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CN-122011525-A - Ultraviolet-resistant rubber composite material and preparation method thereof

CN122011525ACN 122011525 ACN122011525 ACN 122011525ACN-122011525-A

Abstract

The invention belongs to the field of rubber materials, and particularly relates to an ultraviolet-resistant rubber composite material and a preparation method thereof. The rubber composite material comprises, by weight, 100 parts of natural rubber, 10-20 parts of a styrene-maleic anhydride-acrylonitrile terpolymer, 5-10 parts of a composite anti-ultraviolet agent, 4-8 parts of an activating agent, 20-40 parts of a reinforcing agent, 2-4 parts of an anti-aging agent, 1-2.8 parts of an accelerator and 1-2.8 parts of a vulcanizing agent, wherein the composite anti-ultraviolet agent comprises nano spherical cerium oxide, an organic micromolecule anti-ultraviolet agent and a modifying agent which are loaded on the surface of the nano spherical cerium oxide, and the mass ratio of the nano spherical cerium oxide, the organic micromolecule anti-ultraviolet agent and the modifying agent is 100 (1-5) (2-6). The rubber composite material provided by the invention has excellent anti-ultraviolet performance and mechanical property.

Inventors

  • ZHANG YE
  • CHENG HONGDA
  • HAN CHANGYU
  • Yu Mengdie

Assignees

  • 中国科学院长春应用化学研究所

Dates

Publication Date
20260512
Application Date
20260310

Claims (10)

  1. 1. The ultraviolet-resistant rubber composite material is characterized by comprising the following raw materials in parts by weight: 100 parts of natural rubber; 10-20 parts of a styrene-maleic anhydride-acrylonitrile terpolymer; 5-10 parts of a composite anti-ultraviolet agent; 4-8 parts of an activating agent; 20-40 parts of a reinforcing agent; 2-4 parts of an anti-aging agent; 1-2.8 parts of an accelerator; 1-2.8 parts of vulcanizing agent; The composite anti-ultraviolet agent comprises nano spherical cerium oxide, and an organic micromolecule anti-ultraviolet agent and a modifier which are loaded on the surface of the nano spherical cerium oxide, wherein the mass ratio of the nano spherical cerium oxide to the organic micromolecule anti-ultraviolet agent to the modifier is 100 (1-5) (2-6).
  2. 2. The ultraviolet resistant rubber composite material according to claim 1, wherein the particle size of the nano spherical cerium oxide is 200-400 nm, and the specific surface area is 100-200 m 2 /g.
  3. 3. The ultraviolet resistant rubber composite according to claim 1, wherein the small organic molecule ultraviolet resistant agent is one or more of 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole and bis (2, 6-tetramethyl-4-piperidine) sebacate.
  4. 4. The ultraviolet resistant rubber composite according to claim 1, wherein the modifier is one or more of bis- [ gamma- (triethoxysilane) propyl ] amine, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, and gamma-mercaptopropyl trimethoxysilane.
  5. 5. The ultraviolet resistant rubber composite material according to claim 1, wherein the weight average molecular weight of the styrene-maleic anhydride-acrylonitrile terpolymer is 4000-6000, and the molar ratio of the repeating units corresponding to styrene, the repeating units corresponding to maleic anhydride and the repeating units corresponding to acrylonitrile in the styrene-maleic anhydride-acrylonitrile terpolymer is (4-6): 2-3.
  6. 6. The ultraviolet resistant rubber composite material according to claim 1, wherein the activator is zinc oxide and stearic acid, and the mass ratio of the zinc oxide to the stearic acid is (3-5): 1; The reinforcing agent is one or more of carbon black, white carbon black, calcium carbonate, clay, talcum powder, barium sulfate and montmorillonite; The anti-aging agent is one or more of 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-alpha-naphthylamine, N-phenyl-beta-naphthylamine, 2, 6-di-tert-butyl-p-cresol, N-isopropyl-N '-phenyl-p-phenylenediamine, 2-mercaptobenzimidazole, N-isopropyl-N' -phenyl-p-phenylenediamine, 2 '-methylenebis (4-methyl-6-tert-butylphenol) and N, N' -di (beta-naphthyl) p-phenylenediamine; The accelerator is one or more of 2,2 '-dithiodibenzothiazyl, 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, diphenyl guanidine, di-o-toluene guanidine, N-tetramethyl dithio-carboamine, tetraethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, N-cyclohexyl-2-benzothiazole sulfenamide, N-tertiary butyl-2-benzothiazole sulfenamide and N, N' -dicyclohexyl-2-benzothiazole sulfenamide; the vulcanizing agent is one or more of sublimed sulfur, precipitated sulfur and insoluble sulfur.
  7. 7. A method for preparing the ultraviolet resistant rubber composite material according to any one of claims 1 to 6, comprising the following steps: mixing and vulcanizing natural rubber, a styrene-maleic anhydride-acrylonitrile terpolymer, a composite ultraviolet resistant agent, an activating agent, a reinforcing agent, an anti-aging agent, an accelerator and a vulcanizing agent to obtain the ultraviolet resistant rubber composite material.
  8. 8. The method of claim 7, wherein the composite anti-uv agent is prepared by: i) Mixing an organic micromolecular anti-ultraviolet agent, a part of modifier and a solvent to obtain an anti-ultraviolet agent mixed solution; ii) mixing the nanosphere-shaped cerium oxide with a part of the modifier to obtain modified nanospheres; Step i) and step ii) are not sequential; iii) Spraying the ultraviolet resistant agent mixed solution on the surface of the modified nanospheres, and evaporating to remove the solvent to obtain the composite ultraviolet resistant agent.
  9. 9. The preparation method according to claim 8, wherein the mass ratio of the modifier in step i) to the modifier in step ii) is 1 (0.5-2).
  10. 10. The method according to claim 8, wherein in step ii), the mixing temperature is 80 to 100 ℃, the vacuum degree is 0.05 to 0.08mpa, and the time is 1 to 2 hours.

