A wear-resistant and high-tear strength composite rubber material and preparation method thereof

Abstract

The invention discloses a wear-resistant and high-tear strength composite rubber material and a preparation method thereof, belonging to the technical field of rubber material processing, and is used to solve the technical problem that in the preparation process of the composite rubber material in the prior art, the reinforcing effect of fillers on the wear resistance, tear resistance and mechanical strength of a rubber matrix needs to be further improved; the invention comprises the following components in parts by weight: 100-110 parts of internal mixing rubber, 1-2 parts of a vulcanizing accelerator and 2-3 parts of a vulcanizing agent, and the composite polybutadiene is prepared by reinforcing modified polybutadiene with aramid pulp, modified carbon black and modified graphene, and then the prepared composite polybutadiene and silicone rubber are used to reinforce and modify styrene-butadiene rubber, and the crosslinking degree between material molecules is increased and the material composition is optimized, so that not only the wear resistance and tear resistance of the composite rubber material are effectively improved, but also the mechanical property of the composite rubber material is improved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber material processing, and in particular to a wear-resistant and high-tear strength composite rubber material and a preparation method thereof. Background Art

[0002] As an important industrial material, rubber materials are widely used in many fields such as automobiles, machinery, construction, aerospace, etc. With the rapid development of industrial technology, rubber materials are increasingly used in various fields, especially in the fields of mechanical equipment, automobile manufacturing, aerospace, chemical pipelines and building seals, which put forward higher requirements on the wear resistance, tear resistance and comprehensive performance of rubber materials. Traditional rubber materials are often difficult to meet the needs of long-term use under complex working conditions, and are prone to wear, tear and other problems, affecting the operating efficiency and safety of the equipment. Therefore, it is particularly important to develop a wear-resistant and high-tear-strength composite rubber material and its preparation method.

[0003] Common wear-resistant rubber materials in the prior art mainly improve their wear resistance by adding various fillers and reinforcing agents such as carbon black, white carbon black, and short fibers. However, these materials have problems such as uneven filler dispersion and weak bonding with the rubber matrix during the preparation process, which makes it difficult to significantly improve the mechanical properties of the composite materials. Although some studies have shown that the introduction of nanomaterials such as graphite and carbon nanotubes into the rubber matrix through nanotechnology can significantly improve the wear resistance and mechanical properties of the rubber, the dispersion effect of these nanomaterials in rubber is still a difficult problem, and different reinforcing materials have different effects on the rubber properties. How to select suitable reinforcing materials, optimize the preparation process, and make full use of the synergistic effect between materials to further improve the comprehensive properties of the composite rubber materials such as wear resistance and tear resistance is a technical problem that needs to be solved urgently.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a wear-resistant and high-tear strength composite rubber material and a preparation method thereof, so as to solve the technical problem in the prior art that the wear resistance, tear resistance and mechanical strength of the rubber matrix enhanced by fillers during the preparation of the composite rubber material need to be further improved.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A composite rubber material with high wear resistance and tear resistance, comprising the following components in parts by weight: 100-110 parts of internal mixing rubber, 1-2 parts of vulcanization accelerator and 2-3 parts of vulcanizing agent;

[0008] The internal rubber compound comprises the following components in parts by weight: 80-100 parts of styrene-butadiene rubber, 15-17 parts of silicone rubber, 20-25 parts of composite polybutadiene and 3-5 parts of auxiliary additives;

[0009] The composite polybutadiene is obtained by processing the following steps:

[0010] A1. Add polybutadiene and toluene to a nitrogen-protected reactor and stir. Raise the reactor temperature to 70-80°C and stir until the system is dissolved. Add KH-590 to the reactor and stir for 20-30 minutes. Add initiator to the reactor and keep the reaction temperature for 3-5 hours. Post-treat to obtain modified polybutadiene.

[0011] The synthetic reaction principle of modified butadiene is:

[0012] Dilauroyl peroxide is a commonly used free radical initiator. When heated, it decomposes to produce free radicals. These free radicals can attack the unsaturated double bonds on the polybutadiene molecules to form polybutadiene free radicals. The free radicals can then react with the thiol groups on KH-590 to form covalent bonds, thereby grafting KH-590 onto the polybutadiene molecules to form modified polybutadiene with triethoxysilane modified polybutadiene.

[0013] A2. Add aramid pulp, modified carbon black, modified graphene, modified polybutadiene, xylene and catalyst solution into a ball mill, ball mill for 4 hours, and post-treat to obtain composite polybutadiene.

[0014] The synthetic reaction principle of composite polybutadiene is:

[0015] The ball mill continuously impacts and rubs the balls, and xylene as a solvent helps to disperse and mix the raw materials. The mechanical force during the ball milling process causes the interfaces between the raw materials to intertwine and entangle with each other to form a physical bond. The acetic acid solution adjusts the pH value to provide an acidic system for the ball milling system, which promotes the hydrolysis of triethoxysilane on the modified polybutene to form chemical bonds with the active groups on the surface of aramid pulp, modified carbon black, and modified graphene, thereby forming a composite butadiene with cross-linked bonds of aramid pulp, modified carbon black, modified graphene, and modified polybutadiene.

[0016] Furthermore, the silicone rubber is hexamethylhexavinylcyclohexasiloxane, the vulcanization accelerator is composed of 2-thiolbenzothiazole, N-tert-butyl-2-benzothiazolesulfonamide and zinc diethyldithiocarbamate in a weight ratio of 2:1:1, and the vulcanizing agent is composed of sulfur and diisopropylbenzene peroxide in a weight ratio of 3:1.

