CN104592161A - Method for producing rubber vulcanization accelerator CBS by crude product MBT - Google Patents
Method for producing rubber vulcanization accelerator CBS by crude product MBT Download PDFInfo
- Publication number
- CN104592161A CN104592161A CN201410848247.9A CN201410848247A CN104592161A CN 104592161 A CN104592161 A CN 104592161A CN 201410848247 A CN201410848247 A CN 201410848247A CN 104592161 A CN104592161 A CN 104592161A
- Authority
- CN
- China
- Prior art keywords
- mbt
- crude product
- product mbt
- oxidization
- 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
Abstract
The invention relates to a method for producing a rubber vulcanization accelerator CBS by a crude product MBT. The method comprises the following steps: respectively adding phenylamine, carbon dioxide and molten sulfur into a high-pressure kettle; reacting for 3-6 hours at a reaction temperature of 250-280 DEGC under pressure of 9-11 MPa to synthesize a rubber vulcanization accelerator MBT crude product; conveying the crude product MBT obtained by the reaction into a high-speed stirring and water-containing oxidization kettle for stirring the crude product MBT and water for 0.5-2 hours, and cooling to obtain crude product MBT particles; adding a cyclohexane solution into the oxidization kettle, and dropwise adding a hydrogen peroxide oxidization after uniformly mixing the crude product MBT with the cyclohexane; detecting with a starch potassium iodide solution at an oxidization end point, performing suction filtration on a reaction mixture, and washing a filter cake with a cyclohexylamine aqueous solution with mass content of 5-10%; and performing water-washing until the filer cake is neutral, and drying the filter cake to obtain the qualified vulcanization accelerator CBS. According to the method disclosed by the invention, the raw material MBT synthesizing process is adding molten sulfur, so that an MBT refining process is cancelled, the product yield is high, the quality is good and the environmental pollution is small.
Description
Technical field
The invention belongs to the preparation method of rubber ingredients, particularly a kind of method of being produced rubber vulcanizing accelerator CBS by crude product MBT.
Background technology
Accelerant N-cyclohexylbenzothiazole sulphenamide (CBS or CZ) is rear validity half ultra fast accelerator that a kind of height is active, and scorching quality is excellent, process safety, and curing time is short, is the requisite a kind of primary accelerator of current rubber industry.The difference of the existing production technique foundation oxygenant of CBS can be divided into time sodium method, peroxide passivation, anaerobic agent synthesis method and oxygen method four kinds.Domestic manufacturer mainly takes first two production method, and its main process, for be dropped into according to a certain percentage in reactor by the raw materials such as water, hexahydroaniline, accelerant MBT, drips oxidizing synthesis under certain condition and is promoted agent CBS.Concrete reaction equation is as follows:
Here raw material accelerant MBT used is finished product raw material, and price is higher, can generate a large amount of brine waste and peculiar smell in its production process, more difficult.Mention crude product MBT in Chinese patent CN200810139263 and produce accelerator CBS, eliminate MBT treating process.Also illustrate MBT synthesis technique, the feeding mode wherein mentioning raw material sulphur, for being dissolved to dithiocarbonic anhydride, forming molten sulphur liquid and feeds intake.But dithiocarbonic anhydride is inflammable explosive article, there is great potential safety hazard in operating process, is unfavorable for safety in production; Meanwhile, its oxygenant dripped is clorox, and the reaction end waste water generated containing a large amount of sodium-chlor is difficult to process, thus becomes the bottleneck problem of restriction accelerator CBS production, urgently to be resolved hurrily; Go out molten state crude product MBT in hexahydroaniline solution, temperature reaches as high as 100 DEG C, requires higher to equipment sealing, safety etc.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of rubber vulcanizing accelerator CBS, crude product MBT building-up process changes molten for dithiocarbonic anhydride sulphur technique into molten sulfur and feeds intake, and reduces process safety risk; With MBT crude product for the direct synthesis accelerant CBS of raw material, and adopt environmental protection hydrogen peroxide as oxygenant, this technique eliminates MBT treating process, and technical process is short, and cost is low, and products obtained therefrom yield is high, quality good; Do not produce high slat-containing wastewater, environmental pollution is little.
For achieving the above object, the present invention is realized by following technical proposals.
