CN111187193A - Preparation method of rubber additive 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane - Google Patents
Preparation method of rubber additive 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane Download PDFInfo
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Abstract
The invention provides a preparation method of 1, 6-bis (N, N-dibenzyl carbamyl disulfide) hexane as a rubber additive, which comprises the steps of taking 1, 6-dimercaptohexane as a raw material, firstly reacting with hydrogen peroxide to form 1, 2-dithiocyclooctane, then reacting the 1, 2-dithiocyclooctane with chlorine to form 1, 6-secondary octane sulfonyl chloride, and reacting the 1, 6-secondary octane sulfonyl chloride with dibenzyl dithiocarbamate to form a final product. The synthesis process is simple and easy to operate, the reaction time is shortened, and the production efficiency and yield are improved; toxic and harmful substance formaldehyde and 1, 6-disulfurylhulfanylhexane disodium salt hydrate are not used, a large amount of organic wastewater containing inorganic salt is reduced, the used solvent can be recycled after simple treatment, and the process is relatively clean and environment-friendly.
Description
Technical Field
The invention relates to a preparation method of 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane serving as a rubber additive, and belongs to the technical field of preparation of rubber additives.
Background
The natural rubber can generate a reversion phenomenon in the high-temperature or long-time vulcanization process, so that the crosslinking density of vulcanized rubber is reduced, and the mechanical property and the dynamic property of the vulcanized rubber are further reduced. The 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane is a novel efficient multifunctional crosslinking agent, has the functions of a vulcanization accelerator and reversion resistance, and the formed crosslinking bond has the stability of a monothio bond and a disulfide bond and the flexibility similar to a polysulfide crosslinking bond, so that a stable crosslinking network can be formed in the vulcanization process, the reversion resistance of rubber materials is improved, and the service life and the driving safety of tires are improved.
At present, 1, 6-disulfo-hexanedisodium 1, 6-disulfo-hexanediyl and sodium dibenzyl dithiocarbamate are mostly used as raw materials in the existing synthesis process at home and abroad, formaldehyde, toluene and alkali are used as catalysts to prepare the 1, 6-di (N, N-dibenzyl carbamyl disulfide) hexane, the process can generate a large amount of high-salt organic wastewater which contains formaldehyde and toluene and is difficult to treat, and the process has the disadvantages of low reaction rate, low production efficiency, complex process, low yield and no practical production requirement.
Disclosure of Invention
Aiming at the defects of the existing 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane preparation process, the invention provides a preparation method of 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane as a rubber additive, which takes 1, 6-dimercaptohexane as a raw material and provides a new process route for the preparation of 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane.
The molecular structural formula of 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane is as follows, the invention provides a new process route for preparing 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane, and the process has the advantages of easy operation, short reaction time, high production efficiency, high yield and the like, and the specific implementation mode is as follows:
a preparation method of 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane as a rubber additive is obtained by reacting dibenzyl dithiocarbamate with 1, 6-octane disulfonate, and the reaction formula is as follows:
further, in the above method, the 1, 6-disulfonyl octane is obtained by reacting 1, 2-dithiocyclooctane with chlorine, and the reaction formula is as follows:
further, in the above method, the 1, 2-dithiocyclooctane used is obtained by reacting 1, 6-dimercaptohexane with hydrogen peroxide, and the reaction formula is as follows:
further, the specific reaction process of the 1, 6-dimercaptohexane and the hydrogen peroxide is as follows: heating 1, 6-dimercaptohexane to reaction temperature, then dropping hydrogen peroxide into the 1, 6-dimercaptohexane for oxidation reaction, separating liquid after reaction, and drying the obtained organic phase to obtain the 1, 2-dithiocyclooctane.
Further, 1, 6-dimercaptohexane and hydrogen peroxide (H)2O2In terms of) is 1:1.0 to 1.2, preferably 1: 1.05.
Furthermore, the concentration of the hydrogen peroxide solution can be selected at will, and the industrial grade hydrogen peroxide with the concentration of about 40-55wt% is preferably adopted.