[0017] Further, in step A1, the amount ratio of the polybutadiene, toluene, KH-590 and initiator is 3g:20mL:1g:0.05g, the initiator is dilauroyl peroxide, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, anhydrous ethanol is added to the reactor, a large amount of solid is precipitated, stirred and crushed for 20-30min, filtered, the filter cake is washed with anhydrous ethanol 3 times and then dried, and the filter cake is transferred to a temperature of 60-70°C In a drying oven, the mixture is dried to constant weight to obtain modified polybutadiene; in step A2, the amount ratio of the aramid pulp, modified carbon black, modified graphene, modified polybutadiene, xylene and catalyst solution is 7g:2g:1g:30g:50mL:7mL, the catalyst solution is 1mol / L acetic acid solution, and the post-treatment includes: after the reaction is completed, the reactant is taken out from the ball mill, and the reactant is extracted with xylene for 6-8h to obtain composite polybutadiene.

[0018] Further, the modified carbon black is obtained by processing the following steps:

[0019] B1. Add carbon black and pretreatment solution into a reactor and stir. Raise the temperature of the reactor to 80-90°C and keep warm for 30-50 minutes. Post-treat to obtain pretreated carbon black.

[0020] B2, adding the pre-treated carbon black, dopamine hydrochloride and buffer into the reactor and stirring, raising the temperature of the reactor to 40-50°C, keeping the temperature for reaction for 20-22h, and post-treating to obtain activated carbon black;

[0021] B3, adding activated carbon black and silver nitrate into a reaction kettle and stirring, raising the temperature of the reaction kettle to 45-55°C, keeping the temperature for reaction for 2-3h, and post-treating to obtain loaded carbon black;

[0022] B4. Add the loaded carbon black and the plating solution into a reactor and stir, react at room temperature for 3-4 hours, and perform post-treatment to obtain modified carbon black.

[0023] The synthetic reaction principle of modified carbon black is:

[0024] The carbon black is oxidized and etched by the cooperation of nitric acid and hydrogen peroxide to make it rougher and increase the specific surface area. At the same time, functional groups such as carboxyl and hydroxyl groups are introduced on the surface of the carbon black. Sodium dodecyl sulfate as a surfactant helps to disperse the carbon black particles and prevents them from agglomerating during the reaction, thereby improving the treatment effect. Dopamine hydrochloride undergoes its own oxidative polymerization reaction in a buffer environment to generate polydopamine with strong adhesion, which is coated on the surface of the pre-treated carbon black to prepare activated carbon black. The polydopamine layer coated on the surface of the activated carbon black itself has weak reducing properties and can remove Ag. +Reduced to Ag nanoparticles loaded on the surface of the polydopamine layer to prepare loaded carbon black; during the plating process of the plating solution, the Ag nanoparticles can serve as catalytic crystal nuclei to become Ni 2+ The reduction center finally reduces the nickel on the surface of polydopamine with Ag nanoparticles as the center. The reduced nickel catalyzes the subsequent Ni 2+ After reduction, the nickel single substance is finally connected into a piece to form a nickel layer with uniform thickness and dense texture, thereby preparing modified carbon black.

[0025] Further, in step B1, the pretreatment solution is composed of 6-8mol / L nitric acid, 10wt% hydrogen peroxide and sodium dodecyl sulfate in a dosage ratio of 10mL:4mL:0.5g, the dosage ratio of the carbon black and the activation solution is 1g:10mL, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then dried, and the filter cake is transferred to a drying oven at a temperature of 70-80°C and dried to constant weight to obtain pre-treated carbon black; in step B2, the buffer is 1mol / L at pH=8.5 Tris hydrochloride solution, the amount ratio of the pre-treatment carbon black, dopamine hydrochloride and buffer solution is 10g:100mL:0.3g, the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, suction filtration, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven with a temperature of 60-70°C, and vacuum dried to constant weight to obtain activated carbon black; in step B3, the concentration of silver nitrate is 0.7-1.3mol / L, the amount ratio of the activated carbon black to silver nitrate is 1g:5mL, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, suction filtration The filter cake is washed with purified water until it is neutral and then drained, and the filter cake is transferred to a drying oven at a temperature of 70-80°C and dried to constant weight to obtain loaded carbon black; in step B4, the plating solution is composed of nickel sulfate, sodium tartrate, sodium oxalate, boric acid and deionized water in a dosage ratio of 1.5g:2g:2g:1g:150mL, and the dosage ratio of the loaded carbon black to the plating solution is 1g:4mL. The post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then drained, and the filter cake is transferred to a drying oven at a temperature of 70-80°C and dried to constant weight to obtain modified carbon black.

[0026] Furthermore, the preparation method of the modified graphene is: adding graphene oxide, deionized water and potassium hydroxide into a reactor, ultrasonically dispersing for 40-60 minutes, stirring, raising the temperature of the reactor to 70-80°C, adding 1-aminopropyl-3-methylimidazolium bromide to the reactor, keeping the temperature for reaction for 60-90 minutes, and post-treating to obtain the modified graphene.

[0027] The synthetic reaction principle of modified graphite is:

[0028] Graphene oxide not only contains SP2 hybridized carbon atoms, but also contains a large number of oxygen-containing functional groups on its surface, such as hydroxyl groups, carboxyl groups, etc. In an alkaline environment, the amino groups on 1-aminopropyl-3-methylimidazolium bromide react with the carboxyl groups on the surface of graphene oxide to undergo amidation reaction, and 1-aminopropyl-3-methylimidazolium bromide is grafted onto graphene oxide to prepare modified graphene.

