CN103524452A - Synthetic method for rubber vulcanization accelerator DZ - Google Patents
Synthetic method for rubber vulcanization accelerator DZ Download PDFInfo
- Publication number
- CN103524452A CN103524452A CN201310467448.XA CN201310467448A CN103524452A CN 103524452 A CN103524452 A CN 103524452A CN 201310467448 A CN201310467448 A CN 201310467448A CN 103524452 A CN103524452 A CN 103524452A
- Authority
- CN
- China
- Prior art keywords
- salt
- oxygenant
- accelerator
- hydrogen peroxide
- mercaptobenzothiazole
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method for a rubber vulcanization accelerator DZ. A mixture of hydrogen peroxide and sulfuric acid is used as an oxidant. M (2-mercaptobenzothiazole) having a mass concentration of 85%-90% is used as a raw material. The method includes adding dicyclohexylamine and isopropanol into a reactor, adding dropwise an M-Na salt at 30-80 DEG C and at a rotate speed of 500-1200 r/min with the dropping rate of the M-Na salt being 2-3 h, and adding the oxidant dropwise at the same time to control the pH to be 9-11; and after the reaction is finished, performing suction filtration, washing with the isopropanol, washing with water, filtering and drying to obtain a rubber vulcanization accelerator DZ product. The method is simple in process. The hydrogen peroxide which is environmental friendly is used as the oxidant, and the reaction is free from production of a large quantity of salt-containing waste water. The method is prone to industrialization. A proper amount of the dicyclohexylamine is used. The produced accelerator DZ has a purity reaching 98% and the yield reaches 85%.
Description
Technical field
The present invention relates to a kind of thiofide N, the production method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ), belongs to rubber vulcanization accelerator DZ production technical field.
Background technology
DZ is delayed action accelerator, is the requisite a kind of primary accelerator of current rubber industry.Be specially adapted to radial, there is sulfuration and promote and adhesive effect.Patent (patent No. 200810053774.5) the method process of delivering on July 8th, 2008 comprises: Virahol and dicyclohexyl amine are joined in stills for air blowing, under the condition stirring, make dicyclohexyl amine fully be dissolved in Virahol, add again sulfuric acid, control pH value simultaneously, then drip M-Na salt, drip oxygenant clorox simultaneously, in reaction process, control pH value, after completion of the reaction suction filtration, washing, filtration, the dry rubber accelerator DZ product that to obtain.Although the DZ quality that the method for this patent obtains has reached 99%, yield does not have concrete numerical value, and needs three kinds of raw materials to drip in operation simultaneously, operation more complicated.Document (scientific and technical information, 2005,7:23) reported the method for the synthetic DZ of large proportioning oxidation style.Captax, dicyclohexyl amine, Virahol are added in reactor and stirred, make its salify; With clorox, as oxygenant, react cooling, suction filtration, washing, filtration, the dry product that to obtain.The dicyclohexyl amine amount that this method is used is large, and the yield of accelerator DZ is not high.Document (China Synthetic Rubber Industry, 1996,19:317) reported the fast synthesis method of accelerator DZ.Captax, dicyclohexyl amine, Virahol 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.This method accelerator DZ yield is low.Aforesaid method all can produce a large amount of brine wastes, to environment.
Summary of the invention
It is a kind of with hydrogen peroxide that the object of the production method of rubber vulcanization accelerator DZ of the present invention is to provide, sulfuric acid is mixed into oxygenant, mass content 85%～90%M (2-mercaptobenzothiazole), dicyclohexyl amine is the method for raw material production rubber vulcanization accelerator DZ, the method is simple to operate, do not produce a large amount of brine wastes, dicyclohexyl amine consumption is appropriate, and the DZ yield, the quality that synthesize are all higher.
Technical scheme of the present invention is as follows:
, sulfuric acid is mixed into oxygenant, 85%～90%M, and dicyclohexyl amine is the method for raw material production rubber vulcanization accelerator DZ, and step is as follows:
1) sulfuric acid in molar ratio: hydrogen peroxide: water is 1:2.5～2.7:9, joins oxygenant
2), by weight promotor (2-mercaptobenzothiazole) M: water is 1:2～2.3, reinforcing body sodium hydroxide is controlled pH=12, joins M-Na salt;
3) by dicyclohexyl amine: the M mol ratio in M of take is 1:1.
