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CN-122011793-A - Modified lignin bio-based anti-aging agent and application thereof in rubber tires

CN122011793ACN 122011793 ACN122011793 ACN 122011793ACN-122011793-A

Abstract

The invention relates to the technical field of anti-aging agents, in particular to a modified lignin bio-based anti-aging agent and application thereof in rubber tires, wherein the anti-aging agent comprises the following components of 30-40 parts of modified lignin, 3-5 parts of silane coupling agent, 5-10 parts of white carbon black, 1-3 parts of polyethylene wax and 100-120 parts of carrier. The anti-aging agent disclosed by the invention adopts the biological base component, so that the pollution can be effectively reduced, the compatibility of lignin and rubber is improved by modifying lignin, the modified lignin is ensured to be uniformly dispersed, the bonding strength of the lignin and a rubber matrix interface is improved, the modified lignin can be cooperatively dispersed with white carbon black to play a reinforcing role, and the mechanical properties such as tensile strength, tear strength and the like of rubber are effectively improved while the filler consumption is reduced.

Inventors

  • ZONG HONGXING
  • LANG XUDONG
  • HU LIXIN
  • OU ZHIJUN

Assignees

  • 江苏国立化工科技有限公司

Dates

Publication Date
20260512
Application Date
20260306

Claims (10)

  1. 1. The biological-based antioxidant of the modified lignin is characterized by comprising, by weight, 30-40 parts of the modified lignin, 3-5 parts of a silane coupling agent, 5-10 parts of white carbon black, 1-3 parts of polyethylene wax and 100-120 parts of a carrier.
  2. 2. The modified lignin bio-based anti-aging agent according to claim 1, wherein the carrier is any one of ethylene propylene diene monomer, polypropylene, polyethylene or vinyl acetate.
  3. 3. The modified lignin bio-based anti-aging agent according to claim 1, wherein the silane coupling agent is KH-550 or KH-560.
  4. 4. The modified lignin bio-based anti-aging agent according to claim 1, wherein the modified lignin preparation method comprises the following steps: S1, adding alkali lignin into a solvent, stirring for 10-20 min, adding bromododecane to obtain a first mixed solution, and regulating the pH value of the first mixed solution to 11-12 by using a sodium hydroxide solution with the mass concentration of 20-30%, and then stirring for 2-4 h at 80-100 ℃ to obtain a first reaction solution, wherein the mass ratio of the alkali lignin to the bromododecane to the solvent is 1:0.3-0.5:10-15; s2, adjusting the pH value of the first reaction solution to 3-4 by using dilute hydrochloric acid with the mass concentration of 15-20%, filtering to obtain solid particles, and washing the solid particles to obtain alkylated lignin; s3, adding the parahydroxybenzoic acid into thionyl chloride, carrying out reflux reaction for 2-3 hours at 60-70 ℃, and carrying out reduced pressure distillation to obtain pretreated parahydroxybenzoic acid, wherein the mass ratio of the parahydroxybenzoic acid to the thionyl chloride is 1:3-4; s4, adding the alkylated lignin into the dimethyl sulfoxide, and stirring for 20-30 min at 50-60 ℃ to obtain a second mixed solution, wherein the mass ratio of the alkylated lignin to the dimethyl sulfoxide is 1:8-10; S5, placing the second mixed solution into a reaction kettle, vacuumizing the reaction kettle until the pressure in the reaction kettle reaches 1000-3000 Pa, then pressurizing by using inert gas until the pressure in the reaction kettle reaches 0.1-0.15 MPa, adding pyridine into the reaction kettle, stopping pressurizing and heating the reaction kettle until the temperature in the reaction kettle reaches 40-50 ℃, adding pretreated parahydroxybenzoic acid into the reaction kettle, then heating and pressurizing the reaction kettle until the temperature in the reaction kettle reaches 100-120 ℃, and keeping the temperature and pressure for 2-4 hours when the pressure reaches 0.2-0.3 MPa, so as to obtain the second reaction solution, wherein the adding amount of pyridine accounts for 1-3% of the initial mass of the second mixed solution, and the adding amount of pretreated parahydroxybenzoic acid accounts for 4-6% of the initial mass of the second mixed solution; and S6, dripping the second reaction liquid into ice water, filtering to obtain a precipitate, and washing and drying the precipitate to obtain the modified lignin.
  5. 5. The modified lignin bio-based anti-aging agent according to claim 4, wherein in the step S1, the solvent is urea, imidazole and deionized water which are mixed according to a mass ratio of 1:0.4-0.6:70-80.
  6. 6. The modified lignin bio-based anti-aging agent according to claim 4, wherein in the step S1, pretreatment is performed before alkali lignin is added into a solvent, the pretreatment method comprises the steps of adding the alkali lignin into an ethanol solution with the mass concentration of 70-80%, and conducting ultrasonic treatment at 20-30 ℃ for 1-2 hours, wherein the power during ultrasonic treatment is 150-300W, and the frequency is 20-40 kHz.
  7. 7. The modified lignin bio-based anti-aging agent according to claim 4, wherein in the step S6, the temperature of the ice water is 0-5 ℃, and the volume ratio of the second reaction solution to the ice water is 1:6-7.
  8. 8. The modified lignin bio-based anti-aging agent according to claim 1 is characterized in that the preparation method of the anti-aging agent comprises the steps of putting modified lignin, a silane coupling agent and a carrier into an internal mixer according to parts by weight, mixing for 1-3 min at 80-100 ℃, adding white carbon black and polyethylene wax, heating to 150-170 ℃, mixing for 5-8 min at a rotating speed of 60-80 r/min, heating to 175-185 ℃ again, mixing for 2-3 min at a rotating speed of 50-60 r/min, obtaining a mixed master batch, and extruding and granulating the mixed master batch at 160-170 ℃ by using a screw extruder to obtain the anti-aging agent.
  9. 9. The use of a modified lignin bio-based anti-aging agent according to any one of claims 1 to 8 in rubber tires.
  10. 10. The application of the rubber tire according to claim 9, wherein the application method is that the anti-aging agent is added into the rubber matrix in the rubber mixing process of the rubber tire, and the addition amount of the anti-aging agent accounts for 5-10% of the total mass of the rubber matrix.

