CN109233035B - Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof - Google Patents
Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
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- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
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- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms
Abstract
The invention provides an anti-reversion agent with a grain diameter of 40-100 mu m for rubber and a novel synthesis method thereof, wherein the synthesis method comprises the following steps: firstly, synthesizing an intermediate 1, 6-bis (N, N ' -dibenzothiazyl carbamyl monosulfur) -hexane at room temperature by adopting a green synthesis process hydrosolvent method under the action of a phase transfer catalyst, reacting the obtained intermediate with sulfur to obtain a primary product 1, 6-bis (N, N ' -dibenzothiazyl carbamyl disulphur) -hexane, and recrystallizing and purifying the primary product to obtain a pure product 1, 6-bis (N, N ' -dibenzothiazyl carbamyl disulphur) -hexane. The synthetic method has the advantages that the solvent can be recycled, no wastewater is generated, the method is environment-friendly and economical, the reaction time is short, the product purity is high, the production efficiency is high, the synthetic process is simple, and the energy consumption is low; the prepared anti-reversion agent for rubber has large granularity, narrow particle size distribution and good processing performance.
Description
Technical Field
The invention relates to the field of rubber processing aid synthesis processes, in particular to a novel synthesis method of an anti-reversion agent for rubber.
Background
1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane is a novel efficient compound anti-reversion agent, and the anti-reversion mechanism of the agent is as follows: in the process of vulcanizing rubber materials, sulfur-sulfur bonds in the molecular structure are broken, the middle C6 fatty chain and sulfur atoms at two ends of the fatty chain are connected into rubber molecules, and the bond energy of carbon-carbon bonds in the C6 fatty chain is greater than that of sulfur-sulfur bonds formed by sulfur vulcanization, so that a more stable vulcanization crosslinking network is formed, the vulcanization reversion phenomenon of vulcanized rubber can not occur in the production process and the use process, and better mechanical properties and dynamic properties are kept.
In patent CN100522941C, a method for preparing dithiol derivatives is reported, which uses hexamethylene-1, 6-disulfuric acid disodium salt and sodium dibenzyl dithiocarbamate as raw materials, water/toluene as a reaction solvent, adjusts the PH value of the reaction system by adding sodium bicarbonate, and obtains the product after the synthesis reaction through post-treatment unit operations such as extraction, reduced pressure concentration, crystallization, etc., and the preparation method has the following disadvantages: 1) the mass transfer efficiency in heterogeneous system water/toluene is low, so that the reaction rate is low, the industrial production period is long, and the industrial capacity of the product is low; 2) a large amount of alkaline wastewater (containing a small amount of organic solvent toluene) is generated, the Chemical Oxygen Demand (COD) is high, and the biochemical treatment cost is high.
Chinese patent CN105503677B discloses a preparation method of an environment-friendly and efficient vulcanization crosslinking agent 1, 6-bis (N, N-dibenzylcarbamyl disulfide) hexane: firstly, synthesizing an alcoholic solution of sodium dibenzyl dithiocarbamate, then heating and refluxing the alcoholic solution and 1, 6-dichlorohexane for reaction, filtering, washing to obtain an intermediate 1, 6-di (N, N-dibenzylcarbamyl-thio) hexane, and heating and reacting the intermediate and sulfur to generate the product 1, 6-di (N, N-dibenzylcarbamyl-disulfide) hexane serving as the anti-vulcanization reversion agent. The synthesis method adopts toxic volatile solvent methanol, generates a large amount of waste water, pollutes the environment and has higher energy consumption of reflux reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a novel 40-100 mu m rubber vulcanization-reversion resistant agent and a novel synthesis method thereof, the method is a novel industrial synthesis method of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane which is the vulcanization-reversion resistant agent, the process is simple and easy to implement, the operation is simple and convenient, the solvent can be recycled and used, and the industrial cost is low; the prepared anti-reversion agent for rubber has large granularity, narrow particle size distribution and good processing performance, and can effectively reduce dust flying in the subsequent rubber processing.
