CN114276597A - Non-pneumatic tire rubber material with modified white carbon black filler - Google Patents
Non-pneumatic tire rubber material with modified white carbon black filler Download PDFInfo
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Abstract
The invention provides a non-pneumatic tire rubber material with modified white carbon black filler, which comprises 100 parts of waste tire reclaimed rubber powder containing fiber, 50-100 parts of solution polymerized styrene butadiene rubber (SSBR), 50-100 parts of modified white carbon black, 20-40 parts of silane coupling agent and the like; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan. The rubber material for the non-pneumatic tire provided by the invention has the advantages of high wet skid resistance, low rolling resistance and good wear resistance. The modified white carbon black is added into the material, the chitosan is utilized to load the carbon nano tube on the surface of the white carbon black, and the carbon nano tube is uniformly loaded on the surface of the white carbon black, so that the performance of a sizing material is not influenced, the conductivity of the material is improved, and the static accumulation is avoided.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a non-pneumatic tire rubber material with modified white carbon black filler and modified white carbon black for producing non-pneumatic tire rubber.
Background
The tire is one of the main application products of rubber products, half of the rubber consumption in the world is used for manufacturing the tire, and the development of the rubber material applied to the tire needs strong theoretical support and innovation. Although solid tires are not the mainstream products in tires, they are widely used in important fields such as mineral mining, engineering construction and cargo transportation due to their good load-carrying capacity and safety. In practical application, although solid rubber tires have many advantages, the further popularization and application of the solid rubber tires are limited due to poor performance of carcass materials and over-simple structure.
The selection of the carcass material of the solid tire is the key of tire manufacturing, the rubber material is used as a material with high elasticity and stress deformation recoverability, the application in the aspect of tire manufacturing has been for many years, and the rubber is selected as the carcass material of the current mainstream solid tire.
Tires are required to have a combination of safety, economy, and comfort. Conventional tire rubbers are produced by blending and using Natural Rubber (NR), Butadiene Rubber (BR), and Emulsion Styrene Butadiene Rubber (ESBR), and it is difficult for such rubber compounds to achieve the aim of both high wet skid resistance and low rolling resistance. The hysteresis loss and glass transition temperature (Tg) of the tire rubber greatly affect the wet skid resistance. SSBR is one of styrene-butadiene rubbers and is also a very widely used compound as a tire material. The SSBR has adjustable relative molecular mass, belongs to special rubber in styrene butadiene rubber, and is suitable for producing tire rubber. The SSBR has the advantages of low Tg, small extrusion shrinkage, stable size, low power in the mixing process and small heat generation, and can enable the rubber compound to have low hysteresis heat generation and high wear resistance when being used for tire materials. However, since the end structure of the SSBR molecule affects the rolling resistance and wet skid resistance of the rubber material, there is a need for modification to further improve the wet skid resistance and reduce the rolling resistance.
Rubber materials often require the addition of fillers in the manufacture of articles for both household and industrial use. Of the various components of the rubber, the amount of filler is the greatest, with the exception of the raw rubber. The addition of the filler can improve the physical and mechanical properties of the rubber product, such as stress at definite elongation, tensile strength, tear strength and the like, and various properties such as wear resistance, heat resistance, cold resistance, oil resistance and the like, prolong the service life of the product, improve the processability of the rubber product to a certain extent and reduce the production cost. White carbon black is a newly developed reinforcing filler in the rubber industry.
The white carbon black is hydrated silicon dioxide (SiO)2) Containing partially crystallized water and having the formula Si02-nH2O, primary particles having a particle size of 10nm to 40nm are easily agglomerated because the surfaces thereof are rich in silicon hydroxyl groups. White carbon black is a commonly used enhanced filler in the rubber field, is insoluble in water and can be mutually soluble with solvents such as strong base and the like. The white carbon black has a very special surface structure, presents obvious porosity, has a large surface area, has good chemical stability, and has excellent high-temperature resistance, flame retardance and electrical insulation. The Si-O structure of the white carbon black and the silicon hydroxyl groups on the surface enable the white carbon black to have weak affinity with rubber molecular chains, so that the dispersion effect is poor, in other words, due to the existence of the surface hydroxyl groups, the surface energy is increased, so that aggregates are easily formed by the interaction among particles, and larger aggregates are easily formed among the aggregates, so that the applicability of the product is greatly influenced. Meanwhile, the problem that static electricity cannot be led out exists in a sizing material filled with a large amount of white carbon black, and currently, an antistatic agent is usually added to solve the problem, however, the effect is not good, and meanwhile, the addition of the antistatic agent influences other properties of the sizing material.
