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CN-122011533-A - High-strength anti-aging styrene butadiene rubber and preparation method thereof

CN122011533ACN 122011533 ACN122011533 ACN 122011533ACN-122011533-A

Abstract

The invention discloses high-strength anti-aging styrene-butadiene rubber and a preparation method thereof, and belongs to the field of synthetic rubber modification. The preparation method comprises the steps of synthesizing porous network ZnO aggregated by 6.5nm ZnO nano particles by a hydrothermal method by using PVP K30 and polyvinyl alcohol 600 as 1:1 composite surfactants, not drying after synthesis to avoid aggregation, carrying out surface modification by a silane coupling agent KH560, carrying out sectional temperature control mixing with auxiliary agents such as styrene butadiene rubber, carbon black N330 and the like, and carrying out pre-crosslinking and gradient heating vulcanization to obtain the finished product. The porous network structure allows the rubber slurry to fully permeate, improves the contact area of the filler and the matrix, realizes high-efficiency reinforcement with low doping amount, enables the ZnO nano particles to convert ultraviolet light into visible light, enhances aging resistance by matching with the scattering effect of the porous structure, improves interface compatibility by modifying and optimizing the coupling agent, solves the problems of agglomeration and difficult performance of the traditional filler, and enables the finished product to have high strength and excellent aging resistance and to adapt to the requirements of multiple scenes such as tires, sealing elements and the like.

Inventors

  • WANG ZHI
  • CAI FUPING
  • WANG JIAN
  • HU ZHONGBAO
  • DONG XU

Assignees

  • 浙江维泰橡胶有限公司

Dates

Publication Date
20260512
Application Date
20260209

Claims (7)

  1. 1. The preparation method of the high-strength anti-aging styrene-butadiene rubber is characterized by comprising the following steps of: S1, hydrothermal synthesis of porous reticular ZnO, namely dissolving 2.4-3.6 g of zinc acetate dihydrate in 80-100 mL of deionized water, adding 1.5-2.0 g of compound surfactant, stirring for 20-25 min, wherein the compound surfactant is formed by PVP K30 and polyvinyl alcohol 600 according to a mass ratio of 1:1, filling the mixed solution into a reaction kettle, reacting for 8-12 h at 140-160 ℃, and centrifugally washing after the reaction is finished to obtain undried porous reticular ZnO, wherein the porous reticular ZnO is formed by aggregating ZnO nano particles with a particle size of about 6.5 nm; S2, preparing a surface-modified porous network ZnO mixed solution, namely adding absolute ethyl alcohol into the porous network ZnO obtained in the step S1 for ultrasonic dispersion, adding a silane coupling agent KH560 for stirring, and heating and volatilizing to remove 4/5 volume of absolute ethyl alcohol to obtain the surface-modified porous network ZnO mixed solution; S3, mixing, namely after styrene-butadiene rubber is plasticated, adding the mixed solution obtained in the step S2, carbon black N330 and stearic acid for mixing, cooling, and then adding sulfur and a promoter CZ for continuous mixing to obtain a mixed rubber; S4, vulcanizing and post-treating, namely pre-crosslinking, gradient heating and vulcanizing the rubber compound, and naturally cooling to room temperature to obtain the high-strength anti-aging styrene-butadiene rubber.
  2. 2. The preparation method of claim 1, wherein in the step S2, the consumption of the absolute ethyl alcohol is 100-120 mL, the ultrasonic dispersion time is 10-15min, the consumption of the silane coupling agent KH560 is 2-3 mL, and the stirring time is 30-40 min.
  3. 3. The preparation method according to claim 1, wherein in the step S3, the styrene-butadiene rubber is used in an amount of 100-120 g, the plasticating temperature is 80-90 ℃, the plasticating speed is 60-80 r/min, and the plasticating time is 6-8 min.
  4. 4. The preparation method according to claim 1, wherein in the step S3, the mixing temperature of the mixed solution, the carbon black N330 and the stearic acid is 90-100 ℃, the mixing time is 10-12 min, the mixing temperature after cooling is 70-80 ℃, and the mixing time is 6-8 min.
  5. 5. The preparation method of claim 1, wherein in the step S3, the carbon black N330 is used in an amount of 20-30 g, the stearic acid is used in an amount of 1.2-1.5 g, the sulfur is used in an amount of 2.0-2.5 g, and the accelerator CZ is used in an amount of 1-1.2 g.
  6. 6. The preparation method according to claim 1, wherein in the step S4, the pre-crosslinking temperature is 130-140 ℃, the pre-crosslinking pressure is 9MPa, the pre-crosslinking time is 5-8 min, the gradient heating rate is 3-5 ℃ per min, the vulcanization temperature is 150-160 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 18-20 min.
  7. 7. A high-strength anti-aging styrene-butadiene rubber, characterized in that the high-strength anti-aging styrene-butadiene rubber is produced by the production method of any one of claims 1 to 6.