In one embodiment of the present invention, there is provided 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane as an anti-reversion agent for rubber, wherein at least 90% of the particles have a particle size of 40 to 100 μm;
in another embodiment of the present invention, there is also provided a novel method for synthesizing an anti-reversion agent for rubber, characterized by comprising the steps of:
(1) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamoyl-thio) -hexane intermediate
Adding dibenzylamine, carbon disulfide, a sodium hydroxide solution and 1, 6-dichlorohexane as raw materials and a phase transfer catalyst as a catalyst into a reaction kettle containing water or mother liquor, after the reaction is finished, centrifuging, washing with water, and drying a filter cake to obtain 1, 6-bis (N, N' -dibenzothiazyl carbamoyl monosulfur) -hexane, and collecting and recycling a washing mother liquor A;
(2) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane crude product
Sequentially adding sulfur and an organic solvent into the 1, 6-bis (N, N '-dibenzothiazyl carbamoyl monosulfur) -hexane synthesized in the step (1) for reaction, and removing the organic solvent by reduced pressure distillation after the reaction is finished to obtain a 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane primary product;
(3) purification of 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane
Adding ethyl acetate into the primary 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane product prepared in the step (2), heating to dissolve, cooling to a temperature lower than 10 ℃, discharging, centrifuging to obtain white powder, and collecting and recycling mother liquor B; and drying, spraying oil, crushing and packaging the white powder to obtain a finished product.
Further, a novel synthesis method of the anti-reversion agent for rubber is provided, and comprises the following steps:
(1) firstly, adding solvent water or mother liquor mechanically into a reaction kettle, then sequentially adding dibenzylamine and a phase transfer catalyst, cooling to 0-5 ℃, beginning to dropwise add carbon disulfide, continuing to dropwise add a 32% sodium hydroxide aqueous solution after 1-2 hours of dropwise addition, keeping the dropwise addition temperature not more than 10 ℃, then slowly dropwise adding 1, 6-dichlorohexane after the dropwise addition is finished, keeping the dropwise addition temperature at 0-5 ℃, stirring and reacting for 2.5-6 hours at room temperature after the dropwise addition is finished, centrifuging and washing, collecting and recycling the mother liquor A, and drying a filter cake to obtain 1, 6-bis (N, N' -dibenzothiazyl carbamoyl-monosulfur) -hexane;
(2) sequentially adding sulfur and an organic solvent into the 1, 6-bis (N, N '-dibenzothiazyl carbamoyl monosulfur) -hexane prepared in the step (1), reacting at the temperature of 80-100 ℃ for 6-8h, and removing the organic solvent by reduced pressure distillation after the reaction is finished to obtain a 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane primary product;
(3) adding ethyl acetate into the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane prepared in the step (2), heating, dissolving and refluxing for 30min, cooling to a temperature lower than 10 ℃, discharging, centrifuging to obtain a white powder product, and collecting and recycling mother liquor B;
(4) and (4) drying, oil spraying, crushing and packaging the product obtained in the step (3) to obtain the finished product 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane as the anti-reversion agent.
The two-stage processing technique of the anti-reversion agent 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane subsequent rubber mixing is as follows: the conditions of the first-stage mixing process are (roll temperature 80 ℃, roller rotating speed 60rpm), and the mixing process is as follows: adding 100 parts of weighed natural rubber, 25 parts of N234 carbon black, 4.4 parts of zinc oxide, 2 parts of SA stearic acid, 1.5 parts of 4020 anti-aging agent, 1 part of 9332F rubber protective wax and 25 parts of N234 carbon black into an internal mixer in sequence, mixing for 260S, cleaning, discharging rubber, placing the rubber material into an open mill, mixing for 5min, and then placing the rubber material into the air for natural cooling for 4h to obtain master batch; the two-stage mixing process conditions are (roll temperature 60 ℃, roller rotating speed 40rpm), and the mixing process comprises the following steps: and (3) adding the primary master batch, weighed 0.6 part of sulfur, 1 part of accelerator and 1.5 parts of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane into an internal mixer in sequence, mixing for 100 seconds, discharging rubber to obtain final rubber batch, rolling the final rubber batch on an open mill for 5 times, and then cutting rubber and discharging sheets.
