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CN-122011612-A - Chlorosulfonated polyethylene rubber with high heat resistance and preparation method thereof

CN122011612ACN 122011612 ACN122011612 ACN 122011612ACN-122011612-A

Abstract

The invention discloses high-heat-resistance chlorosulfonated polyethylene rubber and a preparation method thereof, and belongs to the technical field of rubber preparation. The high heat resistance chlorosulfonated polyethylene rubber consists of, by weight, 84-96 parts of chlorosulfonated polyethylene rubber, 8-15 parts of vulcanizing agent, 30-43 parts of carbon black, 10-18 parts of chlorinated paraffin, 2-6 parts of heat resistance auxiliary agent, 1-4 parts of antioxidant, 1-2 parts of stearic acid and 0.5-2.2 parts of polyethylene wax. The chlorosulfonated polyethylene rubber prepared by using the above materials has excellent oxidation resistance and thermal stability.

Inventors

  • ZHANG YIJUN

Assignees

  • 江西华琪合成橡胶有限公司

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A chlorosulfonated polyethylene rubber with high heat resistance is characterized by comprising, by weight, 84-96 parts of chlorosulfonated polyethylene rubber, 8-15 parts of vulcanizing agent, 30-43 parts of carbon black, 10-18 parts of chlorinated paraffin, 2-6 parts of heat-resistant auxiliary agent, 1-4 parts of antioxidant, 1-2 parts of stearic acid and 0.5-2.2 parts of polyethylene wax, wherein the heat-resistant auxiliary agent is prepared from p-hydroxyacetophenone, 3, 5-bis (trifluoromethyl) benzaldehyde, morpholine, chloroacetyl chloride, 5-amino-1, 3, 4-thiadiazole-2-thiol and potassium carbonate, and the antioxidant is prepared from chitosan oligosaccharide, 1-methyl-2-pyrrolidone, methyl iodide and N, N' -carbonyldiimidazole.
  2. 2. The high heat resistance chlorosulfonated polyethylene rubber according to claim 1, wherein the preparation method of the heat resistance auxiliary agent comprises the following steps: Q1, adding p-hydroxyacetophenone and 3, 5-bis (trifluoromethyl) benzaldehyde into a container filled with ethanol, stirring and mixing, adding a sodium hydroxide aqueous solution, continuously stirring at room temperature for reaction, adding into an ice water bath after the reaction is finished, adjusting pH, performing vacuum filtration, washing, performing suction filtration, and drying to obtain an intermediate I; q2, adding morpholine and N, N-dimethylformamide into a container, stirring, adding chloroacetyl chloride in an ice bath environment, stirring for reaction, extracting, drying, and distilling under reduced pressure to obtain an intermediate II; adding 5-amino-1, 3, 4-thiadiazole-2-mercaptan, potassium carbonate and acetonitrile into a container, stirring and mixing, adding an intermediate II, stirring at room temperature for reaction, distilling under reduced pressure, separating out solids, filtering, washing and drying to obtain an intermediate III; And Q3, adding the intermediate III, methylene dichloride and chloroacetyl chloride into a container, stirring for reaction, extracting, drying, distilling under reduced pressure to obtain an intermediate IV, adding the intermediate I, potassium carbonate and acetonitrile into the container, heating and stirring, adding the intermediate IV, heating and refluxing for reaction, distilling under reduced pressure after the reaction is finished, separating out solids, filtering, washing, drying and purifying to obtain the heat-resistant auxiliary agent.
  3. 3. The chlorosulfonated polyethylene rubber with high heat resistance according to claim 2, wherein the dosage ratio of p-hydroxyacetophenone, 3, 5-bis (trifluoromethyl) benzaldehyde, ethanol and aqueous sodium hydroxide solution in Q1 is (3.812-4.026) g to (8.317-8.764) g to (58-66) mL to (30-35) mL.