The tire tread is required to have high speed and safety performance, comfort performance, energy-saving performance and the like, and the tread rubber is required to have performances of three aspects of high wet skid resistance, low rolling resistance and good wear resistance. Therefore, further modification of a rubber material for a tire is required to satisfy the three properties of high wet skid resistance, low rolling resistance and good abrasion resistance.
Disclosure of Invention
The technical problem is as follows: in order to solve the defects of the prior art, the invention aims to provide a low rolling resistance and high grip non-pneumatic tire rubber material.
The technical scheme is as follows: the invention provides a modified white carbon black filler non-pneumatic tire rubber material, which comprises 100 parts of waste tire regenerated rubber powder containing fibers, 50-100 parts of solution polymerized styrene-butadiene rubber (SSBR), 50-100 parts of modified white carbon black, 20-40 parts of a silane coupling agent, 10-30 parts of aramid fibers, 5-10 parts of modified carbon fibers, 6-10 parts of an anti-aging agent, 6-10 parts of sulfur, 10-30 parts of aromatic oil, 1-6 parts of zinc oxide, 1-6 parts of stearic acid and 1-6 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan.
Preferably, the non-pneumatic tire rubber material with the modified white carbon black filler comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 80 parts of solution polymerized styrene-butadiene rubber (SSBR), 80 parts of modified white carbon black, 30 parts of a silane coupling agent, 20 parts of aramid fibers, 8 parts of modified carbon fibers, 8 parts of an anti-aging agent, 8 parts of sulfur, 20 parts of aromatic oil, 3 parts of zinc oxide, 3 parts of stearic acid and 3 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 40% of the mass of the white carbon black, and the mass of the carbon nano tubes is 50% of the mass of the chitosan.
Preferably, the modified white carbon black is prepared by the following method:
(1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing, and adding K5-10% of chitosan2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2) adding multi-or single-walled carbon nanotubes to HNO3/H2SO4Mixing with mixed acid solution to obtain 0.02-0.05g/mL carbon nanotube solution, heating to boiling state, refluxing for 40-70min, filtering with filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60h；HNO3And H2SO4The mass of (2-4) to 1;
(3) dissolving the carbon nano tube acidified in the step (2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan.
Preferably, the fiber-containing waste tire reclaimed rubber powder is prepared by the following method: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; and in the process that the fine particles are pushed to advance by the screw in the machine cavity of the screw desulfurization machine, the rubber material is desulfurized and regenerated at the temperature of 250-350 ℃ under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, so that the fiber-containing waste tire regenerated rubber powder is obtained.
More preferably, the softener is a vegetable oil, pine tar or tall oil; the activating agent is prepared from the following components in a mass ratio of 10: (1-3): (1-2): (2-4) a composition of calcium hydroxide, calcium sulfate, calcium oxide and dextrin, or a mixture of the calcium hydroxide, the calcium sulfate, the calcium oxide and the dextrin in a mass ratio of 10: (1-3): (1-2): (2-4) magnesium hydroxide, titanium dioxide, iron oxide and carboxymethyl cellulose.
Preferably, the modified carbon fiber is prepared by adopting the following method: and (3) placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain the modified carbon fiber with the surface subjected to oxidation treatment.