Concrete technical scheme is as follows:
Produced the method for rubber vulcanizing accelerator CBS by crude product MBT, as shown in Figure 1, step is as follows:
(1) aniline, dithiocarbonic anhydride, melting sulphur are dropped into autoclave respectively, feed molar proportioning aniline: sulphur: dithiocarbonic anhydride is 1:(1 ~ 1.2): (1 ~ 1.5); Temperature of reaction is 250 DEG C ~ 280 DEG C, and pressure is 9 ~ 11MPa, reacts 3 ~ 6 hours synthetic rubber accelerant MBT crude products;
(2) reaction gained crude product MBT is delivered to high-speed stirring to be filled with water stills for air blowing, crude product MBT and quality are than being 1:5 ~ 10, and stir 0.5 ~ 2h, cooling obtains crude product MBT particle;
(3) hexahydroaniline solution is added stills for air blowing, hexahydroaniline strength of solution is for being 1:3 ~ 5 for 30 ~ 50% (w/w), crude product MBT and hexahydroaniline mol ratio;
(4) mix rear dropping hydrogen peroxide oxidant, hydrogen peroxide concentration is 5% ~ 10% (w/w), oxidizing temperature 25 ~ 50 DEG C, and oxidization time is 2 ~ 4h; Oxidation terminal detects with starch potassium iodide solution, and starch potassium iodide reagents becomes indigo plant and is then oxidized end;
(5) reaction mixture carries out suction filtration, and filter cake is with the Aqueous Solution of Cyclohexylamine of mass content 5 ~ 10% washing 2 ~ 3 times; Then to be washed to neutrality, qualified aniline fluid bed after filtration cakes torrefaction, is obtained.
The invention has the advantages that: crude product MBT building-up process changes molten for dithiocarbonic anhydride sulphur technique into molten sulfur and feeds intake, reduce process safety risk; With MBT crude product for the direct synthesis accelerant CBS of raw material, and adopt environmental protection hydrogen peroxide as oxygenant, this technique eliminates MBT treating process, and technical process is short, and cost is low, and products obtained therefrom yield is high, quality good; Do not produce high slat-containing wastewater, environmental pollution is little.
Accompanying drawing explanation
Fig. 1: be schematic flow sheet of the present invention.
Embodiment
Below by specific embodiment, the present invention is described in further detail:
Following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
(1) synthesis accelerant MBT crude product: aniline 450kg, the melting sulphur 155kg, the dithiocarbonic anhydride 368kg that obtain from Crouse's operation are dropped into autoclave respectively.Temperature of reaction is 250 DEG C, and resulting pressure is 9.05MPa, reacts 5 hours synthetic rubber accelerant MBT crude products.Crude product MBT content reaches more than 85%.
(2) crude product MBT is utilized to prepare accelerator CBS:
A, dispersion: will put into 4t water in stills for air blowing, open and stir.Crude product M is carried stills for air blowing, stirs 0.5h, cooling obtains the less crude product MBT of particle diameter.Water is released from reactor.
B, oxidation: the hexahydroaniline of 4790kg30% is added stills for air blowing.Mix rear dropping hydrogen peroxide oxidant, hydrogen peroxide concentration is 5%.Oxidizing temperature 50 DEG C, oxidization time is 2h.When starch potassium iodide reagents becomes blue, detect and arrive oxidation terminal.
C, the reaction mixture being reacted to terminal is carried out suction filtration, filter cake washs 2 times with the Aqueous Solution of Cyclohexylamine of mass content 10%; Then to be washed to neutrality, qualified aniline fluid bed after filtration cakes torrefaction, is obtained.
Embodiment 2
(1) synthesis accelerant MBT crude product: aniline 450kg, the melting sulphur 186kg, the dithiocarbonic anhydride 552kg that obtain from Crouse's operation are dropped into autoclave respectively.Temperature of reaction is 260 DEG C, and resulting pressure is 11MPa, reacts 3 hours synthetic rubber accelerant MBT crude products.Crude product MBT content reaches more than 85%.
(2) crude product MBT is utilized to prepare accelerator CBS:
A, dispersion: will put into 8t water in stills for air blowing, open and stir.Crude product M is carried stills for air blowing, stirs 1h, cooling obtains the less crude product MBT of particle diameter.Water is released from reactor.
B, oxidation: the hexahydroaniline of 4790kg50% is added stills for air blowing.Mix rear dropping hydrogen peroxide oxidant, hydrogen peroxide concentration is 10%.Oxidizing temperature 25 DEG C, oxidization time is 4h.Detect after starch potassium iodide reagents becomes basket and arrive oxidation terminal.