  4. 4. The chlorosulfonated polyethylene rubber with high heat resistance according to claim 2, wherein the ratio of the dosages of morpholine, N-dimethylformamide and chloroacetyl chloride in Q2 is (0.472-0.535) g to (8-12) mL to (0.788-0.903) g, and the ratio of the dosages of 5-amino-1, 3, 4-thiadiazole-2-thiol, potassium carbonate, acetonitrile and intermediate II is (0.711-0.764) g to (1.517-1.562) g to (10-20) mL to (0.882-0.924) g.
  5. 5. The chlorosulfonated polyethylene rubber with high heat resistance according to claim 2, wherein in the Q3, the dosage ratio of the intermediate III, the dichloromethane and the chloroacetyl chloride is (0.752-0.793) g to (10-12) mL to (0.388-0.426) g, and the dosage ratio of the intermediate I, the potassium carbonate, the acetonitrile and the intermediate IV is (1.548-1.642) g to (1.782-1.946) g to (30-35) mL to (1.732-1.798) g.
  6. 6. The high heat resistance chlorosulfonated polyethylene rubber according to claim 1, wherein the antioxidant is prepared by a process comprising the steps of: S1, adding chitosan oligosaccharide into 1-methyl-2-pyrrolidone, stirring and mixing, adding sodium iodide and sodium hydroxide aqueous solution, stirring and reacting under ice bath condition, adding methyl iodide, heating and refluxing for reaction, precipitating, washing, filtering, and vacuum freeze-drying to obtain a solid product; s2, adding 4, 8-dihydroxyquinoline-2-formic acid into dimethyl sulfoxide, then adding N, N' -carbonyl diimidazole, heating and stirring for reaction, adding a solid product, continuing the reaction, and after the reaction is finished, precipitating, washing, filtering, and vacuum freeze-drying to obtain the antioxidant.
  7. 7. The chlorosulfonated polyethylene rubber with high heat resistance according to claim 6, wherein in S1, the dosage ratio of chitosan oligosaccharide, 1-methyl-2-pyrrolidone, sodium iodide, sodium hydroxide aqueous solution and methyl iodide is (4.88-5.22) g to (45-55) mL to (8.8-9.3) g to (28-32) mL to (28-34) mL.
  8. 8. The chlorosulfonated polyethylene rubber having high heat resistance according to claim 6, wherein the ratio of the amount of 4, 8-dihydroxyquinoline-2-carboxylic acid, dimethyl sulfoxide, N' -carbonyldiimidazole and solid product in S2 is (1.21-1.68) g to (10-15) mL to (0.56-0.68) g to (1.01-1.37) g.
  9. 9. The method for producing a chlorosulfonated polyethylene rubber having high heat resistance as claimed in any one of claims 1 to 8, comprising the steps of: Adding chlorosulfonated polyethylene rubber into an internal mixer, plasticating, sequentially adding stearic acid, an antioxidant and a heat-resistant auxiliary agent, mixing, adding carbon black, chlorinated paraffin and polyethylene wax, and fully mixing to obtain a mixture; Step two, the mixture is placed on an open mill for repeated thinning, then vulcanizing agent is added, after uniform mixing, glue pressing and cooling are carried out, and a film is obtained; And thirdly, adding the rubber sheet into a plate vulcanizing machine, vulcanizing, demolding and post-vulcanizing to obtain the chlorosulfonated polyethylene rubber with high heat resistance.
  10. 10. The method for preparing high heat resistance chlorosulfonated polyethylene rubber according to claim 9, wherein in the first step, plasticating is carried out for 1-2 minutes, mixing is carried out for 1-2 minutes, fully mixing is carried out for 6-10 minutes, in the second step, the roll gap of an open mill is 1-2mm, the roll temperature is 45-55 ℃, the roll gap is adjusted to 3-4mm when vulcanizing agent is added, the roll gap is 2-3mm in the rubber pressing process, in the third step, the vulcanization temperature is 160-170 ℃, the pressure is 15-20MPa, the temperature in the post vulcanization process is 150-160 ℃, and the time is 2-4h.