[0029] Furthermore, the amount ratio of the graphene oxide, deionized water, potassium hydroxide and 1-aminopropyl-3-methylimidazolium bromide is 3g:100mL:5g:1g, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80°C, and vacuum dried to constant weight to obtain modified graphene.

[0030] A method for preparing a wear-resistant and high-tear strength composite rubber material comprises the following steps:

[0031] S1, adding styrene-butadiene rubber, silicone rubber and auxiliary additives into an internal mixer, setting the temperature of the internal mixer to 90-100°C, the speed to 70-80r / min, mixing for 2-3min, adding composite polybutadiene into the internal mixer, mixing for 5-10min, cooling after discharge, and obtaining internal mixer rubber;

[0032] S2, set the roller spacing of the open mill to 1-2mm, the temperature to 70-80 ° C, add the internal rubber to the open mill to plasticize and roll the roll, add the vulcanization accelerator to the open mill, after all the materials are eaten, tap the rubber three times on the left and right sides, add the vulcanizing agent to the open mill, tap the rubber three times on the left and right sides, make triangle packages 10-15 times, cool down after discharging, and obtain mixed rubber;

[0033] S3, adding the mixed rubber into a flat plate vulcanizer, vulcanizing, and obtaining a composite rubber material.

[0034] Furthermore, in step S1, the auxiliary additives are composed of an antioxidant, a dispersant, a plasticizer and a flame retardant in a weight ratio of 2:1:5:3, the antioxidant is one or more of antioxidant A, antioxidant H, antioxidant D, and antioxidant CPPD, the dispersant is a stearate, the plasticizer is a phthalate, and the flame retardant is composed of ammonium polyphosphate, aluminum hydroxide and magnesium hydroxide in a weight ratio of 5:3:2; in step S3, the temperature of the flat vulcanizer is 170-180°C, the pressure is 10-14MPa, and the vulcanization time is 30-50min.

[0035] The present invention has the following beneficial effects:

[0036] 1. The wear-resistant and tear-resistant composite rubber material of the present application is prepared by modifying polybutadiene and then reinforcing the modified polybutadiene with aramid pulp, modified carbon black and modified graphene, and then reinforcing and modifying styrene-butadiene rubber with the prepared composite polybutadiene and silicone rubber. After mixing, kneading and vulcanization, the unsaturated olefin double bonds on the composite polybutadiene and silicone rubber can be chemically cross-linked with the styrene-butadiene rubber to construct a three-dimensional multi-dimensional cross-linked network in the composite rubber material, thereby improving the cross-linking degree between material molecules and preparing the composite rubber material. Through the mutual coordination between the material components, not only the wear resistance and tear resistance of the composite rubber material are effectively improved, but also the mechanical properties of the composite rubber material are improved.

[0037] 2. The wear-resistant and tear-resistant composite rubber material of the present application is prepared by modifying polybutadiene and introducing triethoxysilane into the polybutadiene molecular chain to improve its reactivity with inorganic materials, so that when the modified carbon black, modified graphene and aramid pulp are ball-milled and mixed with the modified polybutadiene, they can form a composite network cross-linking system with the modified polybutadiene; graphene itself has excellent mechanical properties and wear resistance, and 1-aminopropyl-3-methylimidazolium bromide is introduced into its surface through chemical modification to increase its surface hydrophilicity and compatibility with other materials, which, on the one hand, enables the modified graphene to be evenly dispersed when preparing the composite polybutadiene, and on the other hand, can promote the combination of graphene and styrene-butadiene rubber to form a stronger interface bond force, reducing the peeling and shedding of materials during wear, thereby improving wear resistance, tear resistance and mechanical strength; carbon black has high mechanical strength and modulus. By modifying it, introducing a nickel metal layer on its surface and compounding it with modified polybutadiene, a fiber-like reinforcement network is formed in the composite rubber material, which has the ability to resist fracture when the material is subjected to external force, and can hinder the expansion and propagation of cracks, thereby delaying the tearing process of the material, preventing the material from tearing rapidly in local areas, and improving the tear resistance of the material. The metal nickel layer modified on the surface of the modified carbon black can effectively improve the wear resistance of the modified carbon black, and compounded with modified graphene to construct a wear-resistant reinforcement system in the composite rubber material, further improving the overall comprehensive performance of the material.

[0038] 3. The wear-resistant and tear-resistant composite rubber material of the present application optimizes the method for preparing composite polybutadiene so that modified polybutadiene can be blended with aramid pulp to form a stable whole. The high strength property of aramid pulp enables aramid pulp fibers to bear part of the load when the composite rubber material is subjected to tensile load, and evenly transfer the load to the entire composite rubber material, thereby improving the tensile strength of the material. In addition, aramid pulp forms a fiber-like reinforcement network in the rubber matrix, which can cooperate with modified graphene and modified carbon black to further improve the mechanical strength and tear resistance of the composite rubber material. Hexamethylhexavinylcyclohexasiloxane has a low viscosity. When it is added to the rubber mixture, it can effectively reduce the viscosity of the entire system and improve the overall processing performance of the composite rubber material. In addition, since the molecular chain structure of hexamethylhexavinylcyclohexasiloxane has a certain flexibility, it can It can play a certain buffering role when the rubber is subjected to tearing force, reduce stress concentration and crack propagation, and thus improve the tear resistance of the composite rubber material. During the mixing and kneading process, the molecular chains of styrene-butadiene rubber, hexamethylhexavinylcyclohexasiloxane and composite polybutadiene are entangled with each other to form an interpenetrating network structure, so that the material can more effectively disperse and transfer stress when subjected to tearing force, thereby enhancing the tear resistance. In addition, during the mixing and kneading process, the rubber molecular chains are oriented and arranged under the action of mechanical shear force. This orderly arrangement is beneficial to improving the tensile strength of the material. Under the action of vulcanization accelerator and vulcanizing agent, the unsaturated olefins on the composite polybutadiene and hexamethylhexavinylcyclohexasiloxane can cross-link with styrene-butadiene rubber to form a cross-linking structure, thereby increasing the cross-linking density of the composite rubber material, thereby increasing the material's ability to more effectively resist deformation and fracture when subjected to tensile force, thereby improving the mechanical strength. DETAILED DESCRIPTION

