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CN-121975345-A - Rubber anti-aging agent composition and preparation method thereof

CN121975345ACN 121975345 ACN121975345 ACN 121975345ACN-121975345-A

Abstract

The invention relates to the technical field of anti-aging agents, and particularly discloses a rubber anti-aging agent composition and a preparation method thereof. The composition consists of halloysite anti-aging agent, functional lignin, interface regulator and modified white carbon black. The halloysite anti-aging agent is modified by a double-silane coupling agent (gamma-mercaptopropyl trimethoxy silane and 3-aminopropyl triethoxy silane), mercapto and amino are introduced into the surface, then the anti-aging agent is loaded, a Zn < 2+ > -phenanthroline complex is anchored to form a stable coordination structure, disulfide bonds and phenylboric acid groups are introduced into functional lignin to form a stable crosslinked network, a long-chain alkyl is introduced into an interface regulator through ring-opening esterification reaction of stearic acid and epoxy groups to enhance interface compatibility, and the modified white carbon black improves dispersion stability. The obtained composition remarkably improves the durability and environmental friendliness of rubber products, and is suitable for high-performance rubber products such as green tires, sealing elements and the like.

Inventors

  • HU LIXIN
  • ZONG HONGXING
  • WU MEIJUN
  • LANG XUDONG

Assignees

  • 江苏国立化工科技有限公司

Dates

Publication Date
20260505
Application Date
20260408

Claims (9)

  1. 1. The rubber antioxidant composition is characterized by comprising, by weight, 60-70 parts of halloysite antioxidants, 25-35 parts of functionalized lignin, 5-10 parts of interface regulators and 2-3 parts of modified white carbon black; The halloysite anti-aging agent is prepared by the following method: A1, mixing activated halloysite powder with a mixed solvent under the protection of nitrogen, adding a bis-silane coupling agent, regulating the pH of a system to 4.5-5.5, stirring for reaction, and filtering, washing and drying after the reaction is finished to obtain modified halloysite; a2, under the protection of nitrogen, mixing 2, 6-di-tert-butyl-p-cresol and a light stabilizer 770, melting, adding modified halloysite, uniformly stirring, and solidifying to obtain the anti-aging agent loaded halloysite; a3, mixing the phenanthroline, zinc acetate and water, and stirring until the mixture is completely dissolved to obtain a mixed solution; and A4, adding the mixed solution into the halloysite loaded with the anti-aging agent under stirring, continuously stirring uniformly, drying, crushing and sieving to obtain the halloysite anti-aging agent.
  2. 2. The rubber antioxidant composition according to claim 1, wherein the bis-silane coupling agent in the step A1 is formed by mixing gamma-mercaptopropyl trimethoxysilane and 3-aminopropyl triethoxysilane according to a mass ratio of 1-1.2:1.
  3. 3. The rubber antioxidant composition according to claim 1, wherein the mass ratio of2, 6-di-tert-butyl-p-cresol, light stabilizer 770 and modified halloysite in the step A2 is 4-6:4-6:100.
  4. 4. The rubber antioxidant composition of claim 1, wherein the functionalized lignin is prepared by the process of: B1, under the protection of nitrogen, dissolving the enzymolysis lignin in a sodium hydroxide solution, adding maleic anhydride, stirring for reaction, cooling to room temperature after the reaction is finished, and regulating the pH value of the system to 5-6 to obtain a carboxylated lignin solution; B2, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated lignin solution under the protection of nitrogen, stirring for reaction, and obtaining an activated reaction solution after the reaction is finished; B3, adding L-cysteine and 3-aminophenylboric acid into the activation reaction liquid under the protection of nitrogen, regulating the pH of the system to 6.5-7.5, stirring for reaction, and obtaining a difunctional grafting reaction liquid after the reaction is finished; And B4, adding dimethyl sulfoxide into the difunctional grafting reaction liquid, stirring for reaction, adjusting the pH value of the system to 3.5-4.5 after the reaction is finished, filtering, washing, drying, crushing and sieving to obtain the functional lignin.
  5. 5. The rubber antioxidant composition according to claim 4, wherein the mass ratio of the enzymatic lignin, the maleic anhydride and the sodium hydroxide solution in the step B1 is 10:1.8-2.2:35-40.
  6. 6. The rubber antioxidant composition according to claim 4, wherein the mass ratio of the carboxylated lignin solution, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the N-hydroxysuccinimide in the step B2 is 100:3.5-4.5:3-3.5.
  7. 7. The rubber antioxidant composition of claim 1, wherein the interfacial modifier is prepared by the process of: C1, carrying out vacuum dehydration on epoxidized soybean oil to obtain dehydrated epoxidized soybean oil; And C2, mixing the dehydrated epoxidized soybean oil and stearic acid, adding tetrabutylphosphonium bromide, stirring for reaction under the protection of nitrogen, filtering while the reaction is hot after the reaction is finished, collecting filtrate, and cooling to room temperature to obtain the interface regulator.
  8. 8. The rubber antioxidant composition of claim 1, wherein the modified white carbon black is prepared by the following method: dispersing precipitation white carbon black in deionized water, adding octadecylamine, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing, drying, pulverizing and sieving to obtain modified white carbon black.
  9. 9. A process for preparing the rubber antioxidant composition of any one of claims 1 to 8, comprising the steps of: S1, dispersing halloysite anti-aging agent in deionized water, and shearing and emulsifying to obtain slurry; s2, dissolving the functionalized lignin in deionized water, adding slurry and an interface regulator, regulating the pH value of the system to 7.8-8.2, homogenizing and emulsifying to obtain a basic mixture; s3, adding the modified white carbon black into the basic mixture, uniformly stirring, and performing spray drying and screening to obtain the rubber antioxidant composition.