Further, the reaction temperature of the 1, 6-dimercaptohexane and the hydrogen peroxide is 0-80 ℃, and more preferably 25-30 ℃. And (4) after dropping the hydrogen peroxide solution, continuously reacting for 0.5-3.0 hours, preferably reacting for 1.5 hours. At the preferred reaction temperature and reaction time, the product yield is higher.
Further, the specific reaction process of the 1, 2-dithiocyclooctane and the chlorine gas is as follows: mixing the 1, 2-dithiocyclooctane and a solvent, then reducing the reaction temperature, introducing chlorine gas to carry out chlorination reaction, and obtaining the 1, 6-secondary octane sulfonyl chloride. The molar ratio of the 1, 2-dithiocyclooctane to the chlorine gas is 1: 1.0-1.2, preferably 1: 1.05.
Further, the reaction temperature of the 1, 2-dithiocyclooctane and the chlorine gas is-15 to 5 ℃, and more preferably-15 to-10 ℃. The reaction time of the 1, 2-dithiocyclooctane and chlorine gas is 1 to 5.0 hours, and more preferably 2.0 hours. At the preferred reaction temperature and reaction time, the product yield is higher.
Further, the solvent used for the reaction of 1, 2-dithiocyclooctane and chlorine gas is a linear hydrocarbon or aromatic hydrocarbon solvent, such as n-hexane, benzene, toluene, mineral spirits, etc., preferably mineral spirits. When the preferred solvent is used, the yield of the product is high.
Further, the specific reaction process of the dibenzyl dithiocarbamate and the 1, 6-secondary octane sulfonyl chloride comprises the following steps: cooling the aqueous solution of dibenzyl dithiocarbamate to the reaction temperature, then adding 1, 6-secondary octane sulfonyl chloride for reaction, heating the reaction solution after the reaction until oil and water phases are formed, separating the water phases, washing the oil phases with water, cooling and crystallizing to obtain the 1, 6-bis (N, N-dibenzyl carbamyl disulfide) hexane. And cooling the oil phase after water washing for crystallization, and separating and drying the crystals after complete crystallization to obtain the 1, 6-di (N, N-dibenzylcarbamyl disulfide) hexane product. The mother liquor after crystal separation can be distilled to recover water therein, and the residual salt can be reused or sold as industrial salt.
Further, the molar ratio of the dibenzyl dithiocarbamate to the 1, 6-octane disulfonate is 2.0-2.2: 1, preferably 2.05: 1.
Further, the reaction temperature of the dibenzyl dithiocarbamate and the 1, 6-secondary octane sulfonyl chloride is-15 to 5 ℃, and preferably-15 to-10 ℃. The reaction time of the dibenzyl dithiocarbamate and the 1, 6-octane sulfonyl chloride is 1.0-5.0 hours, and preferably 4.0 hours. At the preferred reaction temperature and reaction time, the product yield is higher.
Further, the dibenzyl dithiocarbamate is a water-soluble inorganic salt of dibenzyl dithiocarbamate, and is preferably sodium dibenzyl dithiocarbamate. When the dibenzyl dithiocarbamate is the sodium salt, the reaction is as follows:
the invention has the following beneficial effects:
1. the synthesis process is simple and easy to operate, the reaction time is shortened, and the production efficiency and yield are improved;
2. toxic and harmful substances such as formaldehyde and the like are not used, 1, 6-disulfurylsulfanyl hexane disodium salt hydrate is not used, a large amount of organic wastewater containing inorganic salt is reduced, and the process is relatively clean and environment-friendly;
3. the used solvent can be reused after simple treatment, thereby reducing the cost, reducing the discharge of waste water and lightening the environmental protection pressure.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, but the scope of the present invention is not limited thereto.
Unless otherwise specified, the raw materials used in the following examples are all commercially available products.