The invention also provides a preparation method of the non-pneumatic tire rubber material with the modified white carbon black filler, which comprises the following steps:
(1) preparing fiber-containing waste tire reclaimed rubber powder: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; in the process that the fine particles are pushed to advance by a screw in a machine cavity of a screw desulfurization machine, the rubber material is desulfurized and regenerated at the temperature of 250-350 ℃ under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, and the fiber-containing waste tire regenerated rubber powder is obtained;
(2) preparing modified white carbon black:
(2.1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing uniformly, adding K with the mass of 5-10% of chitosan2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2.2) adding Multi-walled or Single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.02-0.05g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 40-70min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60 h; HNO3And H2SO4The mass of (2-4) to 1;
(2.3) dissolving the carbon nano tube acidified in the step (2.2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (2.1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan; (3) preparing modified carbon fibers: placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain modified carbon fiber subjected to surface oxidation treatment;
(4) preparing a rubber material of the non-pneumatic tire:
(4.1) adding the waste tire reclaimed rubber powder containing fibers, the solution polymerized styrene-butadiene rubber SSBR, the modified white carbon black, the silane coupling agent, the anti-aging agent, the stearic acid and the zinc oxide into an internal mixer for internal mixing, wherein the rubber discharging temperature is controlled to be 135-155 ℃;
(4.2) mixing on an open mill, controlling the roll temperature at 50-60 ℃, slowly adding sulfur, aramid fiber, modified carbon fiber, aromatic oil and hydrogenated DCPD resin, mixing for 1-2h, cooling and standing for 8 h;
and (4.3) vulcanizing the mixed system in the step (4.2) by adopting a flat vulcanizing machine, wherein the pressure and the temperature required by vulcanization are provided in the vulcanizing step, the total pressure of the flat vulcanizing machine is 210N, the maximum hydraulic pressure is 17MPa, the vulcanizing temperature is 150 ℃ and 155 ℃, and the vulcanizing time is 30-120 minutes.
Preferably, the dosage of each raw material is as follows: 100 parts of waste tire reclaimed rubber powder containing fibers, 50-100 parts of solution polymerized styrene-butadiene rubber (SSBR), 50-100 parts of modified white carbon black, 20-40 parts of silane coupling agent, 10-30 parts of aramid fiber, 5-10 parts of modified carbon fiber, 6-10 parts of anti-aging agent, 6-10 parts of sulfur, 10-30 parts of aromatic oil, 1-6 parts of zinc oxide, 1-6 parts of stearic acid and 1-6 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan.
The invention also provides a modified white carbon black filler for the non-pneumatic tire rubber material, which comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan.
The invention also provides a preparation method of the modified white carbon black filler for the non-pneumatic tire rubber material, which comprises the following steps:
(1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing, and adding K2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2) adding multi-or single-walled carbon nanotubes to HNO3/H2SO4Mixing with mixed acid solution to obtain 0.02-0.05g/mL carbon nanotube solution, heatingRefluxing for 40-70min under boiling state, filtering with filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60 hr; HNO3And H2SO4The mass of (2-4) to 1;
(3) dissolving the carbon nano tube acidified in the step (2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan.
Has the advantages that: the rubber material for the non-pneumatic tire provided by the invention has the advantages of high wet skid resistance, low rolling resistance and good wear resistance.
The material is prepared by recycling waste tires and utilizing a screw desulfurization technology to obtain fiber-containing waste tire reclaimed rubber powder, so that the product quality maintains the performance of all used SSBR rubber, and the regeneration process is simple, green and environment-friendly.
The modified white carbon black is added into the material, and the surface of the white carbon black is loaded on the carbon nano tube by utilizing chitosan, so that the surface performance and the specific surface area of the white carbon black are increased, and the strength of the rubber material is improved; meanwhile, the carbon nano tube is used as a framework, so that the compatibility and the crosslinking property of the rubber and the carbon black are greatly improved; more importantly, the carbon nano tubes are uniformly loaded on the surface of the white carbon black, so that the performance of the sizing material is not influenced, the conductivity of the white carbon black is improved, and the static accumulation is avoided.
The modified carbon fiber subjected to surface oxidation treatment is added in the material, so that the wear resistance of the rubber material is further improved.
Detailed Description
The following examples are given to further describe the present invention in detail with reference to specific embodiments. The following examples are intended to illustrate the invention, but not to limit the scope of the invention.
The experimental procedures in the following examples are conventional, except for the specific illustrations. The raw materials and test reagents used in the examples were commercially available products except for those specifically mentioned.
Example 1
The non-pneumatic tire rubber material with the modified white carbon black filler comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 80 parts of solution polymerized styrene-butadiene rubber (SSBR), 80 parts of modified white carbon black, 30 parts of silane coupling agent, 20 parts of aramid fibers, 8 parts of modified carbon fibers, 8 parts of anti-aging agent, 8 parts of sulfur, 20 parts of aromatic oil, 3 parts of zinc oxide, 3 parts of stearic acid and 3 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 40% of the mass of the white carbon black, and the mass of the carbon nano tubes is 50% of the mass of the chitosan.