Description

Rubber anti-aging agent composition and preparation method thereof Technical Field The invention relates to the technical field of anti-aging agents, in particular to a rubber anti-aging agent composition and a preparation method thereof. Background Rubber articles are widely used in various industrial applications, particularly in the fields of automobiles, construction, aviation, and the like. However, rubber products often face oxidation, thermal aging, ozone aging and dynamic stress during long-term use, resulting in molecular chain breakage, crosslinking and surface cracking, which severely reduces mechanical properties, elasticity and service life. The main causes of these performance failures are the breakage of the polymer chain structure and the formation of oxidation products, which are particularly evident in long-term exposure to oxygen, ozone, ultraviolet light and high temperature environments. In order to effectively prolong the service life of rubber, an anti-aging agent becomes an indispensable rubber additive. The anti-aging agent suppresses aging of rubber mainly by blocking free radicals of oxidation reaction. Currently, the antioxidants used in the rubber industry are mostly small molecular compounds, mainly including phenols (such as 2, 6-di-t-butyl-p-cresol), amines (such as 6 PPD), and the like. However, these small molecule antioxidants, while having good anti-aging effects, have significant drawbacks including: The coating has the advantages of (1) low molecular weight, high migration rate in a rubber matrix, remarkable attenuation of protective effect after long-term use, (2) easy occurrence of frosting phenomenon, influence on the appearance and interface adhesion performance of the product, and (3) incapability of regeneration after consumption and low resource utilization rate. In order to improve mobility, researchers try to load an anti-aging agent on carriers such as halloysite, lignin and the like, but the problems of insufficient active sites of the carriers, low embedding rate of the anti-aging agent, poor compatibility with rubber and the like exist, and a part of dynamic bond (such as disulfide bond) modification systems have self-repairing potential but lack a synergistic mechanism for releasing the anti-aging agent, and functional components such as metal complexes and the like are easy to migrate or run off in the rubber system and are difficult to play a stabilizing role for a long time. Therefore, there is a need to develop a rubber antioxidant composition having high migration resistance, damage self-repairing ability and excellent aging stability. Disclosure of Invention The invention provides a rubber antioxidant composition and a preparation method thereof, and aims to solve the problems of large migration loss, poor protection durability, insufficient functional cooperativity and the like of the existing rubber antioxidant. In a first aspect, the invention provides a rubber antioxidant composition, which adopts the following technical scheme: the rubber antioxidant composition comprises, by weight, 60-70 parts of halloysite antioxidants, 25-35 parts of functionalized lignin, 5-10 parts of interface regulators and 2-3 parts of modified white carbon black. Preferably, the halloysite anti-aging agent is prepared by the following method: A1, mixing activated halloysite powder with a mixed solvent under the protection of nitrogen, adding a bis-silane coupling agent, regulating the pH of a system to 4.5-5.5, stirring for reaction, and filtering, washing and drying after the reaction is finished to obtain modified halloysite; a2, under the protection of nitrogen, mixing 2, 6-di-tert-butyl-p-cresol and a light stabilizer 770, melting, adding modified halloysite, uniformly stirring, and solidifying to obtain the anti-aging agent loaded halloysite; a3, mixing the phenanthroline, zinc acetate and water, and stirring until the mixture is completely dissolved to obtain a mixed solution; and A4, adding the mixed solution into the halloysite loaded with the anti-aging agent under stirring, continuously stirring uniformly, drying, crushing and sieving to obtain the halloysite anti-aging agent. By adopting the technical scheme, the bis-silane coupling agent is grafted on hydroxyl sites on the surface of halloysite through hydrolysis condensation reaction, the molten 2, 6-di-tert-butyl-p-cresol and the light stabilizer 770 are stirred, diffused and filled into the nanotube cavities of halloysite, then zinc acetate and phenanthroline undergo coordination reaction, the generated metal complex is deposited at the pipe orifice of halloysite, physical blocking is carried out on the tube, and the migration rate of the anti-aging agent from the tube cavity to the matrix is reduced. Preferably, the mass ratio of the halloysite powder, the disilane coupling agent and the mixed solvent after the activation in the step A1 is 10-15:1-2:100-110. Preferably, the bis-silane coupling agent in