In the following examples, the purity of the obtained 1, 6-bis (N, N-dibenzylcarbamoyldisulfide) hexane was analyzed by liquid chromatography under the following conditions:
high performance liquid chromatograph: agilent 1260;
mobile phase: acetonitrile: 0.1wt% aqueous phosphoric acid solution by volume =90: 10;
a detector: an ultraviolet detector with a wavelength of 220 nm;
a chromatographic column: XDB-C18, 250 mm. times.4.6 mm, particle size 5 μm;
flow rate: 1.0 ml/min;
temperature of the constant temperature column box: 35 +/-1 ℃;
sample introduction amount: 10 μ L.
Example 1
153.4g of 1, 6-dimercaptohexane liquid (98 wt%) is added into a three-neck flask with a thermometer, a stirring and constant-pressure dropping funnel, the three-neck flask is immersed into a water bath kettle, 71.4g of 50% hydrogen peroxide solution is dropwise added to react for 1.5 hours, the temperature of the materials is maintained at 25.0-30.0 ℃ during the reaction, liquid separation and drying are carried out after the reaction is finished, 147.6g of liquid 1, 2-dithiocyclooctane is obtained, and the yield is 99.5%.
147.6g of 1, 2-dithiocyclooctane obtained in the above step and 300g of No. 120 solvent naphtha are added into a three-necked bottle with a jacket and stirring, the materials in the three-necked bottle are cooled to-15 to-10 ℃ by a glycol refrigerant, 74.9g of chlorine (99.0 wt%) is introduced into the three-necked bottle after cooling for reaction, the reaction temperature is maintained to-15 to-10 ℃ during the reaction, the reaction is carried out for 2h, 217.5g of 1, 6-secondary sulfonyl chloride octane is obtained, and the yield is 99.7%.
608.9g of sodium dibenzyl dithiocarbamate (98 wt%) is weighed and dissolved in water to prepare 70% aqueous solution by mass percentage concentration, then the aqueous solution is added into a three-necked bottle with a thermometer, a stirrer and a jacket, the material is cooled to-15 to-10 ℃ by introducing a refrigerant (ethylene glycol) into the three-necked bottle, then 217.5g of 1, 6-secondary octane sulfonyl chloride prepared is added for reaction for 4.0 hours, the reaction temperature is maintained at-15 to-10 ℃, after the reaction is finished, the material is heated to form oil and water two phases, then the water phase is separated and removed, the oil phase is washed for 2-3 times by water, then cooled to-20 to-25 ℃ for crystallization, after the crystallization is finished, the centrifugal separation and drying are carried out to obtain 680.7g of 1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane product, the yield is 99%, the purity is 99.8% by liquid chromatography detection and analysis; and distilling the mother liquor obtained by centrifugal separation for reuse.
Example 2
153.4g of 1, 6-dimercaptohexane liquid (98 wt%) is added into a three-neck flask with a thermometer, a stirring and constant-pressure dropping funnel, the three-neck flask is immersed into a water bath kettle, 74.8g of 50% hydrogen peroxide solution is dropwise added to react for 0.5 hour, the material temperature is maintained at 0-5.0 ℃ during the reaction, liquid separation and drying are carried out after the reaction is finished, 133.5g of liquid 1, 2-dithiocyclooctane is obtained, and the yield is 90%.
133.5g of 1, 2-dithiocyclooctane obtained in the above step and 300g of n-hexane are added into a three-necked flask with a jacket and stirring, the materials in the three-necked flask are cooled to-10 to-5 ℃ by using refrigerant ethylene glycol, 71.0g of chlorine (99.0 wt%) is introduced into the reaction materials in the three-necked flask for reaction, the reaction temperature is maintained to-10 to-5 ℃ during the reaction, the reaction is carried out for 3.0 hours, 182.6g of 1, 6-secondary sulfonyl chloride octane is obtained, and the yield is 92.5%.