The softener is vegetable oil; the activating agent is prepared from the following components in a mass ratio of 10: 2: 1.5: 3, calcium hydroxide, calcium sulfate, calcium oxide, and dextrin.
The modified white carbon black filler comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan.
The preparation method of the non-pneumatic tire rubber material with the modified white carbon black filler comprises the following steps:
(1) preparing fiber-containing waste tire reclaimed rubber powder: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; in the process that the fine particles are pushed to advance by a screw in a machine cavity of a screw desulfurization machine, the rubber material completes desulfurization regeneration under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance at the temperature of 300 ℃, so that fiber-containing waste tire regenerated rubber powder is obtained;
(2) preparing modified white carbon black:
(2.1) dissolving chitosan in 3% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing uniformly, adding K with the mass of 8% of chitosan2S2O8Reacting for 3h at 65 ℃, and drying to obtain chitosan-loaded white carbon black solution; of chitosan and acetic acidThe molar ratio is 1: 2.5;
(2.2) adding Multi-walled or Single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.04g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 60min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 70 deg.C for 50 h; HNO3And H2SO4The mass ratio of (1) to (3);
(2.3) dissolving the carbon nano tube acidified in the step (2.2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 10mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (2.1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein the mass of the chitosan is 40 percent of the mass of the white carbon black, and the mass of the carbon nano tube is 50 percent of the mass of the chitosan; (3) preparing modified carbon fibers: placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain modified carbon fiber subjected to surface oxidation treatment;
(4) preparing a rubber material of the non-pneumatic tire:
(4.1) adding the waste tire reclaimed rubber powder containing fibers, the solution polymerized styrene-butadiene rubber SSBR, the modified white carbon black, the silane coupling agent, the anti-aging agent, the stearic acid and the zinc oxide into an internal mixer for internal mixing, and controlling the rubber discharge temperature to 145 ℃;
(4.2) mixing on an open mill, controlling the roll temperature at 55 ℃, slowly adding sulfur, aramid fiber, modified carbon fiber, aromatic oil and hydrogenated DCPD resin, mixing for 1.5h, cooling and standing for 8 h;
and (4.3) vulcanizing the mixed system in the step (4.2) by adopting a flat vulcanizing machine, wherein the pressure and the temperature required by vulcanization are provided in the vulcanization step, the total pressure of the flat vulcanizing machine is 210N, the maximum hydraulic pressure is 17MPa, the vulcanization temperature is 150 ℃, and the vulcanization time is 80 minutes.
Example 2
The same as example 1 except that: the activating agent is prepared from the following components in a mass ratio of 10: 2: 1.5: 3 magnesium hydroxide, titanium dioxide, iron oxide and carboxymethyl cellulose; the organic silicon compound is acyloxy organosilane;
example 3
The non-pneumatic tire rubber material with the modified white carbon black filler comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 80 parts of solution polymerized styrene-butadiene rubber (SSBR), 80 parts of modified white carbon black, 30 parts of silane coupling agent, 20 parts of aramid fibers, 8 parts of modified carbon fibers, 8 parts of anti-aging agent, 8 parts of sulfur, 20 parts of aromatic oil, 3 parts of zinc oxide, 3 parts of stearic acid and 3 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 40% of the mass of the white carbon black, and the mass of the carbon nano tubes is 50% of the mass of the chitosan.
The softening agent is pine tar; the activating agent is prepared from the following components in a mass ratio of 10: 1: 2: 4 calcium hydroxide, calcium sulfate, calcium oxide, and dextrin.
The modified white carbon black filler comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan.