[0039] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] The density of the polybutadiene used in this application is 0.9 g / cm 3 , molecular weight is 1530-2070; aramid pulp is aramid 1414 pulp, average length is 2-2.5mm, surface area is 8m 2 / g; styrene-butadiene rubber is SBR-1502. Example 1

[0041] This embodiment provides a method for preparing a composite polybutadiene for a wear-resistant and high-tear strength composite rubber material, comprising the following steps:

[0042] S1. Preparation of modified graphene

[0043] Weigh: 30 g of graphene oxide, 1000 mL of deionized water and 50 g of potassium hydroxide are added to a reactor, ultrasonically dispersed for 40 min, stirred, the temperature of the reactor is raised to 70 ° C, 10 g of 1-aminopropyl-3-methylimidazolium bromide is added to the reactor, and the reaction is kept warm for 60 min. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70 ° C, and vacuum dried to constant weight to obtain modified graphene.

[0044] S2. Preparation of modified carbon black

[0045] 6 mol / L nitric acid, 10 wt% hydrogen peroxide and sodium dodecyl sulfate were mixed in a dosage ratio of 10 mL:4 mL:0.5 g to obtain a pretreatment solution;

[0046] Weigh: 50 g of carbon black and 500 mL of pretreatment solution are added to a reactor and stirred. The temperature of the reactor is raised to 80°C and kept warm for 30 minutes. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and dried to constant weight to obtain pretreated carbon black;

[0047] Weigh: 50 g of pre-treated carbon black, 1.5 g of dopamine hydrochloride and 500 mL of buffer solution, add them into a reactor and stir, raise the temperature of the reactor to 40°C, and keep the reaction for 20 hours. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at a temperature of 60°C, and vacuum dry it to constant weight to obtain activated carbon black, wherein the buffer solution is a 1 mol / L Tris hydrochloride solution with a pH of 8.5;

[0048] Weigh: 50 g of activated carbon black and 250 mL of 0.7 mol / L silver nitrate are added to a reactor and stirred. The temperature of the reactor is raised to 45°C and kept warm for 2 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and dried to constant weight to obtain loaded carbon black;

[0049] Nickel sulfate, sodium tartrate, sodium oxalate, boric acid and deionized water were uniformly mixed in a dosage ratio of 1.5 g: 2 g: 2 g: 1 g: 150 mL to obtain a plating solution for later use;

[0050] Weigh: 100 g of loaded carbon black and 400 mL of plating solution are added to the reactor and stirred. The reaction is carried out at room temperature for 3 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and dried to constant weight to obtain modified carbon black.

[0051] S3. Preparation of modified polybutadiene

[0052] Weigh: 300 g of polybutadiene and 2000 mL of toluene are added to a nitrogen-protected reactor and stirred. The temperature of the reactor is raised to 70°C and stirred until the system is dissolved. 100 g of KH-590 is added to the reactor and stirred for 20 min. 5 g of dilauroyl peroxide is added to the reactor and the reaction is kept warm for 3 h. After the reaction is completed, the temperature of the reactor is lowered to room temperature. 1000 mL of anhydrous ethanol is added to the reactor. A large amount of solid is precipitated. Stir and crush for 20 min. Filter by suction. Wash the filter cake with anhydrous ethanol 3 times and then dry it. Transfer the filter cake to a drying oven at 60°C and dry it to constant weight to obtain modified polybutadiene.

[0053] S4. Preparation of composite polybutadiene

[0054] Weigh: 140 g of aramid pulp, 40 g of modified carbon black, 20 g of modified graphene, 600 g of modified polybutadiene, 1000 mL of xylene and 140 mL of 1 mol / L acetic acid solution, add into a ball mill, ball mill for 4 h, take out the reactant from the ball mill, extract the reactant with xylene for 6 h, and obtain composite polybutadiene. Example 2

[0055] This embodiment provides a method for preparing a composite polybutadiene for a wear-resistant and high-tear strength composite rubber material, comprising the following steps:

[0056] S1. Preparation of modified graphene

[0057] Weigh: 30 g of graphene oxide, 1000 mL of deionized water and 50 g of potassium hydroxide, add them to a reactor, ultrasonically disperse for 50 minutes, stir, raise the temperature of the reactor to 75°C, add 1-aminopropyl-3-methylimidazolium bromide 10 g to the reactor, keep warm for 75 minutes, after the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until neutral and then dry, transfer the filter cake to a drying oven at a temperature of 75°C, and vacuum dry to constant weight to obtain modified graphene.