Description

Ultraviolet-resistant rubber composite material and preparation method thereof Technical Field The invention belongs to the field of rubber materials, and particularly relates to an ultraviolet-resistant rubber composite material and a preparation method thereof. Background Natural rubber is used as a polymer material with superior performance, has high elasticity, good wear resistance and higher tensile strength, and is widely applied to various fields such as tires, sealing elements, medical instruments, daily necessities and the like. However, the molecular structure of natural rubber contains a large amount of unsaturated double bonds, so that oxidative degradation reaction is very easy to occur under ultraviolet irradiation, and further ageing phenomena such as mechanical property reduction, cracking, color change and the like are caused, and the service life and the safety of the product are seriously influenced. The traditional method for improving the ultraviolet aging resistance of the natural rubber is mainly to add an organic ultraviolet absorber and an antioxidant into a rubber material. However, these organic additives have problems of easy migration, volatilization and extraction, and after long-term use, the anti-ultraviolet effect of the organic additives is gradually reduced, which limits the application of rubber materials to a certain extent. In addition, the mechanical properties of the material are often difficult to be simultaneously considered when the anti-ultraviolet agent is simply added. Therefore, how to maintain and even enhance the mechanical strength of the natural rubber while improving the ultraviolet aging resistance of the natural rubber is always a research hot spot and a difficult point in the field. Along with the continuous expansion of the application scene of the rubber product, like outdoor products, automobile tires, building sealing materials and the like, the weather resistance and the service life of the rubber product are more required. Therefore, the natural rubber composite material with long-acting, high-efficiency and ultraviolet resistance and excellent comprehensive mechanical property is developed, and has important practical significance and application value. Disclosure of Invention In view of the above, the invention aims to provide an ultraviolet-resistant rubber composite material and a preparation method thereof. The invention provides an ultraviolet-resistant rubber composite material, which comprises the following raw materials in parts by weight: 100 parts of natural rubber; 10-20 parts of a styrene-maleic anhydride-acrylonitrile terpolymer; 5-10 parts of a composite anti-ultraviolet agent; 4-8 parts of an activating agent; 20-40 parts of a reinforcing agent; 2-4 parts of an anti-aging agent; 1-2.8 parts of an accelerator; 1-2.8 parts of vulcanizing agent; The composite anti-ultraviolet agent comprises nano spherical cerium oxide, and an organic micromolecule anti-ultraviolet agent and a modifier which are loaded on the surface of the nano spherical cerium oxide, wherein the mass ratio of the nano spherical cerium oxide to the organic micromolecule anti-ultraviolet agent to the modifier is 100 (1-5) (2-6). Preferably, the particle size of the nano spherical cerium oxide is 200-400 nm, and the specific surface area is 100-200 m 2/g. Preferably, the organic small molecule anti-ultraviolet agent is one or more of 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole and bis (2, 6-tetramethyl-4-piperidine) sebacate. Preferably, the modifier is one or more of bis- [ gamma- (triethoxysilyl) propyl ] amine, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, vinyl triethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-mercaptopropyl trimethoxysilane. Preferably, the weight average molecular weight of the styrene-maleic anhydride-acrylonitrile terpolymer is 4000-6000, and the molar ratio of the repeating units corresponding to styrene, the repeating units corresponding to maleic anhydride and the repeating units corresponding to acrylonitrile in the styrene-maleic anhydride-acrylonitrile terpolymer is (4-6): 2-3. Preferably, the activator is zinc oxide and stearic acid, and the mass ratio of the zinc oxide to the stearic acid is (3-5): 1; The reinforcing agent is one or more of carbon black, white carbon black, calcium carbonate, clay, talcum powder, barium sulfate and montmorillonite; The anti-aging agent is one or more of 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-alpha-naphthylamine, N-phenyl-beta-naphthylamine, 2, 6-di-tert-butyl-p-cresol, N-isopropyl-N '-phenyl-p-phenylenediamine, 2-mercaptobenzimidazole, N-isopropyl-N' -phenyl-p-pheny