The preparation method of the non-pneumatic tire rubber material with the modified white carbon black filler comprises the following steps:
(1) preparing fiber-containing waste tire reclaimed rubber powder: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; in the process that the fine particles are pushed to advance by a screw in a machine cavity of a screw desulfurization machine, the rubber material completes desulfurization regeneration under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, so that fiber-containing waste tire regenerated rubber powder is obtained;
(2) preparing modified white carbon black:
(2.1) dissolving chitosan in 2% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing uniformly, adding K with the mass of 5% of chitosan2S2O8Reacting for 2h at 60 ℃, and drying to obtain chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is1：2；
(2.2) adding Multi-walled or Single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.02g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 40min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60 deg.C for 60 h; HNO3And H2SO4The mass of (A) is 2: 1;
(2.3) dissolving the carbon nano tube acidified in the step (2.2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (2.1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein the mass of the chitosan is 30 percent of the mass of the white carbon black, and the mass of the carbon nano tube is 40 percent of the mass of the chitosan; (3) preparing modified carbon fibers: placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain modified carbon fiber subjected to surface oxidation treatment;
(4) preparing a rubber material of the non-pneumatic tire:
(4.1) adding the waste tire reclaimed rubber powder containing fibers, the solution polymerized styrene-butadiene rubber SSBR, the modified white carbon black, the silane coupling agent, the anti-aging agent, the stearic acid and the zinc oxide into an internal mixer for internal mixing, wherein the rubber discharging temperature is controlled to be 135 ℃;
(4.2) mixing on an open mill, controlling the roll temperature at 50 ℃, slowly adding sulfur, aramid fiber, modified carbon fiber, aromatic oil and hydrogenated DCPD resin, mixing for 1h, cooling and standing for 8 h;
and (4.3) vulcanizing the mixed system in the step (4.2) by adopting a flat vulcanizing machine, wherein the pressure and the temperature required by vulcanization are provided in the vulcanization step, the total pressure of the flat vulcanizing machine is 210N, the maximum hydraulic pressure is 17MPa, the vulcanization temperature is 155 ℃, and the vulcanization time is 30 minutes.
Example 4
The same as example 1 except that: the activating agent is prepared from the following components in percentage by mass: 3: 1: 2 magnesium hydroxide, titanium dioxide, iron oxide and carboxymethyl cellulose; the organic silicon compound is bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide;
example 5
The non-pneumatic tire rubber material with the modified white carbon black filler comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 80 parts of solution polymerized styrene-butadiene rubber (SSBR), 80 parts of modified white carbon black, 30 parts of silane coupling agent, 20 parts of aramid fibers, 8 parts of modified carbon fibers, 8 parts of anti-aging agent, 8 parts of sulfur, 20 parts of aromatic oil, 3 parts of zinc oxide, 3 parts of stearic acid and 3 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 40% of the mass of the white carbon black, and the mass of the carbon nano tubes is 50% of the mass of the chitosan.
The softener is tall oil; the activating agent is prepared from the following components in a mass ratio of 10: 3: 1: 2, calcium hydroxide, calcium sulfate, calcium oxide, and dextrin.
The modified white carbon black filler comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan.
The preparation method of the non-pneumatic tire rubber material with the modified white carbon black filler comprises the following steps:
(1) preparing fiber-containing waste tire reclaimed rubber powder: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; in the process that the fine particles are pushed to advance by a screw in a machine cavity of a screw desulfurization machine, the rubber material completes desulfurization regeneration at 350 ℃ under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, and the fiber-containing waste tire regenerated rubber powder is obtained;
(2) preparing modified white carbon black:
(2.1) dissolving chitosan in 4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing uniformly, adding K with the mass of 10% of chitosan2S2O8Reacting for 4h at 70 ℃, and drying to obtain chitosan-loaded white carbon black solution; molar ratio of Chitosan to acetic acidThe ratio is 1: 3;
(2.2) adding Multi-walled or Single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.05g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 70min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 80 deg.C for 40 h; HNO3And H2SO4The mass of (1) is 4: 1;
(2.3) dissolving the carbon nano tube acidified in the step (2.2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (2.1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein the mass of the chitosan is 50 percent of the mass of the white carbon black, and the mass of the carbon nano tube is 60 percent of the mass of the chitosan; (3) preparing modified carbon fibers: placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain modified carbon fiber subjected to surface oxidation treatment;
(4) preparing a rubber material of the non-pneumatic tire:
(4.1) adding the waste tire reclaimed rubber powder containing fibers, the solution polymerized styrene-butadiene rubber SSBR, the modified white carbon black, the silane coupling agent, the anti-aging agent, the stearic acid and the zinc oxide into an internal mixer for internal mixing, wherein the rubber discharging temperature is controlled to be 155 ℃;
(4.2) mixing on an open mill, controlling the roll temperature at 60 ℃, slowly adding sulfur, aramid fiber, modified carbon fiber, aromatic oil and hydrogenated DCPD resin, mixing for 2 hours, cooling and standing for 8 hours;
and (4.3) vulcanizing the mixed system in the step (4.2) by adopting a flat vulcanizing machine, wherein the pressure and the temperature required by vulcanization are provided in the vulcanization step, the total pressure of the flat vulcanizing machine is 210N, the maximum hydraulic pressure is 17MPa, the vulcanization temperature is 155 ℃, and the vulcanization time is 120 minutes.