[0058] S2. Preparation of modified carbon black

[0059] 7 mol / L nitric acid, 10 wt% hydrogen peroxide and sodium dodecyl sulfate were mixed in a dosage ratio of 10 mL:4 mL:0.5 g to obtain a pretreatment solution;

[0060] Weigh: 50 g of carbon black and 500 mL of pretreatment solution, add them into a reactor and stir, raise the temperature of the reactor to 85°C, and keep it warm for 40 minutes. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral, and then drain it. Transfer the filter cake to a drying oven at a temperature of 75°C and dry it to constant weight to obtain pretreated carbon black;

[0061] Weigh: 50 g of pre-treated carbon black, 1.5 g of dopamine hydrochloride and 500 mL of buffer solution, add them into a reactor and stir, raise the temperature of the reactor to 45°C, and keep the reaction for 21 hours. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at a temperature of 65°C, and vacuum dry to constant weight to obtain activated carbon black, wherein the buffer solution is a 1 mol / L Tris hydrochloride solution with a pH of 8.5;

[0062] Weigh: 50 g of activated carbon black and 250 mL of 1.0 mol / L silver nitrate, add them into a reactor and stir, raise the temperature of the reactor to 50°C, and keep the reaction for 2.5 hours. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral, and then drain, transfer the filter cake to a drying oven at a temperature of 75°C, and dry it to constant weight to obtain loaded carbon black;

[0063] Nickel sulfate, sodium tartrate, sodium oxalate, boric acid and deionized water were uniformly mixed in a dosage ratio of 1.5 g: 2 g: 2 g: 1 g: 150 mL to obtain a plating solution for later use;

[0064] Weigh: 100 g of loaded carbon black and 400 mL of plating solution are added to the reactor and stirred. The reaction is carried out at room temperature for 3.5 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 75°C and dried to constant weight to obtain modified carbon black.

[0065] S3. Preparation of modified polybutadiene

[0066] Weigh: 300 g of polybutadiene and 2000 mL of toluene are added to a nitrogen-protected reactor and stirred. The temperature of the reactor is raised to 75°C and stirred until the system is dissolved. 100 g of KH-590 is added to the reactor and stirred for 25 min. 5 g of dilauroyl peroxide is added to the reactor and the reaction is kept warm for 4 h. After the reaction is completed, the temperature of the reactor is lowered to room temperature. 1000 mL of anhydrous ethanol is added to the reactor. A large amount of solid is precipitated. Stir and crush for 25 min. Filter by suction. Wash the filter cake with anhydrous ethanol 3 times and then dry it. Transfer the filter cake to a drying oven at 65°C and dry it to constant weight to obtain modified polybutadiene.

[0067] S4. Preparation of composite polybutadiene

[0068] Weigh: 140 g of aramid pulp, 40 g of modified carbon black, 20 g of modified graphene, 600 g of modified polybutadiene, 1000 mL of xylene and 140 mL of 1 mol / L acetic acid solution, add into a ball mill, ball mill for 4 h, take out the reactant from the ball mill, extract the reactant with xylene for 7 h, and obtain composite polybutadiene. Example 3

[0069] This embodiment provides a method for preparing a composite polybutadiene for a wear-resistant and high-tear strength composite rubber material, comprising the following steps:

[0070] S1. Preparation of modified graphene

[0071] Weigh: 30 g of graphene oxide, 1000 mL of deionized water and 50 g of potassium hydroxide are added to a reactor, ultrasonically dispersed for 60 min, stirred, the temperature of the reactor is raised to 80 ° C, 10 g of 1-aminopropyl-3-methylimidazolium bromide is added to the reactor, and the reaction is kept warm for 90 min. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 80 ° C, and vacuum dried to constant weight to obtain modified graphene.

[0072] S2. Preparation of modified carbon black

[0073] 8 mol / L nitric acid, 10 wt% hydrogen peroxide and sodium dodecyl sulfate were mixed in a dosage ratio of 10 mL:4 mL:0.5 g to obtain a pretreatment solution;

[0074] Weigh: 50 g of carbon black and 500 mL of pretreatment solution, add them into a reactor and stir, raise the temperature of the reactor to 90°C, and keep it warm for 50 minutes. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral, and then drain it. Transfer the filter cake to a drying oven at 80°C and dry it to constant weight to obtain pretreated carbon black;

[0075] Weigh: 50 g of pre-treated carbon black, 1.5 g of dopamine hydrochloride and 500 mL of buffer solution, add them into a reactor and stir, raise the temperature of the reactor to 50°C, and keep the reaction for 22 hours. After the reaction is completed, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at a temperature of 70°C, and vacuum dry it to constant weight to obtain activated carbon black, wherein the buffer solution is a 1 mol / L Tris hydrochloride solution with a pH of 8.5;

[0076] Weigh: 50 g of activated carbon black and 250 mL of 1.3 mol / L silver nitrate are added to a reactor and stirred. The temperature of the reactor is raised to 55°C and kept for reaction for 3 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 80°C and dried to constant weight to obtain loaded carbon black;

[0077] Nickel sulfate, sodium tartrate, sodium oxalate, boric acid and deionized water were uniformly mixed in a dosage ratio of 1.5 g: 2 g: 2 g: 1 g: 150 mL to obtain a plating solution for later use;

[0078] Weigh: 100 g of loaded carbon black and 400 mL of plating solution are added to the reactor and stirred. The reaction is carried out at room temperature for 4 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, and the filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 80°C and dried to constant weight to obtain modified carbon black.

