CN103073521A - Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) - Google Patents
Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) Download PDFInfo
- Publication number
- CN103073521A CN103073521A CN2012103611188A CN201210361118A CN103073521A CN 103073521 A CN103073521 A CN 103073521A CN 2012103611188 A CN2012103611188 A CN 2012103611188A CN 201210361118 A CN201210361118 A CN 201210361118A CN 103073521 A CN103073521 A CN 103073521A
- Authority
- CN
- China
- Prior art keywords
- temperature
- reaction
- oxygen
- dibenzothiazyl disulfide
- tertiary butyl
- 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.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS). A specific process as below: adding 30-60ml of ammonia; weighing 33.25g of Dithio-dibenzo thiazole, 0.10-0.25g of a copper ammonia catalyst and a surface active agent under oxygen pressure of 0.2-0.8MPa, and adding into a reaction kettle; slowly injecting 15.36-19.02g of tert-butylamine by a metering pump to generate a target product at a reasonable reaction temperature; and conducting centrifugation, washing and drying to obtain the product NS. The method provided by the invention can effectively reduce the treatment amount of organic wastewater, reduce comprehensive cost, and has advantages of few raw material varieties, high reaction selectivity, high yield and short cycle; and the method is better than a current production method, and can well meet the demand of high-end market.
Description
One, technical field
The invention belongs to the preparing technical field of thiofide, particularly the preparation method of a kind of rubber vulcanization accelerator N-tertiary butyl-2-[4-morpholinodithio sulphenamide (NS).
Two, background technology
In recent years, in the world to the toxicity problem pay attention to day by day of the vulcanization accelerator nitrosamine that easily generation can be carcinogenic in the Rubber processing process.Find after deliberation, the generation of nitrosamine is owing to adding the promotor that the use in man-hour contains secondary amine group at rubber product, belong to this class promotor and common are N-oxygen diethylidene benzothiazole-2-sulphenamide (NOBS), N, N-di-isopropyl-2-[4-morpholinodithio sulphenamide (DIBS) and N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ) etc., this is because such promotor of preparation is all adopted secondary amine group raw material such as morpholine, Diisopropylamine etc., nitrosation reaction can occur in these promotor of containing secondary amine group in air, generate nitrosamine compound.To this, multinomial restricted rules are put into effect in succession.Thereby, replace product as a new generation, the greenization preparation of rubber vulcanization accelerator NS seems particularly important.
NS preparation method existing on the current industrial mainly contains sodium hypochlorite oxidization and hydrogen peroxide oxidation method.Sodium hypochlorite oxidization is first chlorine to be passed into sodium hydroxide solution with the preparation clorox, drops into the 2-benzothiazolyl mercaptan and TERTIARY BUTYL AMINE condensation oxidation makes NS again.The problem that this method exists is complex process, the auxiliary material large usage quantity, and reactant chlorine is corrosive hypertoxic gas, and sodium hydroxide is again highly basic, and is not only higher to equipment requirements, also can cause quite serious pollution to environment, production cost is higher, simultaneously, is difficult to avoid product over oxidation phenomenon, cause reaction preference to reduce, product yield and quality are on the low side.Existing part producing enterprise has selected the alternative sodium hypochlorite oxidization of hydrogen peroxide oxidation method to come synthesis accelerant NS both at home and abroad at present, namely in reactor, drop into TERTIARY BUTYL AMINE, 2-benzothiazolyl mercaptan and solvent, and the dropping hydrogen peroxide makes its generation oxidizing reaction make NS.This kind method is few in synthetic Raw kind, equipment is simple, yet required quantity of solvent is large, high expensive, reaction preference are not high, and the quantity discharged of organic waste water is larger.
Three, summary of the invention
Be the defective that exists in the whole bag of tricks that overcomes preparation NS in the prior art, the invention provides the method that a kind of greenization prepares rubber accelerator NS, this method has remedied prior art deficiency in process of production, more cleans, efficiently and energy-conservationly produces rubber vulcanization accelerator NS.The preparation technology of NS of the present invention is achieved by the following scheme: drop into 30～60ml ammoniacal liquor, depress at 0.2～0.8MPa oxygen, taking by weighing 33.25g dithio-bis-benzothiazole and 0.10～0.25g cuprammonium catalyzer drops in the reaction flask, use volume pump slowly to inject 15.36～19.02g TERTIARY BUTYL AMINE, reasonably generating target product under the temperature of reaction, by operations such as centrifugal, washing, oven dry, get desired product NS.Its purity 〉=99%, first fusing point 〉=106.0 ℃, outward appearance is off-white color.This preparation method has reduced the treatment of Organic Wastewater amount because selecting cheap high purity oxygen to replace hydrogen peroxide as the reaction oxygenant, comprehensive cost reduces, this method has the advantage that raw material variety is few, reaction preference is high, yield is high, the cycle is short concurrently simultaneously, obviously be better than existing production method, can satisfy admirably the demand of high-end market.