4) by weight Virahol: M (2-mercaptobenzothiazole) than 10～12:1.
In reactor, add dicyclohexyl amine and Virahol, at 30～80 ℃, rotating speed, be under the condition of 500～1200 revs/min, drip M-Na salt speed control at 2～3 hours, drip oxygenant control pH=9-11, after completion of the reaction suction filtration, isopropyl alcohol wash, washing, filtration, the dry rubber accelerator DZ product that to obtain simultaneously.
C
7H
5NS
2+C
12H
23N+1/2H
2SO
4+H
2O
2+NaOH=C
19H
26N
2S
2+1/2Na
2SO
4+3H
2O
The invention has the advantages that: the method process is simple, what oxygenant was used is that environment is not had to the hydrogen peroxide polluting, and reaction does not produce a large amount of brine wastes, be easy to industrialization, the dicyclohexyl amine using is appropriate, and the purity of the accelerator DZ synthesizing reaches 98%, and yield has reached 85%(in M).
Embodiment
Embodiment 1:
Get 15 grams, 98% sulfuric acid, 27.5% 46.4 grams, hydrogen peroxide, 24.3 grams, water is joined oxygenant.Get mass content 85%M50 gram, add 100 grams, water, reinforcing body sodium hydroxide, controlling pH value is 12, joins M-Na salt.Get in 46.1 grams of dicyclohexyl amines and 500 grams of hybrid reactors of Virahol, at 30 ℃, rotating speed, be under the condition of 500 revs/min, drip M-Na salt speed control at 2.0 hours and controlling under pH9 condition and controlling and drip oxygenant flow velocity, M-Na salt drips off, stop oxygenant, suction filtration, isopropyl alcohol wash, washing, filtration, the dry rubber accelerator DZ product that to obtain after completion of the reaction, the purity of accelerator DZ reaches 98%, yield has reached 85%(in M).
Embodiment 2:
Get 15 grams, 98% sulfuric acid, 27.5% 48.2 grams, hydrogen peroxide, 24.3 grams, water is joined oxygenant.Remove mass content 87%M50 gram, add 105 grams, water, reinforcing body sodium hydroxide, controlling pH value is 12, joins M-Na salt.Get in 47.2 grams of dicyclohexyl amines and 550 grams of hybrid reactors of Virahol, at 50 ℃, rotating speed, be under the condition of 900 revs/min, drip M-Na salt speed control at 2.5 hours and controlling under pH10 condition and controlling and drip oxygenant flow velocity, M-Na salt drips off, stop oxygenant, suction filtration, isopropyl alcohol wash, washing, filtration, the dry rubber accelerator DZ product that to obtain after completion of the reaction, the purity of accelerator DZ reaches 98%, yield has reached 85%(in M).
Embodiment 3:
Get 15 grams, 98% sulfuric acid, 27.5% 50.1 grams, hydrogen peroxide, 24.3 grams, water is joined oxygenant.Get mass content 90%M50 gram, add 115 grams, water, reinforcing body sodium hydroxide, controlling pH value is 12, joins M-Na salt.Get in 48.8 grams of dicyclohexyl amines and 600 grams of hybrid reactors of Virahol, at 80 ℃, rotating speed, be under the condition of 1200 revs/min, drip M-Na salt speed control at 3.0 hours and controlling under pH11 condition and controlling and drip oxygenant flow velocity, M-Na salt drips off, stop oxygenant, suction filtration, isopropyl alcohol wash, washing, filtration, the dry rubber accelerator DZ product that to obtain after completion of the reaction, the purity of accelerator DZ reaches 98%, yield has reached 85%(in M).
