml/ minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611193305.4A CN106699684A (en) | 2016-12-21 | 2016-12-21 | Method for producing rubber vulcanization accelerator CZ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611193305.4A CN106699684A (en) | 2016-12-21 | 2016-12-21 | Method for producing rubber vulcanization accelerator CZ |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106699684A true CN106699684A (en) | 2017-05-24 |
Family
ID=58938668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611193305.4A Pending CN106699684A (en) | 2016-12-21 | 2016-12-21 | Method for producing rubber vulcanization accelerator CZ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106699684A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105303A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| 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 |
-
2016
- 2016-12-21 CN CN201611193305.4A patent/CN106699684A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105303A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037295B (en) | A kind of method for producing sulfenamide thiofide | |
| CN101717379B (en) | Production method of rubber vulcanizing accelerator CBS | |
| CN102838560A (en) | Method for synthesizing rubber vulcanization accelerator NS by using sodium hypochlorite as oxidizer | |
| CN106632141A (en) | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method | |
| CN101215272A (en) | Method of producing rubber vulcanization accelerator DM | |
| CN101215273A (en) | Method of producing rubber vulcanization accelerator DM | |
| CN104610193A (en) | Preparation method of rubber vulcanizing accelerator TBBS | |
| CN103524453A (en) | Synthetic method for rubber vulcanization accelerator NS by solvent method | |
| CN102827104A (en) | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer | |
| CN101735171A (en) | Method for synthesizing thiofide NS by oxygen oxidation method | |
| CN101134748A (en) | Method for producing rubber vulcanization accelerator DM | |
| CN106699684A (en) | Method for producing rubber vulcanization accelerator CZ | |
| CN101367777A (en) | Novel production method of rubber vulcanization accelerant CZ | |
| CN104592161A (en) | Method for producing rubber vulcanization accelerator CBS by crude product MBT | |
| CN102838564A (en) | Preparation method of rubber vulcanization accelerator DCBS | |
| 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 | |
| CN102850294A (en) | Method for synthesizing rubber vulcanizing promoter CZ (N-cyclohexylbenzothiazole-2-sulphenamide) via two-step process by using hydrogen peroxide as oxidant | |
| CN102838561A (en) | Production method of rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) | |
| CN104311506A (en) | Synthetic process of rubber vulcanization accelerator CBS | |
| CN103073521B (en) | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) | |
| CN104557770A (en) | Method for synthesizing rubber vulcanization accelerator NS by taking sodium hypochlorite as oxidant | |
| CN106316981A (en) | Preparation method of N-cyclohexyl-2-benzothiazolesulfenamide | |
| CN101717381A (en) | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant | |
| CN103508978A (en) | Method for producing rubber vulcanization accelerator CZ with two-dropping method | |
| CN104230844A (en) | Preparation method of vulcanization accelerator CZ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170524 |
|
| RJ01 | Rejection of invention patent application after publication |