[0079] S3. Preparation of modified polybutadiene

[0080] Weigh: 300 g of polybutadiene and 2000 mL of toluene are added to a nitrogen-protected reactor and stirred. The temperature of the reactor is raised to 80°C and stirred until the system is dissolved. 100 g of KH-590 is added to the reactor and stirred for 30 min. 5 g of dilauroyl peroxide is added to the reactor and the reaction is kept warm for 5 h. After the reaction is completed, the temperature of the reactor is lowered to room temperature. 1000 mL of anhydrous ethanol is added to the reactor. A large amount of solid is precipitated. Stir and crush for 30 min, filter, wash the filter cake with anhydrous ethanol 3 times and then dry it. The filter cake is transferred to a drying oven at 70°C and dried to constant weight to obtain modified polybutadiene.

[0081] S4. Preparation of composite polybutadiene

[0082] Weigh: 140 g of aramid pulp, 40 g of modified carbon black, 20 g of modified graphene, 600 g of modified polybutadiene, 1000 mL of xylene and 140 mL of 1 mol / L acetic acid solution, add into a ball mill, ball mill for 4 h, take out the reactant from the ball mill, extract the reactant with xylene for 8 h, and obtain composite polybutadiene. Example 4

[0083] This embodiment provides a method for preparing a composite rubber material with high wear resistance and tear resistance, comprising the following steps:

[0084] Step 1: Prepare the rubber mixture

[0085] The antioxidant A, calcium stearate, dibutyl phthalate and flame retardant are uniformly mixed in a weight ratio of 2:1:5:3 to obtain an auxiliary additive, wherein the flame retardant is composed of ammonium polyphosphate, aluminum hydroxide and magnesium hydroxide in a weight ratio of 5:3:2;

[0086] Weigh 80 parts of styrene-butadiene rubber, 15 parts of hexamethylhexavinylcyclohexasiloxane, 20 parts of the composite polybutadiene prepared in Example 1 and 3 parts of auxiliary additives by weight, add them into an internal mixer, set the temperature of the internal mixer to 90° C., the speed to 70 r / min, mix for 2 min, add the composite polybutadiene into the internal mixer, mix for 5 min, cool after discharging, and obtain internal mixer rubber;

[0087] Step 2: Preparation of rubber compound

[0088] 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide and zinc diethyldithiocarbamate are uniformly mixed in a weight ratio of 2:1:1 to obtain a vulcanization accelerator for later use;

[0089] Mix sulfur and dicumyl peroxide in a weight ratio of 3:1 to obtain a vulcanizing agent for later use;

[0090] Set the roller gap of the mixing mill to 1 mm and the temperature to 70°C;

[0091] Weigh by weight: add 100 parts of mixed rubber to an open mill to plasticize and make a roll, add 1 part of vulcanization accelerator to the open mill, and after all the materials are consumed, tap the rubber three times on the left and right sides respectively, add 2 parts of vulcanizing agent to the open mill, tap the rubber three times on the left and right sides again, make triangle rolls 10 times, cool down after discharging, and obtain mixed rubber;

[0092] Step 3: Preparation of composite rubber material

[0093] The mixed rubber was added into a flat plate vulcanizer, and the temperature of the flat plate vulcanizer was set to 170°C, the pressure to 10 MPa, the vulcanization time to 30 min, and the material was discharged after cooling to obtain a composite rubber material. Example 5

[0094] This embodiment provides a method for preparing a composite rubber material with high wear resistance and tear resistance, comprising the following steps:

[0095] Step 1: Prepare the rubber mixture

[0096] The antioxidant H, zinc stearate, diisooctyl phthalate and flame retardant are uniformly mixed in a weight ratio of 2:1:5:3 to obtain an auxiliary additive, wherein the flame retardant is composed of ammonium polyphosphate, aluminum hydroxide and magnesium hydroxide in a weight ratio of 5:3:2;

[0097] Weigh by weight: 90 parts of styrene-butadiene rubber, 16 parts of hexamethylhexavinylcyclohexasiloxane, 23 parts of the composite polybutadiene prepared in Example 2 and 4 parts of auxiliary additives, add them into an internal mixer, set the temperature of the internal mixer to 95° C., the speed to 75 r / min, mix for 2.5 min, add the composite polybutadiene into the internal mixer, mix for 7 min, cool after discharge, and obtain internal mixer rubber;

[0098] Step 2: Preparation of rubber compound

[0099] 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide and zinc diethyldithiocarbamate are uniformly mixed in a weight ratio of 2:1:1 to obtain a vulcanization accelerator for later use;

[0100] Mix sulfur and dicumyl peroxide in a weight ratio of 3:1 to obtain a vulcanizing agent for later use;

[0101] Set the roll gap of the mixing mill to 1.5 mm and the temperature to 75°C;

[0102] Weigh by weight: 105 parts of mixed rubber are added to an open mill to plasticize and roll the roll, 1.5 parts of vulcanization accelerator are added to the open mill, and after all the materials are consumed, the rubber is tapped three times on the left and right sides respectively, 2.5 parts of vulcanizing agent are added to the open mill, and the rubber is tapped three times on the left and right sides again, and triangle rolls are made 15 times. After discharging the materials, the temperature is lowered to obtain mixed rubber;

[0103] Step 3: Preparation of composite rubber material

[0104] The mixed rubber was added into a flat plate vulcanizer, and the temperature of the flat plate vulcanizer was set to 175°C, the pressure to 12 MPa, the vulcanization time to 40 min, and the material was discharged after cooling to obtain a composite rubber material. Example 6

[0105] This embodiment provides a method for preparing a composite rubber material with high wear resistance and tear resistance, comprising the following steps:

[0106] Step 1: Prepare the rubber mixture

[0107] The antioxidant CPPD, barium stearate, dimethyl phthalate and flame retardant are uniformly mixed in a weight ratio of 2:1:5:3 to obtain an auxiliary additive, wherein the flame retardant is composed of ammonium polyphosphate, aluminum hydroxide and magnesium hydroxide in a weight ratio of 5:3:2;

[0108] Weigh by weight: 100 parts of styrene-butadiene rubber, 17 parts of hexamethylhexavinylcyclohexasiloxane, 25 parts of the composite polybutadiene prepared in Example 3 and 5 parts of auxiliary additives, add them into an internal mixer, set the temperature of the internal mixer to 100° C., the speed to 80 r / min, mix for 3 min, add the composite polybutadiene into the internal mixer, mix for 10 min, cool after discharge, and obtain internal mixer rubber;

[0109] Step 2: Preparation of rubber compound

[0110] 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide and zinc diethyldithiocarbamate are uniformly mixed in a weight ratio of 2:1:1 to obtain a vulcanization accelerator for later use;

[0111] Mix sulfur and dicumyl peroxide in a weight ratio of 3:1 to obtain a vulcanizing agent for later use;

[0112] Set the roller gap of the mixing mill to 2 mm and the temperature to 80°C;

[0113] Weigh by weight: add 110 parts of mixed rubber to an open mill to plasticize and roll, add 2 parts of vulcanization accelerator to the open mill, tap the rubber three times on the left and right sides respectively after all the materials are consumed, add 3 parts of vulcanizing agent to the open mill, tap the rubber three times on the left and right sides again, make triangle rolls 15 times, cool down after discharging, and obtain mixed rubber;

[0114] Step 3: Preparation of composite rubber material

[0115] The mixed rubber was added into a flat plate vulcanizer, the temperature of the flat plate vulcanizer was set to 180°C, the pressure was set to 14 MPa, the vulcanization time was set to 50 min, the temperature was lowered and the material was discharged to obtain a composite rubber material.

[0116] Comparative Example 1

[0117] The difference between this comparative example and Example 6 is that hexamethylhexavinylcyclohexasiloxane is not added in step 1.

[0118] Comparative Example 2

[0119] The difference between this comparative example and Example 6 is that, in the preparation process of the composite polybutadiene prepared in Example 3 used in step 1, step S1 is omitted, and the modified graphene in step S4 is replaced by the graphene oxide in step S1.

[0120] Comparative Example 3

[0121] The difference between this comparative example and Example 6 is that in the preparation process of the composite polybutadiene prepared in Example 3 used in step 1, the modified carbon black in step S4 is replaced by the activated carbon black in step S2.

[0122] Comparative Example 4

[0123] The difference between this comparative example and Example 6 is that in the preparation process of the composite polybutadiene prepared in Example 3 used in Step 1, no aramid pulp is added in Step S4.

[0124] Performance Test:

[0125] The wear resistance, tear resistance and mechanical properties of the composite rubber materials prepared in Examples 4-6 and Comparative Examples 1-4 were tested. The wear resistance was measured by referring to the standard GB / T 9867-2008 "Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrader method)" to measure the relative volume wear of the sample; the tear resistance was measured by referring to the standard GB / T 529-2008 "Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens)" to measure the tear strength of the sample; the mechanical properties were measured by referring to the standard GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber" to measure the tensile strength and elongation at break of the sample. The specific test results are shown in Table 1.

[0126] Table 1. Performance test data of samples

[0127] Group Project <![CDATA[Relative volume wear amount / mm 3 > <![CDATA[Tear strength / kN·m -1 > Tensile strength / MPa Elongation at break / % Example 4 86 63.5 28.8 535 Example 5 82 64.3 29.1 542 Example 6 84 63.8 28.7 531 Comparative Example 1 105 62.4 28.1 501 Comparative Example 2 101 60.3 27.6 483 Comparative Example 3 121 62.9 28.3 511 Comparative Example 4 99 58.4 24.5 467

[0128] Data Analysis:

[0129] Comparing and analyzing the data in Table 1 above, the relative volume wear of the composite rubber material prepared by the present invention is reduced to 82 mm 3 The tear strength reaches 64.3 kN / m, the tensile strength reaches 29.1 MPa, and the elongation at break reaches 542%. All performance parameters are better than those of the comparative example, indicating that the present invention strengthens the modified polybutadiene by aramid pulp, modified carbon black, and modified graphene to prepare composite polybutadiene, and then uses the prepared composite polybutadiene and silicone rubber to strengthen and modify the styrene-butadiene rubber. By increasing the crosslinking degree between material molecules and optimizing the material composition, not only the wear resistance and tear resistance of the composite rubber material are effectively improved, but also the mechanical properties of the composite rubber material are improved.