Wherein, the weight ratio of the carbon disulfide, the 1, 6-dichlorohexane, the sodium hydroxide solution, the dibenzylamine and the solvent water in the step (1) is 1: (0.8-2.0): (1.0-2.0): (1.0-3.0): (10-15), preferably 1: (1-1.5): (1.0-1.5): (1.0-2.5): (12-15), and more preferably 1: (1-1.2): (1.2-1.5): (1.2-2.3): (12.5-13.5).
In the step (1), the preferable dropping temperature of the carbon disulfide is 3-5 ℃, the preferable dropping temperature of the sodium hydroxide aqueous solution is 8-10 ℃, and the preferable dropping temperature of the 1, 6-dichlorohexane is 3-5 ℃.
The phase transfer catalyst used in the step (1) is tetrabutylammonium bromide or triethylbenzylammonium chloride, and the preferable dosage of the catalyst is 6-8% of the mass of dibenzylamine.
The preferable 1, 6-dichlorohexane in the step (1) is reacted for 3 to 6 hours after the dripping is finished.
The organic solvent in the step (2) is preferably toluene, xylene or chlorobenzene.
The preferable molar ratio of 1, 6-bis (N, N' -dibenzylcarbamoylthio) hexane to sulfur in the step (2) is 1: (2.0-2.5), the mass ratio of the 1, 6-bis (N, N' -dibenzothiazyl carbamyl-thio) -hexane to the organic solvent is 1: (2-5).
In the step (3), the mass ratio of the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane to the ethyl acetate is 1: (1.0-2.0), preferably 1: (1.5-2.0).
Specifically, the synthetic route of the invention is as follows:
step (1) synthetic route
Step (2) synthetic route
Compared with the prior art, the invention has the following beneficial effects:
1) the mother liquor can be recycled after the reaction is finished, no wastewater is generated, and the method is green, environment-friendly and economical.
2) The synthesis process of the intermediate 1, 6-bis (N, N' -dibenzothiazole carbamyl-thio) -hexane adopts water as a solvent, is green and environment-friendly, and is matched with a phase transfer catalyst, and the phase transfer catalyst can improve the mass transfer efficiency of oil/water two phases, accelerate the reaction rate and improve the yield.
3) The synthesis reaction of the intermediate 1, 6-bis (N, N' -dibenzothiazyl carbamyl-thio) -hexane is carried out at room temperature, the required energy consumption is low, and the operation is simple and easy.
4) The synthesis method adopts a crystallization process, so that the obtained product has high purity and wide application value.
5) The product obtained by the synthesis method has narrow particle size distribution and large particle size, the material has good fluidity in the downstream rubber processing process, the dust concentration is lower in the actual processing and production process, and the hazard degree of occupational diseases is reduced.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto, and all other modifications derived from or suggested by the present disclosure should be considered as the scope of the invention.
The particle size of the reversion preventive 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane described herein was measured by the Mie scattering principle using a BT-9300S laser particle size distribution apparatus. The sedimentation medium is deionized water, and the dispersant is an aqueous solution of sodium hexametaphosphate.