Description

Chlorosulfonated polyethylene rubber with high heat resistance and preparation method thereof Technical Field The invention belongs to the technical field of rubber preparation, and particularly relates to high-heat-resistance chlorosulfonated polyethylene rubber and a preparation method thereof. Background Chlorosulfonated polyethylene rubber is used as a special rubber material, and has certain application in various industrial fields, but has obvious defects in heat resistance, and further development is severely restricted. The upper limit of the long-term use temperature of the common chlorosulfonated polyethylene rubber is lower, usually about 120 ℃, and when the common chlorosulfonated polyethylene rubber is in a higher-temperature environment, the molecular chain structure of the common chlorosulfonated polyethylene rubber is easy to thermally degrade, so that the rubber is aged rapidly. Under the continuous action of high temperature, the physical properties of the rubber can be greatly attenuated, such as the key indexes of tensile strength, elongation at break and the like are obviously reduced, the hardness is increased, the elasticity is lost, and the normal use state cannot be maintained. In application scenes such as peripheral components of an automobile engine, sealing of high-temperature industrial pipelines and the like, the problem of insufficient heat resistance is particularly remarkable, the components are easy to damage due to high temperature, potential safety hazards such as leakage are caused, normal operation of equipment is affected, and safety accidents can be caused. Therefore, how to effectively improve the heat resistance of chlorosulfonated polyethylene rubber and overcome the heat resistance defect of the chlorosulfonated polyethylene rubber is a key technical problem to be solved in the field. The patent CN119350736B discloses a heat-resistant rubber composition and a preparation method of synthetic rubber, wherein the raw materials of the heat-resistant rubber composition comprise nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent, an activating agent, a vulcanizing agent, a vulcanization accelerator, a crosslinking assistant and a heat-resistant modification auxiliary agent, the heat-resistant modification auxiliary agent consists of nano ZrO 2 doped octafunctional styrene-POSS and nano HfO 2 doped octafunctional styrene-POSS, and the synthetic rubber is prepared by adopting the heat-resistant rubber composition. The synthetic rubber prepared by the invention has excellent heat resistance, wear resistance, stable mechanical property and long service life. Although the synthetic rubber prepared according to the above method has excellent properties, there is room for improvement in heat resistance and oxidation resistance. In the extremely high temperature or long-term thermal oxidation aging environment, the interface effect between the nano ions and the rubber matrix is possibly weakened, so that the heat conduction efficiency is changed, the local part is easy to overheat and accelerate aging, meanwhile, the migration rate of the anti-aging agent at high temperature is accelerated, the consumption is increased, the capturing capability of free radicals is reduced, the oxidation resistance protection effect is poor, the performance stability of the rubber composition under complex and severe working conditions is influenced, and the wider application of the rubber composition is limited. Disclosure of Invention The invention aims to provide chlorosulfonated polyethylene rubber with high heat resistance and a preparation method thereof, which are used for solving the technical problems of poor heat resistance and oxidation resistance of rubber in the prior art. In order to achieve the above purpose, the present invention adopts the following technical scheme: The invention provides high heat resistance chlorosulfonated polyethylene rubber, which comprises the following components, by weight, 84-96 parts of chlorosulfonated polyethylene rubber, 8-15 parts of vulcanizing agent, 30-43 parts of carbon black, 10-18 parts of chlorinated paraffin, 2-6 parts of heat resistance auxiliary agent, 1-4 parts of antioxidant, 1-2 parts of stearic acid and 0.5-2.2 parts of polyethylene wax. Preferably, the preparation method of the heat-resistant auxiliary agent comprises the following steps: Q1, adding p-hydroxyacetophenone and 3, 5-bis (trifluoromethyl) benzaldehyde into a container filled with ethanol, stirring and mixing, adding a sodium hydroxide aqueous solution, continuously stirring at room temperature for reaction, adding into an ice water bath after the reaction is finished, adjusting pH, performing vacuum filtration, washing, performing suction filtration, and drying to obtain an intermediate I; q2, adding morpholine and N, N-dimethylformamide into a container, stirring, adding chloroacetyl chloride in an ice bath environment, stirring