514.4g sodium dibenzyl dithiocarbamate (98 wt%) is weighed and dissolved in water to prepare aqueous solution with the mass percentage concentration of about 70%, then the aqueous solution is added into a three-necked bottle with a thermometer, a stirrer and a jacket, the material is cooled to-10 to-5 ℃ by introducing glycol refrigerant into the three-necked bottle, then 182.6g1, 6-octane disulfonate prepared is added for reaction for 3.0 hours, the reaction temperature is maintained at-10 to-5 ℃, the material is heated after the reaction is finished to form oil and water two phases, then the water phase is separated and removed, the oil phase is washed for 2-3 times by water, then the temperature is reduced to-20 to-25 ℃ for crystallization, after the crystallization is finished, the centrifugal separation and drying are carried out to obtain 580.7g1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane product, the yield is 98%, the purity is 96.8 percent through liquid chromatography detection and analysis; and distilling the mother liquor obtained by centrifugal separation for reuse.
Example 3
122.7g of 1, 6-dimercaptohexane liquid (98 wt%) is added into a three-neck flask with a thermometer, a stirring and constant-pressure dropping funnel, the three-neck flask is immersed into a water bath kettle, 56.6g of 50% hydrogen peroxide solution is dropwise added to react for 2.0 hours, the material temperature is maintained to be 40.0-50.0 ℃, liquid separation and drying are carried out after the reaction is finished, and 115.1g of liquid 1, 2-dithiocyclooctane is obtained, wherein the yield is 93.2%.
Adding 115.1g of 1, 2-dithiocyclooctane and 240g of toluene obtained in the previous step into a three-necked flask with a jacket and stirring, cooling the materials in the three-necked flask to 0-5 ℃ by using coolant ethylene glycol, introducing 64.0 wt% of chlorine (99.0 wt%) into the three-necked flask reaction materials for reaction, maintaining the reaction temperature at 0-5 ℃ during the reaction, and reacting for 1 hour to obtain 162.4g of 1, 6-bis (sulfonyl chloride) octane, wherein the yield is 95.4%.
Weighing 480.0g of sodium dibenzyldithiocarbamate (98 wt%), dissolving in water to prepare an aqueous solution with the mass percentage concentration of about 70%, adding the aqueous solution into a three-necked bottle with a thermometer, a stirrer and a jacket, introducing an ethylene glycol refrigerant into the three-necked bottle to cool the material to 0-5 ℃, adding 162.4g of 1, 6-diphosphonooctane prepared above for reaction for 5 hours, maintaining the reaction temperature at 0-5 ℃, heating the material after the reaction is finished to form an oil phase and a water phase, separating and removing the water phase, washing the oil phase for 2-3 times with water, cooling to-10 to-5 ℃ for crystallization, centrifugally separating and drying after the crystallization is finished to obtain 497.9g of 1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane product, wherein the yield is 97%, detecting and analyzing by liquid chromatography, the purity is 97.4%; and distilling the mother liquor obtained by centrifugal separation for reuse.
Example 4
Adding 137.8g of 1, 6-dimercaptohexane liquid (98 wt%) into a three-neck flask with a thermometer, a stirring and constant-pressure dropping funnel, immersing the three-neck flask into a water bath kettle, dropwise adding 73.3g of 50% hydrogen peroxide solution, reacting for 2.5 hours, keeping the material temperature at 70-80 ℃, separating and drying after the reaction is finished to obtain 123.5g of liquid 1, 2-dithiocyclooctane, wherein the yield is 92.7%.
Adding 123.5g of 1, 2-dithiocyclooctane obtained in the above step and 200g of 1 xylene into a jacketed and stirred three-necked bottle, cooling the materials in the three-necked bottle to-5-0 ℃ by using coolant ethylene glycol, introducing 68.7g of chlorine (99.0 wt%) into the reaction materials in the three-necked bottle for reaction, maintaining the reaction temperature at-5-0 ℃ during the reaction, and reacting for 2 hours to obtain 176.2g of 1, 6-disulfonyl chloride octane, wherein the yield is 96.5%.