Claims (1)
1. a synthetic rubber accelerator D Z method, is mixed into oxygenant with hydrogen peroxide, sulfuric acid, 85%～90% captax, and dicyclohexyl amine is raw material, it is characterized in that: proportioning raw materials is:
1) sulfuric acid in molar ratio: hydrogen peroxide: water is 1:2.5～2.7:9, joins oxygenant
2), by weight promotor (2-mercaptobenzothiazole) M: water is 1:2～2.3, reinforcing body sodium hydroxide is controlled pH=12, joins M-Na salt;
3) by dicyclohexyl amine: 2-mercaptobenzothiazole mol ratio is 1:1;
4) by weight Virahol: 2-mercaptobenzothiazole is than 10～12:1;
In reactor, add dicyclohexyl amine and Virahol, at 30～80 ℃, rotating speed, be under the condition of 500～1200 revs/min, drip M-Na salt speed control at 2～3 hours, drip oxygenant control pH=9-11, after completion of the reaction suction filtration, isopropyl alcohol wash, washing, filtration, the dry rubber accelerator DZ product that to obtain simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467448.XA CN103524452A (en) | 2013-09-30 | 2013-09-30 | Synthetic method for rubber vulcanization accelerator DZ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467448.XA CN103524452A (en) | 2013-09-30 | 2013-09-30 | Synthetic method for rubber vulcanization accelerator DZ |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103524452A true CN103524452A (en) | 2014-01-22 |
Family
ID=49926856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310467448.XA Pending CN103524452A (en) | 2013-09-30 | 2013-09-30 | Synthetic method for rubber vulcanization accelerator DZ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524452A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143856A (en) * | 2007-09-10 | 2008-03-19 | 天津市科迈化工有限公司 | Method of producing rubber vulcanization accelerator DZ |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
| CN102838565A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Production method of rubber vulcanization accelerator DZ |
-
2013
- 2013-09-30 CN CN201310467448.XA patent/CN103524452A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143856A (en) * | 2007-09-10 | 2008-03-19 | 天津市科迈化工有限公司 | Method of producing rubber vulcanization accelerator DZ |
| CN101723916A (en) * | 2008-11-03 | 2010-06-09 | 刘要进 | Method for producing rubber vulcanization accelerator DZ |
| CN102838565A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Production method of rubber vulcanization accelerator DZ |
Non-Patent Citations (1)
| Title |
|---|
| 张越 等: "用粗M合成橡胶硫化促进剂DZ", 《化学推进剂与高分子材料》, 31 December 1999 (1999-12-31) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037295A (en) | Method for producing sulfenamide rubber vulcanization accelerator | |
| CN102367238A (en) | Method for synthesizing accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide | |
| CN102838565A (en) | Production method of rubber vulcanization accelerator DZ | |
| CN102391206A (en) | Method for producing rubber vulcanization accelerator DZ | |
| CN102976990B (en) | Crystallization purification method of thiourea | |
| CN103524450A (en) | Synthetic method for accelerator DZ by using methanol as solvent | |
| CN101462980B (en) | Industrial production method of 2,6-difluorobenzamide | |
| 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 | |
| CN103396292B (en) | Method for industrially producing A,A'-dihydroxy-1,3-diisobutylbenzene | |
| CN109734106B (en) | Method for preparing high-concentration sodium bisulfite solution by using industrial waste | |
| CN104211657A (en) | Refining method of rubber vulcanizing accelerant M | |
| CN103524454A (en) | Method for producing rubber vulcanization accelerant DZ by solvent method | |
| CN103524452A (en) | Synthetic method for rubber vulcanization accelerator DZ | |
| CN101157663A (en) | Method for producing rubber vulcanization accelerator NS | |
| CN103524451A (en) | Synthetic method for rubber vulcanization accelerator DZ by mother liquor circulation | |
| CN104557770A (en) | Method for synthesizing rubber vulcanization accelerator NS by taking sodium hypochlorite as oxidant | |
| CN102229549B (en) | Method for preparing isooctyl mercaptoacetate | |
| CN103539757A (en) | Method for synthesizing rubber vulcanization accelerator CZ | |
| CN104557774A (en) | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking isopropanol as solvent | |
| CN104557772A (en) | Synthesis method for producing accelerator N, N-dicyclohexyl-2-benzothiazolyl sulfenamide by taking methanol as solvent | |
| CN103102327A (en) | Preparation method of rubber accelerator DZ (N,N-Dicyclohexyl-2-benzothiazolsulfene amide) | |
| CN104447329A (en) | Preparation method of 2-chloroacetoacetic acid ethyl ester | |
| CN104557769A (en) | Production method of rubber vulcanization accelerator N,N-dicyclohexyl-2-benzothiazole sulfenamide | |
| CN103102328A (en) | Preparation method of rubber accelerator NS (N-tert-butyl benzothiazole-2-sulphenamide) | |
| CN103351350B (en) | Industrial preparation method of isocyanuric acid lead salt |
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: 20140122 |