[0130] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0131] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0132] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A composite rubber material with wear resistance and high tear resistance, characterized in that: The invention comprises the following components in parts by weight: 100-110 parts of internal mixing rubber, 1-2 parts of vulcanization accelerator and 2-3 parts of vulcanizing agent; The internal rubber compound comprises the following components in parts by weight: 80-100 parts of styrene-butadiene rubber, 15-17 parts of silicone rubber, 20-25 parts of composite polybutadiene and 3-5 parts of auxiliary additives; The composite polybutadiene is obtained by processing the following steps: A1. Add polybutadiene and toluene to a nitrogen-protected reactor and stir. Raise the reactor temperature to 70-80°C and stir until the system is dissolved. Add KH-590 to the reactor and stir for 20-30 minutes. Add initiator to the reactor and keep the reaction temperature for 3-5 hours. Post-treat to obtain modified polybutadiene. A2, adding aramid pulp, modified carbon black, modified graphene, modified polybutadiene, xylene and catalyst solution into a ball mill, ball milling for 4 hours, and post-processing to obtain composite polybutadiene; The modified carbon black is obtained by processing the following steps: B1. Add carbon black and pretreatment solution into a reactor and stir. Raise the temperature of the reactor to 80-90°C and keep warm for 30-50 minutes. Post-treat to obtain pretreated carbon black. B2, adding the pre-treated carbon black, dopamine hydrochloride and buffer into the reactor and stirring, raising the temperature of the reactor to 40-50°C, keeping the temperature for reaction for 20-22h, and post-treating to obtain activated carbon black; B3, adding activated carbon black and silver nitrate into a reaction kettle and stirring, raising the temperature of the reaction kettle to 45-55°C, keeping the temperature for reaction for 2-3h, and post-treating to obtain loaded carbon black; B4, adding the loaded carbon black and the plating solution into a reactor and stirring, reacting at room temperature for 3-4 hours, and post-treating to obtain modified carbon black; The preparation method of the modified graphene comprises: adding graphene oxide, deionized water and potassium hydroxide into a reaction kettle, ultrasonically dispersing for 40-60 minutes, stirring, raising the temperature of the reaction kettle to 70-80° C., adding 1-aminopropyl-3-methylimidazolium bromide into the reaction kettle, keeping the temperature for reaction for 60-90 minutes, and post-treating to obtain the modified graphene.

2. The wear-resistant and high-tear-strength composite rubber material according to claim 1, characterized in that: The silicone rubber is hexamethylhexavinylcyclohexasiloxane, the vulcanization accelerator is composed of 2-thiolbenzothiazole, N-tert-butyl-2-benzothiazolesulfonamide and zinc diethyldithiocarbamate in a weight ratio of 2:1:1, and the vulcanizing agent is composed of sulfur and diisopropylbenzene peroxide in a weight ratio of 3:

1.

3. The wear-resistant and high-tear-strength composite rubber material according to claim 1, characterized in that: In step A1, the amount ratio of the polybutadiene, toluene, KH-590 and the initiator is 3g:20mL:1g:0.05g, and the initiator is dilauroyl peroxide; in step A2, the amount ratio of the aramid pulp, modified carbon black, modified graphene, modified polybutadiene, xylene and the catalyst solution is 7g:2g:1g:30g:50mL:7mL, and the catalyst solution is 1mol / L acetic acid solution.

4. The wear-resistant and high-tear-strength composite rubber material according to claim 1, characterized in that: In step B1, the pretreatment solution is composed of 6-8 mol / L nitric acid, 10 wt% hydrogen peroxide and sodium dodecyl sulfate in a dosage ratio of 10 mL: 4 mL: 0.5 g, and the dosage ratio of the carbon black to the pretreatment solution is 1 g: 10 mL; in step B2, the buffer is a 1 mol / L Tris hydrochloride solution with a pH of 8.5, and the dosage ratio of the pretreatment carbon black, dopamine hydrochloride and the buffer is 10 g: 100 mL: 0.3 g; in step B3, the concentration of the silver nitrate is 0.7-1.3 mol / L, and the dosage ratio of the activated carbon black to the silver nitrate is 1 g: 5 mL; in step B4, the plating solution is composed of nickel sulfate, sodium tartrate, sodium oxalate, boric acid and deionized water in a dosage ratio of 1.5 g: 2 g: 2 g: 1 g: 150 mL, and the dosage ratio of the loaded carbon black to the plating solution is 1 g: 4 mL.

5. The wear-resistant and high-tear-strength composite rubber material according to claim 1, characterized in that: The usage ratio of the graphene oxide, deionized water, potassium hydroxide and 1-aminopropyl-3-methylimidazolium bromide is 3g:100mL:5g:1g.

6. The method for preparing a wear-resistant and high-tear strength composite rubber material according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, adding styrene-butadiene rubber, silicone rubber and auxiliary additives into an internal mixer, setting the temperature of the internal mixer to 90-100°C, the speed to 70-80r / min, mixing for 2-3min, adding composite polybutadiene into the internal mixer, mixing for 5-10min, cooling after discharge, and obtaining internal mixer rubber; S2, set the roller spacing of the open mill to 1-2mm, the temperature to 70-80 ° C, add the internal rubber to the open mill to plasticize and roll the roll, add the vulcanization accelerator to the open mill, after all the materials are eaten, tap the rubber three times on the left and right sides, add the vulcanizing agent to the open mill, tap the rubber three times on the left and right sides, make triangle packages 10-15 times, cool down after discharging, and obtain mixed rubber; S3, adding the mixed rubber into a flat plate vulcanizer, vulcanizing, and obtaining a composite rubber material.

7. The method for preparing a wear-resistant and high-tear strength composite rubber material according to claim 6, characterized in that: In step S1, the auxiliary additives are composed of an antioxidant, a dispersant, a plasticizer and a flame retardant in a weight ratio of 2:1:5:3, the antioxidant is one or more of antioxidant A, antioxidant H, antioxidant D, and antioxidant CPPD, the dispersant is a stearate, the plasticizer is a phthalate, and the flame retardant is composed of ammonium polyphosphate, aluminum hydroxide and magnesium hydroxide in a weight ratio of 5:3:2; in step S3, the temperature of the flat vulcanizer is 170-180°C, the pressure is 10-14MPa, and the vulcanization time is 30-50min.