Weighing 510.3g of sodium dibenzyldithiocarbamate (98 wt%), dissolving in water to prepare an aqueous solution with the mass percentage concentration of about 70%, adding the aqueous solution into a three-necked bottle with a thermometer, a stirrer and a jacket, introducing an ethylene glycol refrigerant into the three-necked bottle to cool the material to-5-0 ℃, adding 176.2g of 1, 6-secondary octane sulfonyl chloride prepared above to react for 1 hour, maintaining the reaction temperature at-5-0 ℃, heating the material after the reaction is finished to form an oil phase and a water phase, removing the liquid phase of the aqueous phase, washing the oil phase for 2-3 times with water, cooling to-10-0 ℃ to crystallize, centrifugally separating and drying after the crystallization is finished to obtain 527.9g of 1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane product with the yield of 94.8%, detecting and analyzing by liquid chromatography, the purity is 98.1%; and distilling the mother liquor obtained by centrifugal separation for reuse.
Example 5
Adding 153.4g of 1, 6-dimercaptohexane liquid (98 wt%) into a three-neck flask with a thermometer, a stirring and constant-pressure dropping funnel, immersing the three-neck flask into a water bath kettle, dropwise adding 81.6g of 50% hydrogen peroxide solution, reacting for 2.5 hours, keeping the material temperature at 10-30 ℃ during the reaction, separating liquid and drying after the reaction is finished to obtain 142.4g of liquid 1, 2-dithiocyclooctane, wherein the yield is 96%.
142.4g of 1, 2-dithiocyclooctane and 300g of benzene obtained in the above are added into a three-necked flask with a jacket and stirring, the materials in the three-necked flask are cooled to-10 to-5 ℃ by using coolant ethylene glycol, 82.6g of chlorine (99.0 wt percent) is introduced into the reaction materials in the three-necked flask for reaction, the reaction temperature is maintained to-10 to-5 ℃ in the process, the reaction is carried out for 4.5 hours, 205.7g of 1, 6-secondary sulfonyl chloride octane is obtained, and the yield is 97.7%.
593.7g of sodium dibenzyl dithiocarbamate (98 wt%) is weighed and dissolved in water to prepare an aqueous solution with the mass percentage concentration of about 70%, then the aqueous solution is added into a three-necked bottle with a thermometer, a stirrer and a jacket, the material is cooled to-10 to-5 ℃ by introducing an ethylene glycol refrigerant into the three-necked bottle, then 205.7g of 1, 6-secondary octane sulfonyl chloride prepared is added for reaction for 1.6 hours, the reaction temperature is maintained at-10 to-5 ℃, after the reaction is finished, the material is heated to form oil and water two phases, then the water phase is separated and removed, the oil phase is washed for 2-3 times by water, then cooled to-15 to-10 ℃ for crystallization, after the crystallization is finished, the centrifugal separation and drying are carried out to obtain 630g of 1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane product, the yield is 96.9%, the purity is 98.5 percent through liquid chromatography detection and analysis; and distilling the mother liquor obtained by centrifugal separation for reuse.
Claims (10)
1. A preparation method of rubber auxiliary agent 1, 6-di (N, N-dibenzyl carbamyl disulfide) hexane is characterized by comprising the following steps: obtained by the reaction of dibenzyl dithiocarbamate and 1, 6-secondary sulfonyl chloride octane, and the reaction formula is as follows:
2. the method of claim 1, wherein: the 1, 6-secondary octane sulfonyl chloride is obtained by reacting 1, 2-dithiocyclooctane with chlorine, and the reaction formula is as follows:
3. the method of claim 2, wherein: the 1, 2-dithiocyclooctane is obtained by reacting 1, 6-dimercaptohexane with hydrogen peroxide, and has the following reaction formula:
4. the method of claim 1,2 or 3, wherein: cooling the aqueous solution of dibenzyl dithiocarbamate to the reaction temperature, then adding 1, 6-secondary octane sulfonyl chloride for reaction, heating the reaction solution after the reaction until oil and water phases are formed, separating the water phases, washing the oil phases with water, cooling and crystallizing to obtain the 1, 6-bis (N, N-dibenzyl carbamyl disulfide) hexane.