1, the present invention is raw materials used
1.1, dithio-bis-benzothiazole: off-white color crystallization, relative density 1.45～1.54g/cm
3, nontoxic little hardship.Fusing point is greater than 175 ℃.Dissolve in chloroform, be partially soluble in benzene, ethanol and tetracol phenixin, water insoluble, gasoline and ethyl acetate.
1.2, TERTIARY BUTYL AMINE: colourless inflammable liquid, the relative density 0.70g/cm in the time of 25 ℃
3, 44.5 ℃ of boiling points can be miscible with water, ethanol, acetone etc.The pungency ammonia odor is arranged.
1.3, oxygen: colourless under the normal temperature, odorless, tasteless is 1.43g/L in normal conditions lower density, and is not soluble in water under the normal pressure, and standard atmosphere is depressed solubilized 30ml oxygen in the 1L water.
1.4, ammoniacal liquor: 25% aqueous solution.Density is 0.91g/cm in the time of 20 ℃
3, strong sharp aroma is arranged, can dissolve numerous organic compound.
1.5, the cuprammonium catalyzer: the four ammino copper complexs that made by cupric oxalate and ammoniacal liquor.
1.6, TW-20: nonionogenic tenside.Relative density 1.01g/cm
3, 321 ℃ of boiling points contain more hydrophilic radical in the molecule, can be miscible with water, methyl alcohol, ethanol and ethyl acetate, be insoluble to paraffin, expressed oil and V.M.. naphtha.Have the effects such as good emulsifying, diffusion, solubilising.
2, production formula of the present invention:
Dibenzothiazyl disulfide (mol): ammoniacal liquor (1)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): TERTIARY BUTYL AMINE (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyzer (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): tensio-active agent (g)=1.0: (0.00015～0.00025)
3, production process of the present invention:
In having the 1L autoclave of temperature, pressure-detecting device and permanent magnetic stirrer, add 30～60ml ammoniacal liquor, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyzer 0.10～0.25g and minute quantity tensio-active agent TW-20 under the violent stirring, temperature control to 10～25 ℃, passing into oxygen, to make pressure be 0.2～0.8MPa, the TERTIARY BUTYL AMINE that in 1.5～3.5h, adds 15.36～19.02g, this moment, temperature in the kettle raise, 30～42 ℃ of control temperature, reaction 1～2h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir.White precipitate is through washing, dewater, be drying to obtain product.
4, the advantage of synthesis technique involved in the present invention:
4.1, do not use inorganic acid and highly basic in the synthesis technique flow process, to production unit without strong corrosion;
4.2, technique is simple, single stage method can be synthesized target product, and is with short production cycle;
4.3, the materials kind is few, oxygenant is high purity oxygen, low production cost;
4.4, in the building-up process without waste gas, waste sludge discharge, wastewater treatment capacity reduces greatly, has substantially accomplished cleaner production;
4.5, compare to the like product that other method is produced, product appearance is white, first fusing point is higher than 106 ℃, purity 〉=99%;
4.6, in rubber applications test, show that curing time is short, scorch safety is good, resistance toheat is excellent and the advantage such as anti-reversion.Compare to the product that other method is produced, then show remarkable vulcanization of rubber application performance.
Four, description of drawings:
Fig. 1 is the preparation method's of rubber vulcanization accelerator N-tertiary butyl of the present invention-2-[4-morpholinodithio sulphenamide process flow sheet.