Example 1
A new synthesis method of an anti-reversion agent for rubber comprises the following preparation steps:
(1) 1670kg of deionized water, 315.2kg of dibenzylamine and 19kg of tetrabutylammonium bromide serving as a catalyst are sequentially put into a 5000L reaction kettle, frozen saline water is introduced for cooling and stirring to reduce the temperature to 5 ℃, 133.6kg of carbon disulfide is slowly dripped into the reaction kettle through an overhead tank, the dripping temperature is not more than 5 ℃, 199kg of 32% sodium hydroxide solution is continuously dripped after the dripping is finished within 2 hours, the dripping temperature is not more than 10 ℃, 125kg of 1, 6-dichlorohexane is slowly dripped into the reaction kettle after the dripping is finished, the dripping temperature is not more than 5 ℃, the stirring is carried out at room temperature after the dripping is finished, after the reaction is finished, the intermediate 1, 6-bis (N, N' -dibenzothiamidoyl-thio) -hexane is obtained after centrifuging, washing and drying a filter cake, and the mother liquor A is collected and recycled.
(2) And (2) sequentially adding the 1, 6-bis (N, N '-dibenzothiazyl carbamoyl monosulfur) -hexane prepared in the step (1), 52kg of sulfur and 1000kg of toluene solvent into the reaction kettle, reacting at 80 ℃ for 6 hours, then carrying out reduced pressure distillation to remove toluene, obtaining a primary 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane product, and collecting fractions for recycling.
(3) And (3) adding 760kg of ethyl acetate into the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane primary product prepared in the step (2), heating to dissolve for 30min, cooling to a temperature lower than 10 ℃, discharging, performing centrifugal separation to obtain a white powder product, and collecting and recycling the mother liquor B.
(4) The obtained filter cake product is subjected to vacuum double-cone drying for 5 hours at 70 ℃, oil spraying, crushing and packaging to obtain the finished product 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane as the anti-vulcanization reversion agent, the total yield is 91.3 percent by calculation, the product content is 98.8 percent by detection and analysis, the melting point is 91.7 ℃, the ash content is 0.05 percent, the oil content is 7.2 percent, and the particle size d (90) is 59.26 mu m.
In the downstream final rubber processing process, the field dust concentration of the synthesized 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane as the anti-reversion agent is 88.5mg/m in the process of feeding the anti-reversion agent into an internal mixer through a JC-1000 handheld intelligent dust detector3。
Examples 2, 3, 4 the procedure of example 1 was repeated except that: the reaction time of the step (1) is respectively 4, 5 and 6 hours. The analytical results are shown in Table 1.
TABLE 1 examples of different reaction times for step (1)
Example 5
The procedure of example 1 was repeated except that: the catalyst used in the step (1) is 19kg of triethylbenzylammonium chloride, the final calculation can obtain the total yield of 92.3 percent, the product content is 98.2 percent, the melting point is 91.5 ℃, the ash content is 0.03 percent, the oil content is 6.7 percent, the particle size d (90) is 72.33 mu m, and the field dust concentration is 85.1mg/m3。
Example 6
The procedure of example 1 was repeated except that: in the step (2)The solvent is 1000kg chlorobenzene, the final calculation can obtain the total yield of 91.3 percent, the content of the product is 98.2 percent through detection and analysis, the melting point is 92.0 ℃, the ash content is 0.07 percent, the oil content is 6.5 percent, the particle size d (90) is 71.33 mu m, and the concentration of the on-site dust is 86.1mg/m3。
Example 7
2292kg of filtrate centrifugally recovered in the step (1) in the example 1 is directly reused as a solvent, and other steps are the same as the step 1, the total yield of the obtained product is 90.7 percent by calculation, the product content is 96.1 percent by detection and analysis, the melting point is 91.2 ℃, the ash content is 0.04 percent, the oil content is 6.9 percent, the particle size d (90) is 58.13 mu m, and the field dust concentration is 89.1mg/m3。
Comparative example:
a series of experiments were carried out in accordance with the example of the process for preparing dithiol derivatives of patent CN100522941C, and 1, 6-bis (N, N '-dibenzothiazyl carbamoyldisulfide) -hexane having a particle size d (90) of 12.99 μm and a dust concentration of 150.2mg/m in-situ of the process of charging 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane into an internal mixer as measured by a JC-1000 hand-held smart dust detector3。
Claims (11)
1. 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane as an anti-reversion agent for rubber, characterized in that: wherein at least 90% of the particles have a particle size of 40-100 μm;
the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane is prepared by the following steps:
(1) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamoyl-thio) -hexane intermediate
Adding dibenzylamine, carbon disulfide, a sodium hydroxide solution and 1, 6-dichlorohexane as raw materials and a phase transfer catalyst as a catalyst into a reaction kettle using water or mother liquor, centrifuging after the reaction is finished, washing with water, drying a filter cake to obtain 1, 6-bis (N, N' -dibenzothiazyl carbamoyl monosulfur) -hexane, and collecting and recycling the washing mother liquor A;
(2) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane crude product
Sequentially adding sulfur and an organic solvent into the 1, 6-bis (N, N '-dibenzothiazyl carbamoyl monosulfur) -hexane synthesized in the step (1) for reaction, and removing the organic solvent by reduced pressure distillation after the reaction is finished to obtain a 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane primary product;
(3) purification of 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane
Adding ethyl acetate into the primary 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane product prepared in the step (2), heating to dissolve, cooling to a temperature lower than 10 ℃, discharging, centrifuging to obtain white powder, and collecting and recycling mother liquor B; then drying, spraying oil, crushing and packaging the white powder to obtain a finished product;
wherein the phase transfer catalyst in the step (1) is tetrabutylammonium bromide or triethylbenzylammonium chloride.
2. A novel process for synthesizing an anti-reversion agent for rubber according to claim 1, comprising the steps of:
(1) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamoyl-thio) -hexane intermediate
Adding dibenzylamine, carbon disulfide, a sodium hydroxide solution and 1, 6-dichlorohexane as raw materials and a phase transfer catalyst as a catalyst into a reaction kettle using water or mother liquor, centrifuging after the reaction is finished, washing with water, drying a filter cake to obtain 1, 6-bis (N, N' -dibenzothiazyl carbamoyl monosulfur) -hexane, and collecting and recycling the washing mother liquor A;
(2) synthesis of 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane crude product
Sequentially adding sulfur and an organic solvent into the 1, 6-bis (N, N '-dibenzothiazyl carbamoyl monosulfur) -hexane synthesized in the step (1) for reaction, and removing the organic solvent by reduced pressure distillation after the reaction is finished to obtain a 1, 6-bis (N, N' -dibenzothiazyl carbamoyl disulfide) -hexane primary product;
(3) purification of 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane
Adding ethyl acetate into the primary 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane product prepared in the step (2), heating to dissolve, cooling to a temperature lower than 10 ℃, discharging, centrifuging to obtain white powder, and collecting and recycling mother liquor B; and drying, spraying oil, crushing and packaging the white powder to obtain a finished product.
3. The method of claim 2, wherein: the weight ratio of the carbon disulfide, the 1, 6-dichlorohexane, the sodium hydroxide solution, the dibenzylamine and the solvent water is 1: (0.8-2.0): (1.0-2.0): (1.0-3.0): (10-15).
4. The method of claim 2, wherein: in the step (2), the molar ratio of the 1, 6-bis (N, N' -dibenzothiazyl carbamyl monosulfur) -hexane to the sulfur is 1: (2.0-2.5), the mass ratio of the 1, 6-bis (N, N' -dibenzothiazyl carbamyl-thio) -hexane to the organic solvent is 1: (2-5).
5. The method of claim 2, wherein: in the step (3), the mass ratio of the 1, 6-bis (N, N' -dibenzothiazyl carbamyl disulfide) -hexane to the ethyl acetate is 1: (1.0-2.0).