C, the reaction mixture being reacted to terminal is carried out suction filtration, filter cake washs 3 times with the Aqueous Solution of Cyclohexylamine of mass content 5%; Then to be washed to neutrality, qualified aniline fluid bed after filtration cakes torrefaction, is obtained.
Embodiment 3:
(1) synthesis accelerant MBT crude product: aniline 450kg, the melting sulphur 170.5kg, the dithiocarbonic anhydride 442kg that obtain from Crouse's operation are dropped into autoclave respectively.Temperature of reaction is 280 DEG C, and resulting pressure is 9.8MPa, reacts 4 hours synthetic rubber accelerant MBT crude products.Crude product MBT content reaches more than 85%.
(2) crude product MBT is utilized to prepare accelerator CBS:
A, dispersion: will put into 6t water in stills for air blowing, open and stir.Crude product M is carried stills for air blowing, stirs 2h, cooling obtains the less crude product MBT of particle diameter.Water is released from reactor.
B, oxidation: the hexahydroaniline of 4790kg40% is added stills for air blowing.Mix rear dropping hydrogen peroxide oxidant, hydrogen peroxide concentration is 7%.Oxidizing temperature 45 DEG C, oxidization time is 3h.When starch potassium iodide reagents becomes blue, detect and arrive oxidation terminal.
C, the reaction mixture being reacted to terminal is carried out suction filtration, filter cake washs 2 times with the Aqueous Solution of Cyclohexylamine of mass content 7%; Then to be washed to neutrality, qualified aniline fluid bed after filtration cakes torrefaction, is obtained.
Claims (1)
1. produced the method for rubber vulcanizing accelerator CBS by crude product MBT, it is characterized in that step is as follows:
(1) aniline, dithiocarbonic anhydride, melting sulphur are dropped into autoclave respectively, feed molar proportioning aniline: sulphur: dithiocarbonic anhydride is 1:(1 ~ 1.2): (1 ~ 1.5); Temperature of reaction is 250 DEG C ~ 280 DEG C, and pressure is 9 ~ 11MPa, reacts 3 ~ 6 hours synthetic rubber accelerant MBT crude products;
(2) reaction gained crude product MBT is delivered to high-speed stirring to be filled with water stills for air blowing, crude product MBT and quality are than being 1:5 ~ 10, and stir 0.5 ~ 2h, cooling obtains crude product MBT particle;
(3) hexahydroaniline solution is added stills for air blowing, hexahydroaniline strength of solution is 30 ~ 50% (w/w), crude product MBT and hexahydroaniline mol ratio is 1:3 ~ 5;
(4) mix rear dropping hydrogen peroxide oxidant, hydrogen peroxide concentration is 5% ~ 10% (w/w); Oxidizing temperature 25 ~ 50 DEG C, oxidization time is 2 ~ 4h, and starch potassium iodide reagents change indigo plant is then oxidized terminal and arrives;
(5) reaction mixture carries out suction filtration, and filter cake is with the Aqueous Solution of Cyclohexylamine of mass content 5 ~ 10% washing 2 ~ 3 times; Then to be washed to neutrality, qualified aniline fluid bed after filtration cakes torrefaction, is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410848247.9A CN104592161A (en) | 2014-12-29 | 2014-12-29 | Method for producing rubber vulcanization accelerator CBS by crude product MBT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410848247.9A CN104592161A (en) | 2014-12-29 | 2014-12-29 | Method for producing rubber vulcanization accelerator CBS by crude product MBT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104592161A true CN104592161A (en) | 2015-05-06 |
Family
ID=53118265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410848247.9A Pending CN104592161A (en) | 2014-12-29 | 2014-12-29 | Method for producing rubber vulcanization accelerator CBS by crude product MBT |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104592161A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912534A (en) * | 2019-04-10 | 2019-06-21 | 淄博拓研化学科技有限公司 | Crude product M dioxygen oxidation method produces accelerator CBS cleaning procedure |
| 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 |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
| CN116478110A (en) * | 2023-03-28 | 2023-07-25 | 烟台恒鑫化工科技有限公司 | Preparation method and application of rubber vulcanization accelerator |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436346A (en) * | 1991-12-21 | 1995-07-25 | Akzo Nobel N.V. | Process for the preparation of benzothiazolyl-2-sulphenamides |