Five, embodiment
Raw materials used among the preparation method of rubber vulcanization accelerator N-tertiary butyl of the present invention-2-[4-morpholinodithio sulphenamide is dibenzothiazyl disulfide, TERTIARY BUTYL AMINE, oxygen, ammoniacal liquor, cuprammonium catalyzer and tensio-active agent; Its formula rate is as follows:
Dibenzothiazyl disulfide (mol): ammoniacal liquor (1)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): TERTIARY BUTYL AMINE (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyzer (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): tensio-active agent (g)=1.0: (0.00015～0.00025)
Embodiment one:
In having the 1L autoclave of temperature, pressure-detecting device and permanent magnetic stirrer, add 35ml ammoniacal liquor, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyzer 0.12g and tensio-active agent TW-20 0.005g under the violent stirring, temperature control to 20 ℃, passing into oxygen, to make pressure be 0.4MPa, adds the TERTIARY BUTYL AMINE of 16.09g in 2.5h, this moment, temperature in the kettle raise, 40 ℃ of temperature of control, reaction 1.5h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir.White precipitate is through washing, dewater, be drying to obtain product.Its outward appearance is canescence, and after measured, reaction yield is 96.2%, and the first fusing point that obtains product after the reaction is 106.3 ℃, and purity is 98.6%.
Embodiment two:
In having the 1L autoclave of temperature, pressure-detecting device and permanent magnetic stirrer, add 42ml ammoniacal liquor, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyzer 0.18g and tensio-active agent TW-20 0.006g under the violent stirring, temperature control to 16 ℃, passing into oxygen, to make pressure be 0.6MPa, adds the TERTIARY BUTYL AMINE of 15.36g in 2h, this moment, temperature in the kettle raise, 38 ℃ of temperature of control, reaction 1.5h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir.White precipitate is through washing, dewater, be drying to obtain product.Its outward appearance is off-white color, and after measured, reaction yield is 95.8%, and the fusing point that obtains product after the reaction is 106.8 ℃, and purity is 98.9%.
Embodiment three:
In having the 1L autoclave of temperature, pressure-detecting device and permanent magnetic stirrer, add 50ml ammoniacal liquor, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyzer 0.20g and tensio-active agent TW-20 0.008g under the violent stirring, temperature control to 10 ℃, passing into oxygen, to make pressure be 0.5MPa, adds the TERTIARY BUTYL AMINE of 17.55g in 3.0h, this moment, temperature in the kettle raise, 35 ℃ of temperature of control, reaction 2h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir.White precipitate is through washing, dewater, be drying to obtain product.Its outward appearance is white in color, and after measured, reaction yield is 97.4%, and the fusing point that obtains product after the reaction is 107.2 ℃, and purity is 99.1%.
Embodiment four:
In having the 1L autoclave of temperature, pressure-detecting device and permanent magnetic stirrer, add 56ml ammoniacal liquor, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol), cuprammonium catalyzer 0.22g and tensio-active agent TW-200.006g under the violent stirring, temperature control to 10 ℃, passing into oxygen, to make pressure be 0.6MPa, adds the TERTIARY BUTYL AMINE of 18.29g in 3.0h, this moment, temperature in the kettle raise, 35 ℃ of temperature of control, reaction 2h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir.White precipitate is through washing, dewater, be drying to obtain product.Its outward appearance is white in color, and after measured, reaction yield is 98.0%, and the fusing point that obtains product after the reaction is 107.6 ℃, and purity is 99.5%.
Claims (5)
1. the preparation method of rubber vulcanization accelerator N-tertiary butyl-2-[4-morpholinodithio sulphenamide (NS) is characterized in that: raw materials usedly in the method be dibenzothiazyl disulfide, TERTIARY BUTYL AMINE, oxygen, ammoniacal liquor, cuprammonium catalyzer and tensio-active agent; Its formula rate is as follows:
Dibenzothiazyl disulfide (mol): ammoniacal liquor (1)=1.0: (0.3～0.6)
Dibenzothiazyl disulfide (mol): TERTIARY BUTYL AMINE (mol)=1.0: (1.05～1.30)
Dibenzothiazyl disulfide (mol): oxygen (mol)=1.0: (0.55～0.80)
Dibenzothiazyl disulfide (g): cuprammonium catalyzer (g)=1.0: (0.003～0.007)
Dibenzothiazyl disulfide (g): tensio-active agent (g)=1.0: (0.00015～0.00025)
Its production process is: add ammoniacal liquor in the autoclave with temperature, pressure-detecting device and permanent magnetic stirrer, drop into reactant dibenzothiazyl disulfide, cuprammonium catalyzer and tensio-active agent TW-20 under the violent stirring, temperature control to 10～25 ℃, passing into oxygen, to make pressure be 0.2～0.8MPa, in 1.5～3.5h, add TERTIARY BUTYL AMINE, this moment, temperature in the kettle raise, the control temperature is 30～42 ℃, reaction 1～2h, oxygen uptake is seldom the time, terminal point is namely arrived in reaction, stops to stir, and white precipitate is through washing, dewater, be drying to obtain product.