6. The method of claim 2, wherein: the step (1) comprises the following specific preparation steps:
firstly, adding solvent water or mother liquor mechanically into a reaction kettle, then sequentially adding dibenzylamine and a phase transfer catalyst, cooling to 0-5 ℃, beginning to dropwise add carbon disulfide, continuing to dropwise add a 32% sodium hydroxide aqueous solution after 1-2 hours of dropwise addition, keeping the dropwise addition temperature not more than 10 ℃, then slowly dropwise adding 1, 6-dichlorohexane after the dropwise addition is finished, keeping the dropwise addition temperature at 0-5 ℃, stirring and reacting for 2.5-6 hours at room temperature after the dropwise addition is finished, centrifuging and washing, collecting and recycling the mother liquor A, and drying a filter cake to obtain an intermediate 1, 6-bis (N, N' -dibenzothiazyl carbamoyl-thio) -hexane.
7. The method of claim 2, wherein: the phase transfer catalyst is tetrabutylammonium bromide or triethylbenzylammonium chloride, and the dosage of the catalyst is 6-8% of the mass of dibenzylamine.
8. The method of claim 2, wherein: in the step (2), the reaction temperature is 80-100 ℃, the reaction time is 6-8h, and the organic solvent is toluene, xylene or chlorobenzene.
9. The method of claim 6, wherein the carbon disulfide is added dropwise at a temperature of 3-5 ℃ and the aqueous sodium hydroxide solution is added dropwise at a temperature of 8-10 ℃ in step (1).
10. The method of claim 6, wherein the 1, 6-dichlorohexane is added dropwise at a temperature of 3-5 ℃ in the step (1), and the reaction time is 3-6 hours after the addition is completed.
11. Use of 1, 6-bis (N, N' -dibenzothiazyl carbamoyldisulfide) -hexane as an anti-reversion agent for rubber, as claimed in claim 1, or as prepared by the process of any one of claims 2 to 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810962402.8A CN109233035B (en) | 2018-08-22 | 2018-08-22 | Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof |
| PCT/CN2018/113797 WO2020037831A1 (en) | 2018-08-22 | 2018-11-02 | ANTI-VULCANISATION REVERSION AGENT FOR RUBBER HAVING PARTICLE DIAMETER OF 40-100 μM AND NEW SYNTHESIS METHOD THEREFOR |
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| CN201810962402.8A CN109233035B (en) | 2018-08-22 | 2018-08-22 | Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof |
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| CN105152997A (en) * | 2015-08-01 | 2015-12-16 | 江苏麒祥高新材料有限公司 | Preparation method for dithiocarbamic acid serial sulfuration cross-linking agent |
| CN105503677B (en) * | 2015-12-04 | 2017-06-30 | 山东阳谷华泰化工股份有限公司 | A kind of environmental protection, high performance vulcanization crosslinking agent 1,6 2（The sulphur of N, N dibenzyl amino formyl two）The preparation method of hexane |
| CN106832448B (en) * | 2017-02-22 | 2019-02-26 | 双钱集团上海轮胎研究所有限公司 | A kind of tread rubber being used to prepare high-performance tire |
| CN107778548A (en) * | 2017-09-25 | 2018-03-09 | 上海豪元橡胶制品有限公司 | All-steel radial tyre tyre surface glue composition and preparation method thereof |
| CN107759843A (en) * | 2017-09-25 | 2018-03-06 | 上海豪元橡胶制品有限公司 | All-steel radial tyre shoulder wedge composition and preparation method thereof |
| CN107746483A (en) * | 2017-10-16 | 2018-03-02 | 山东恒宇科技有限公司 | Run-flat tire sidewall supports glue and preparation method |
| CN108424552B (en) * | 2018-04-08 | 2020-05-12 | 贾中将 | Rubber shock absorber with high reversion resistance |
| CN108395393A (en) * | 2018-05-15 | 2018-08-14 | 清华大学 | A kind of green synthesis method of thiurams thiofide |
-
2018
- 2018-08-22 CN CN201810962402.8A patent/CN109233035B/en active Active
- 2018-11-02 WO PCT/CN2018/113797 patent/WO2020037831A1/en active Application Filing
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| CN109233035A (en) | 2019-01-18 |
| WO2020037831A1 (en) | 2020-02-27 |
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