5. The method according to claim 1 or 4, wherein:
preferably, the reaction temperature of the dibenzyl dithiocarbamate and the 1, 6-secondary sulfonyl chloride octane is-15-5 ℃, and more preferably-15-10 ℃;
preferably, the reaction time of the dibenzyl dithiocarbamate and the 1, 6-octane disulfonate is 1.0-5.0 hours, and more preferably 4.0 hours;
preferably, the dibenzyl dithiocarbamate is sodium dibenzyl dithiocarbamate.
6. The method of claim 2, wherein: mixing the 1, 2-dithiocyclooctane and a solvent, then reducing the reaction temperature, introducing chlorine gas to carry out chlorination reaction, and obtaining the 1, 6-secondary octane sulfonyl chloride.
7. The method according to claim 2 or 6, wherein:
preferably, the reaction temperature of the 1, 2-dithiocyclooctane and the chlorine gas is-15 to 5 ℃, and more preferably-15 to-10 ℃;
preferably, the reaction time of the 1, 2-dithiocyclooctane and the chlorine gas is 1-5.0 hours, and more preferably 2.0 hours;
preferably, the solvent is a straight-chain hydrocarbon or aromatic hydrocarbon solvent, and more preferably is mineral spirit.
8. The method of claim 3, wherein: heating 1, 6-dimercaptohexane to reaction temperature, then dropping hydrogen peroxide into the 1, 6-dimercaptohexane for oxidation reaction, separating liquid after reaction, and drying the obtained organic phase to obtain the 1, 2-dithiocyclooctane.
9. The method according to claim 3 or 8, wherein: preferably, the reaction temperature of the 1, 6-dimercaptohexane and the hydrogen peroxide is 0-80 ℃, and more preferably 25-30 ℃; preferably, the reaction time of the 1, 6-dimercaptohexane and the hydrogen peroxide is 0.5 to 3.0 hours, and more preferably 1.5 hours.
10. The method of claim 1,2 or 3, wherein: the molar ratio of the 1, 6-dimercaptohexane to the hydrogen peroxide is 1: 1.0-1.2, preferably 1: 1.05; the mol ratio of the 1, 2-dithiocyclooctane to the chlorine is 1: 1.0-1.2, preferably 1: 1.05; the molar ratio of dibenzyl dithiocarbamate to 1, 6-octane disulfonate is 2.0-2.2: 1, preferably 2.05: 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979369A (en) * | 1971-11-19 | 1976-09-07 | Monsanto Company | Method for cross-linking rubber with polysulfides |
| CN100522941C (en) * | 2004-05-26 | 2009-08-05 | 朗盛德国有限责任公司 | Preparation of dithiol derivatives |
| JP2013155144A (en) * | 2012-01-31 | 2013-08-15 | Sumitomo Seika Chem Co Ltd | Method of producing dithiol compound and cyclic disulfide compound |
| JP2014198688A (en) * | 2013-03-29 | 2014-10-23 | 住友精化株式会社 | Production method of cyclic polysulfide compound |
| CN105503677A (en) * | 2015-12-04 | 2016-04-20 | 山东阳谷华泰化工股份有限公司 | Preparation method of environment-friendly and efficient sulfurization crosslinking agent 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane |
-
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- 2019-08-06 CN CN201910719808.8A patent/CN111187193B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979369A (en) * | 1971-11-19 | 1976-09-07 | Monsanto Company | Method for cross-linking rubber with polysulfides |
| CN100522941C (en) * | 2004-05-26 | 2009-08-05 | 朗盛德国有限责任公司 | Preparation of dithiol derivatives |
| JP2013155144A (en) * | 2012-01-31 | 2013-08-15 | Sumitomo Seika Chem Co Ltd | Method of producing dithiol compound and cyclic disulfide compound |
| JP2014198688A (en) * | 2013-03-29 | 2014-10-23 | 住友精化株式会社 | Production method of cyclic polysulfide compound |
| CN105503677A (en) * | 2015-12-04 | 2016-04-20 | 山东阳谷华泰化工股份有限公司 | Preparation method of environment-friendly and efficient sulfurization crosslinking agent 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane |
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