2. preparation method according to claim 1, it is characterized in that: its concrete production process is: have temperature, add 35ml ammoniacal liquor in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol) under the violent stirring, cuprammonium catalyzer 0.12g and tensio-active agent TW-20 0.005g, temperature control to 20 ℃, passing into oxygen, to make pressure be 0.4MPa, the TERTIARY BUTYL AMINE that in 2.5h, adds 16.09g, this moment, temperature in the kettle raise, 40 ℃ of control temperature, reaction 1.5h, oxygen uptake is seldom the time, and terminal point is namely arrived in reaction, stop to stir, white precipitate is through washing, dehydration, be drying to obtain product.
3. preparation method according to claim 1, it is characterized in that: its concrete production process is: have temperature, add 42ml ammoniacal liquor in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol) under the violent stirring, cuprammonium catalyzer 0.18g and tensio-active agent TW-20 0.006g, temperature control to 16 ℃, passing into oxygen, to make pressure be 0.6MPa, the TERTIARY BUTYL AMINE that in 2h, adds 15.36g, this moment, temperature in the kettle raise, 38 ℃ of control temperature, reaction 1.5h, oxygen uptake is seldom the time, and terminal point is namely arrived in reaction, stop to stir, white precipitate is through washing, dehydration, be drying to obtain product.
4. preparation method according to claim 1, it is characterized in that: its concrete production process is: have temperature, add 50ml ammoniacal liquor in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol) under the violent stirring, cuprammonium catalyzer 0.20g and tensio-active agent TW-20 0.008g, temperature control to 10 ℃, passing into oxygen, to make pressure be 0.5MPa, the TERTIARY BUTYL AMINE that in 3.0h, adds 17.55g, this moment, temperature in the kettle raise, 35 ℃ of control temperature, reaction 2h, oxygen uptake is seldom the time, and terminal point is namely arrived in reaction, stop to stir, white precipitate is through washing, dehydration, be drying to obtain product.
5. preparation method according to claim 1, it is characterized in that: its concrete production process is: have temperature, add 56ml ammoniacal liquor in the 1L autoclave of pressure-detecting device and permanent magnetic stirrer, drop into reactant dibenzothiazyl disulfide 33.25g (0.1mol) under the violent stirring, cuprammonium catalyzer 0.22g and tensio-active agent TW-20 0.006g, temperature control to 10 ℃, passing into oxygen, to make pressure be 0.6MPa, the TERTIARY BUTYL AMINE that in 3.0h, adds 18.29g, this moment, temperature in the kettle raise, 35 ℃ of control temperature, reaction 2h, oxygen uptake is seldom the time, and terminal point is namely arrived in reaction, stop to stir, white precipitate is through washing, dehydration, be drying to obtain product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210361118.8A CN103073521B (en) | 2012-09-20 | 2012-09-20 | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210361118.8A CN103073521B (en) | 2012-09-20 | 2012-09-20 | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073521A true CN103073521A (en) | 2013-05-01 |
| CN103073521B CN103073521B (en) | 2017-02-15 |
Family
ID=48150240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210361118.8A Active CN103073521B (en) | 2012-09-20 | 2012-09-20 | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073521B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539756A (en) * | 2013-10-16 | 2014-01-29 | 科迈化工股份有限公司 | Method for dehydrating in process of producing rubber vulcanizing accelerant MBTS (2-mercaptobenzothiazole disulfide) by using hydrogen peroxide method |
| CN106866577A (en) * | 2017-01-24 | 2017-06-20 | 蔚林新材料科技股份有限公司 | The method that the oxidation of catalytic molecular oxygen prepares sulfenamide thiofide in water phase |
| CN110354900A (en) * | 2019-08-27 | 2019-10-22 | 聊城宝和化学科技有限公司 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
| CN110776478A (en) * | 2019-11-11 | 2020-02-11 | 山东阳谷华泰化工股份有限公司 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182873A (en) * | 1972-10-04 | 1980-01-08 | Rhone-Poulenc S.A. | Process for the preparation of thiazolesulphenamides |
| EP0029718A1 (en) * | 1979-11-23 | 1981-06-03 | Monsanto Europe S.A./N.V. | Process for the production of sulphenamides |