Description

High-strength anti-aging styrene butadiene rubber and preparation method thereof Technical Field The invention belongs to the technical field of synthetic rubber modification, and particularly relates to high-strength anti-aging styrene-butadiene rubber and a preparation method thereof. Background Styrene-butadiene rubber is one of the most widely used synthetic rubbers at present, and is widely used in the fields of tires, sealing elements, outdoor cable jackets, building waterproof coiled materials and the like by virtue of good processability, wear resistance and cost performance. However, a large number of unsaturated double bonds exist in the molecular chain of the styrene-butadiene rubber, and the styrene-butadiene rubber is extremely easy to be subjected to oxidative degradation and crosslinking aging induced by environmental factors such as ultraviolet rays, thermal oxygen and the like, so that the elasticity of a product is lost, the hardness is increased, the service life is greatly shortened, meanwhile, the acting force among the molecular chains of the pure styrene-butadiene rubber is weak, the mechanical strength is insufficient, and inorganic reinforcing particles are required to be added to improve the performance. Inorganic particles such as white carbon black, carbon black and talcum powder are commonly used as styrene-butadiene rubber modifiers in industry, wherein the white carbon black and the carbon black can improve the mechanical strength of rubber through filling and reinforcement, layered inorganic particles such as talcum powder and the like can improve the ageing resistance through physical separation, but the inorganic particles all have obvious short plates, the white carbon black has high surface hydroxyl content, is easy to agglomerate and has poor compatibility with a rubber matrix, uniform dispersion is difficult to realize when the inorganic particles are used together with a coupling agent, the carbon black has excellent reinforcing effect but weak ultraviolet blocking capability, the ultraviolet ageing resistance of the rubber cannot be synchronously improved, and the talcum powder and the like can block part of ultraviolet rays but have low reinforcing efficiency and the toughness of the rubber is easy to be reduced after the inorganic particles are added. In order to achieve the modification targets of reinforcement and ageing resistance at the same time, the industry generally needs to compound a plurality of inorganic particles, the total addition amount is higher, the inorganic phase occupation ratio of a rubber system is greatly improved, the processing fluidity is deteriorated, stress concentration is easily generated due to uneven dispersion among different particles, and the comprehensive performance of rubber products is seriously affected. In the prior art, although the modification effect of inorganic particles is optimized through nanocrystallization and surface modification, the surface energy of nanoscale white carbon black, carbon black and the like is high, the agglomeration problem is more remarkable, the inorganic particles are of compact structures, the contact area with a rubber matrix is limited, the modification efficiency is low, and the expected effect can be achieved only by higher addition amount. Meanwhile, the functional limitation of single inorganic particles is difficult to break through, new problems of component compatibility, process complexity and the like are brought about by compounding use, and the high-strength and ageing-resistant co-promotion of the styrene-butadiene rubber with low doping amount cannot be realized. Therefore, a novel inorganic modifier with the dual functions of efficient reinforcement and ultraviolet aging resistance is developed, the efficient combination with a rubber matrix is realized through structural design, the total addition amount of inorganic particles is reduced, and the novel inorganic modifier becomes a key for solving the problem of modification of styrene-butadiene rubber. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides high-strength anti-aging styrene butadiene rubber and a preparation method thereof. PVP and polyvinyl alcohol 600 are used as a composite surfactant, porous reticular ZnO formed by aggregating ZnO nano particles with the wavelength of about 5nm is synthesized by a hydrothermal method, efficient aging resistance is realized by utilizing the ultraviolet absorption-visible light conversion function of the nano particles, rubber slurry fully permeates into the porous reticular structure, the contact area of the ZnO and rubber is greatly increased, the enhancement and aging resistance under low addition are realized, the surface modification is carried out on the porous reticular ZnO by a silane coupling agent, the interface combination of the porous reticular ZnO and a styrene-butadiene rubber matrix is enhanced, and finally the high-st