| CN101260088A (en) * | 2008-04-21 | 2008-09-10 | 天津市科迈化工有限公司 | Method for purifying rubber vulcanization accelerator MBT |
| 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 |
| CN101759659A (en) * | 2009-11-16 | 2010-06-30 | 天津市科迈化工有限公司 | Method for synthesizing thiofide MBT by liquid sulphur |
-
2014
- 2014-12-29 CN CN201410848247.9A patent/CN104592161A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436346A (en) * | 1991-12-21 | 1995-07-25 | Akzo Nobel N.V. | Process for the preparation of benzothiazolyl-2-sulphenamides |
| 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 |
| CN101260088A (en) * | 2008-04-21 | 2008-09-10 | 天津市科迈化工有限公司 | Method for purifying rubber vulcanization accelerator MBT |
| CN101759659A (en) * | 2009-11-16 | 2010-06-30 | 天津市科迈化工有限公司 | Method for synthesizing thiofide MBT by liquid sulphur |
Non-Patent Citations (3)
| Title |
|---|
| 万志杰: "硫化促进剂CZ生产新工艺介绍", 《天津化工》, vol. 28, no. 5, 30 September 2014 (2014-09-30), pages 29 - 30 * |
| 吴举祥: "粗品M合成硫化促进剂CBS生产工艺研究", 《化学工程师》, no. 5, 31 May 2007 (2007-05-31), pages 45 - 47 * |
| 胡生泳等: "硫化促进剂CZ合成方法进展", 《精细石油化工》, no. 1, 31 January 1997 (1997-01-31), pages 12 - 14 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912534A (en) * | 2019-04-10 | 2019-06-21 | 淄博拓研化学科技有限公司 | Crude product M dioxygen oxidation method produces accelerator CBS cleaning procedure |
| 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 |
| CN110523332A (en) * | 2019-09-16 | 2019-12-03 | 山东尚舜化工有限公司 | A kind of device and method of continuous production aniline fluid bed |
| CN110523332B (en) * | 2019-09-16 | 2021-07-02 | 山东尚舜化工有限公司 | Equipment and method for continuously producing vulcanization accelerator CBS |
| CN116478110A (en) * | 2023-03-28 | 2023-07-25 | 烟台恒鑫化工科技有限公司 | Preparation method and application of rubber vulcanization accelerator |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104592161A (en) | Method for producing rubber vulcanization accelerator CBS by crude product MBT | |
| CN104557639A (en) | Method of preparing 2-nitro-4-methylsulfonyl benzoic acid | |
| CN104610193A (en) | Preparation method of rubber vulcanizing accelerator TBBS | |
| CN101139338A (en) | Preparation of 2,2-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt | |
| CN105037295B (en) | A kind of method for producing sulfenamide thiofide | |
| CN102492235A (en) | Epoxidized soybean oleic acid calcium zinc composite stabilizing agent for PVC (polyvinyl chloride) and its preparation method | |
| CN104230844B (en) | The preparation method of accelerator CZ | |
| CN101906082A (en) | Method for synthesizing TBBS (Tertiarybutyl Benzothiazole Sulfenamide) by mechanically applying mother solution | |
| CN102827104A (en) | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer | |
| CN104311506A (en) | Synthetic process of rubber vulcanization accelerator CBS | |
| CN102838561A (en) | Production method of rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) | |
| CN106632141A (en) | Method for producing rubber vulcanization accelerator CZ (N-Cyclohexyl-Benzothiazole Sulfenamide,) by two-drop method | |
| CN102863402A (en) | Preparation method of accelerator CBS | |
| CN102295620B (en) | Co-production synthesizing technology of rubber vulcanization promoter NS | |
| CN104211657A (en) | Refining method of rubber vulcanizing accelerant M | |
| CN101481429A (en) | Industrial production method for producing chlorinated rubber by aqueous phase suspension | |
| CN103803571B (en) | A kind of method being prepared water glass by copper nickel slag | |
| CN108727297A (en) | A kind of hydrogen peroxide oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide | |
| CN104725534B (en) | Method for preparing chlorosulfonated polyethylene by suspension method | |
| CN106316981A (en) | Preparation method of N-cyclohexyl-2-benzothiazolesulfenamide | |
| CN205761135U (en) | A kind of novel device for realizing lime nitrogen hydrolysis | |
| CN104262288A (en) | Production method of rubber vulcanization accelerator DM | |
| CN108101865B (en) | Preparation method of rubber vulcanization accelerator CBBS | |
| CN108047161A (en) | A kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS | |
| CN101676273B (en) | Method for directly synthesizing accelerant N-tertiary butyl benzothiazole sulfenamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150506 |
|
| WD01 | Invention patent application deemed withdrawn after publication |