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
-
2012
- 2012-09-20 CN CN201210361118.8A patent/CN103073521B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182873A (en) * | 1972-10-04 | 1980-01-08 | Rhone-Poulenc S.A. | Process for the preparation of thiazolesulphenamides |
| EP0029718A1 (en) * | 1979-11-23 | 1981-06-03 | Monsanto Europe S.A./N.V. | Process for the production of sulphenamides |
| US4670556A (en) * | 1983-07-16 | 1987-06-02 | Akzo Nv | Process for the production of thiazolyl-2-sulphenamides |
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| 刘小培等: "Ｎ－叔丁基-2-苯并噻唑次磺酰胺的合成工艺研究进展", 《化学研究》 * |
| 周禾大: "硫化促进剂 NS合成工艺研究", 《江苏化工》 * |
| 徐万平等: "硫化促进剂N-叔丁基-2-苯并噻唑的合成工艺综述", 《工艺，实验》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539756A (en) * | 2013-10-16 | 2014-01-29 | 科迈化工股份有限公司 | Method for dehydrating in process of producing rubber vulcanizing accelerant MBTS (2-mercaptobenzothiazole disulfide) by using hydrogen peroxide method |
| CN106866577A (en) * | 2017-01-24 | 2017-06-20 | 蔚林新材料科技股份有限公司 | The method that the oxidation of catalytic molecular oxygen prepares sulfenamide thiofide in water phase |
| CN106866577B (en) * | 2017-01-24 | 2018-11-23 | 蔚林新材料科技股份有限公司 | The method of catalytic molecular oxygen oxidation preparation sulfenamide thiofide in water phase |
| CN110354900A (en) * | 2019-08-27 | 2019-10-22 | 聊城宝和化学科技有限公司 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
| CN110776478A (en) * | 2019-11-11 | 2020-02-11 | 山东阳谷华泰化工股份有限公司 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073521B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107056649B (en) | A kind of preparation method and applications for the metal-organic framework materials loading schiff bases complex | |
| CN101665515B (en) | P-N collaborative type flame-retardant compound and preparation method thereof | |
| CN107442177B (en) | Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural | |
| CN102688722B (en) | Hydrogenated rosin-based quaternary ammonium salt gemini surfactant and preparation method thereof | |
| CN103073521A (en) | Preparation method of rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) | |
| CN104069891B (en) | The preparation method of the immobilized HP catalyst of a kind of polymer microballoon | |
| CN108262072A (en) | It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application | |
| CN104761718B (en) | A kind of novel polyether amine and its synthetic method as gasoline cleaning agent | |
| CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| CN101139338A (en) | Preparation of 2,2-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt | |
| CN108187745A (en) | A kind of preparation method of methanation catalyst prepared by synthetic gas | |
| CN104119210B (en) | The method preparing polymethoxy dimethyl ether combined by a kind of slurry bed system and fixed bed | |
| CN113754879A (en) | Synthesis method of alkyl polyoxyethylene ether quaternary ammonium salt surfactant | |
| CN103664547B (en) | The method of synthesizing polyoxymethylene dme | |
| CN105642325A (en) | Supported vanadium-based catalyst and preparation method thereof | |
| CN110156717A (en) | A kind of synthetic method of rubber vulcanization accelerator NS | |
| CN105037116B (en) | A kind of method that Aromatic aldehyde compound is prepared using sodium lignin sulfonate | |
| CN108947758A (en) | A method of catalysis dibenzofurans open loop prepares biphenyl | |
| CN106831644B (en) | The method of catalytic molecular oxygen oxidation 2,2 '-two sulphur union II benzothiazoles of preparation in water phase | |
| CN102367230B (en) | Method for synthesizing nitrile from aldoxime | |
| CN110305075A (en) | A kind of method of Co catalysts oxygen method synthesis N cyclohexyl 2 benzothiazole sulfenamide | |
| TWI654178B (en) | Method for preparing dialkyl carbonate | |
| CN104056665A (en) | Application of ionic liquid-modified mesoporous material in decomposition of cyclohexyl hydroperoxide | |
| CN104387238A (en) | Preparation method of branched alkyl phenol | |
| CN108047161A (en) | A kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 457000 Puyang chemical industry cluster area, Henan Patentee after: Polytron Technologies Inc materials Address before: Industrial Demonstration Zone in Puyang city of Henan province 457163 (BU Zhai Xiang) Patentee before: Puyang Willing Chemicals Co., Ltd. |