Description

Modified lignin bio-based anti-aging agent and application thereof in rubber tires Technical Field The invention relates to the technical field of anti-aging agents, in particular to a modified lignin bio-based anti-aging agent and application thereof in rubber tires. Background Tires are an important part of modern automobiles, and are subjected to various deformation, load, force and high and low temperature effects during driving, and the performance of the tires directly influences the economical efficiency and the safety of driving. However, in the use process of the tire, the temperature of the tire can reach 60-80 ℃ or even higher due to ground friction, so that the reaction of oxygen and rubber molecules is accelerated, the rubber tire is aged, and the mechanical property of the rubber tire is affected. Therefore, in the production process of rubber tires, an anti-aging agent needs to be added into the tires to improve the anti-aging performance of the rubber tires, and the existing anti-aging agents mainly comprise amine types, phenols, thioesters, phosphite esters and the like, but most of the anti-aging agents are derived from nonrenewable petrochemical products, and the anti-aging agents pollute the environment in the production and use processes. Because lignin contains a large number of hindered phenol structures, has a certain capturing capacity to free radicals, is a natural anti-aging agent, and has great application potential in the field of rubber anti-aging agents. However, the anti-aging performance of lignin is poor, the aging process of rubber is difficult to effectively inhibit, the dispersibility of lignin in a rubber matrix is poor, the interface combination of lignin and the rubber matrix is weak, and the mechanical properties of rubber products can be reduced after the lignin is added. Disclosure of Invention In order to solve the problems, the invention provides a modified lignin bio-based anti-aging agent and application thereof in rubber tires. The technical scheme is that the modified lignin bio-based anti-aging agent comprises, by weight, 30-40 parts of modified lignin, 3-5 parts of a silane coupling agent, 5-10 parts of white carbon black, 1-3 parts of polyethylene wax and 100-120 parts of a carrier. The anti-aging agent adopts the biological base component, so that pollution can be effectively reduced, the compatibility of lignin and rubber is improved by modifying lignin, the modified lignin is ensured to be uniformly dispersed, the bonding strength of the lignin and a rubber matrix interface is improved, the modified lignin can be cooperatively dispersed with white carbon black to play a reinforcing role, and the mechanical properties such as tensile strength, tear strength and the like of rubber are effectively improved while the filler consumption is reduced. Further, the carrier is any one of ethylene propylene diene monomer, polypropylene, polyethylene or vinyl acetate. The carrier can effectively disperse the modified lignin and is well compatible with the rubber matrix, so that the components of the anti-aging agent can be effectively dispersed in the rubber matrix along with the carrier. Further, the silane coupling agent is KH-550 or KH-560. The silane coupling agent can strengthen the interfacial binding force between the modified lignin and the rubber matrix, so that the modified lignin is fully dispersed in the rubber matrix. Further, the preparation method of the modified lignin comprises the following steps: S1, adding alkali lignin into a solvent, stirring for 10-20 min, adding bromododecane to obtain a first mixed solution, and regulating the pH value of the first mixed solution to 11-12 by using a sodium hydroxide solution with the mass concentration of 20-30%, and then stirring for 2-4 h at 80-100 ℃ to obtain a first reaction solution, wherein the mass ratio of the alkali lignin to the bromododecane to the solvent is 1:0.3-0.5:10-15; s2, adjusting the pH value of the first reaction solution to 3-4 by using dilute hydrochloric acid with the mass concentration of 15-20%, filtering to obtain solid particles, and washing the solid particles to obtain alkylated lignin; s3, adding the parahydroxybenzoic acid into thionyl chloride, carrying out reflux reaction for 2-3 hours at 60-70 ℃, and carrying out reduced pressure distillation to obtain pretreated parahydroxybenzoic acid, wherein the mass ratio of the parahydroxybenzoic acid to the thionyl chloride is 1:3-4; s4, adding the alkylated lignin into the dimethyl sulfoxide, and stirring for 20-30 min at 50-60 ℃ to obtain a second mixed solution, wherein the mass ratio of the alkylated lignin to the dimethyl sulfoxide is 1:8-10; S5, placing the second mixed solution into a reaction kettle, vacuumizing the reaction kettle until the pressure in the reaction kettle reaches 1000-3000 Pa, then pressurizing by using inert gas until the pressure in the reaction kettle reaches 0.1-0.15 MPa, adding pyridine into the react