Example 6
The same as example 1 except that: the activating agent is prepared from the following components in a mass ratio of 10: 1: 2: 4 magnesium hydroxide, titanium dioxide, iron oxide and carboxymethyl cellulose; the organosilicon compound is triethoxysilane;
comparative example 1
The same as example 1 except that: the solution polymerized styrene butadiene rubber SSBR is adopted to replace the waste tire reclaimed rubber powder containing fiber.
Comparative example 2
The same as example 1 except that: common white carbon black is adopted to replace modified white carbon black.
Comparative example 3
The same as example 1 except that: the amount of silane coupling agent in the raw material was 0.
Comparative example 4
The same as example 1 except that: common white carbon black is adopted to replace modified white carbon black, and the dosage of the silane coupling agent in the raw materials is 0.
Comparative example 5
The same as example 1 except that: common carbon fibers are adopted to replace modified carbon fibers.
Comparative example 6
The same as example 1 except that: the solution polymerized styrene butadiene rubber SSBR is adopted to replace the regenerated rubber powder of the waste tire containing fiber; replacing modified carbon black with common carbon black; common carbon fibers are adopted to replace modified carbon fibers.
Examples of the experiments
The product properties of examples 1 to 6 and comparative examples 1 to 6 were tested.
It will be apparent to those skilled in the art that the above description of specific embodiments of the invention is not intended to limit the application of the invention, and that various equivalents and modifications may be made thereto depending on the circumstances. All such substitutions and modifications are intended to be within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The non-pneumatic tire rubber material with the modified white carbon black filler is characterized in that: the rubber material comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 50-100 parts of solution polymerized styrene-butadiene rubber (SSBR), 50-100 parts of modified white carbon black, 20-40 parts of silane coupling agent, 10-30 parts of aramid fiber, 5-10 parts of modified carbon fiber, 6-10 parts of anti-aging agent, 6-10 parts of sulfur, 10-30 parts of aromatic oil, 1-6 parts of zinc oxide, 1-6 parts of stearic acid and 1-6 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan.
2. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 1, is characterized in that: the rubber material comprises 100 parts of waste tire reclaimed rubber powder containing fibers, 80 parts of solution polymerized styrene butadiene rubber (SSBR), 80 parts of modified white carbon black, 30 parts of silane coupling agent, 20 parts of aramid fiber, 8 parts of modified carbon fiber, 8 parts of anti-aging agent, 8 parts of sulfur, 20 parts of aromatic oil, 3 parts of zinc oxide, 3 parts of stearic acid and 3 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 40% of the mass of the white carbon black, and the mass of the carbon nano tubes is 50% of the mass of the chitosan.
3. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 1, is characterized in that: the modified white carbon black is prepared by the following method:
(1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing, and adding K2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2) adding multi-or single-walled carbon nanotubesTo HNO3/H2SO4Preparing 0.02-0.05g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 40-70min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60 h; HNO3And H2SO4The mass of (2-4) to 1;
(3) dissolving the carbon nano tube acidified in the step (2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan.
4. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 1, is characterized in that: the fiber-containing waste tire reclaimed rubber powder is prepared by the following method: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; and in the process that the fine particles are pushed to advance by the screw in the machine cavity of the screw desulfurization machine, the rubber material is desulfurized and regenerated at the temperature of 250-350 ℃ under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, so that the fiber-containing waste tire regenerated rubber powder is obtained.
5. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 4, is characterized in that: the softener is vegetable oil, pine tar or tall oil; the activating agent is prepared from the following components in a mass ratio of 10: (1-3): (1-2): (2-4) a composition of calcium hydroxide, calcium sulfate, calcium oxide and dextrin, or a mixture of the calcium hydroxide, the calcium sulfate, the calcium oxide and the dextrin in a mass ratio of 10: (1-3): (1-2): (2-4) magnesium hydroxide, titanium dioxide, iron oxide and carboxymethyl cellulose.
6. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 1, is characterized in that: the modified carbon fiber is prepared by the following method: and (3) placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain the modified carbon fiber with the surface subjected to oxidation treatment.
7. The non-pneumatic tire rubber material with the modified white carbon black filler, as recited in claim 1, is characterized in that:
(1) preparing fiber-containing waste tire reclaimed rubber powder: cleaning waste tires containing fibers, crushing the waste tires in a crusher to coarse particles of 20-40mm, and carrying out primary magnetic separation on the coarse particles to obtain iron-containing impurities and coarse rubber particles; crushing the coarse rubber particles by a grinder and removing iron-containing impurities by magnetic separation for the second time to obtain fine particles of 5-10 mm; in the process that the fine particles are pushed to advance by a screw in a machine cavity of a screw desulfurization machine, the rubber material is desulfurized and regenerated at the temperature of 250-350 ℃ under the action of an activating agent, a softening agent and shearing force generated when the screw is pushed to advance, and the fiber-containing waste tire regenerated rubber powder is obtained;
(2) preparing modified white carbon black:
(2.1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing uniformly, adding K with the mass of 5-10% of chitosan2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2.2) adding Multi-walled or Single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.02-0.05g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 40-70min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60 h; HNO3And H2SO4The mass of (2-4) to 1;
(2.3) dissolving the carbon nano tube acidified in the step (2.2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (2.1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan;
(3) preparing modified carbon fibers: placing the carbon fiber in a high-frequency induction furnace, carrying out thermal oxidation treatment in the air atmosphere, and cooling along with the furnace to obtain modified carbon fiber subjected to surface oxidation treatment;
(4) preparing a rubber material of the non-pneumatic tire:
(4.1) adding the waste tire reclaimed rubber powder containing fibers, the solution polymerized styrene-butadiene rubber SSBR, the modified white carbon black, the silane coupling agent, the anti-aging agent, the stearic acid and the zinc oxide into an internal mixer for internal mixing, wherein the rubber discharging temperature is controlled to be 135-155 ℃;
(4.2) mixing on an open mill, controlling the roll temperature at 50-60 ℃, slowly adding sulfur, aramid fiber, modified carbon fiber, aromatic oil and hydrogenated DCPD resin, mixing for 1-2h, cooling and standing for 8 h;
and (4.3) vulcanizing the mixed system in the step (4.2) by adopting a flat vulcanizing machine, wherein the pressure and the temperature required by vulcanization are provided in the vulcanizing step, the total pressure of the flat vulcanizing machine is 210N, the maximum hydraulic pressure is 17MPa, the vulcanizing temperature is 150 ℃ and 155 ℃, and the vulcanizing time is 30-120 minutes.
8. The non-pneumatic tire rubber material with the modified white carbon black filler as claimed in claim 8, wherein the rubber material is prepared from the following raw materials in parts by weight: the dosage of each raw material is as follows: 100 parts of waste tire reclaimed rubber powder containing fibers, 50-100 parts of solution polymerized styrene-butadiene rubber (SSBR), 50-100 parts of modified white carbon black, 20-40 parts of silane coupling agent, 10-30 parts of aramid fiber, 5-10 parts of modified carbon fiber, 6-10 parts of anti-aging agent, 6-10 parts of sulfur, 10-30 parts of aromatic oil, 1-6 parts of zinc oxide, 1-6 parts of stearic acid and 1-6 parts of hydrogenated DCPD resin; the modified white carbon black comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tubes is 40-60% of the mass of the chitosan.
9. The modified white carbon black filler for the rubber material of the non-pneumatic tire is characterized by comprising the following components in parts by weight: the carbon black-loaded nano carbon tube composite material comprises white carbon black, chitosan loaded on the surface of the white carbon black and carbon nano tubes loaded on the surface of the chitosan, wherein the mass of the chitosan is 30-50% of that of the white carbon black, and the mass of the carbon nano tubes is 40-60% of that of the chitosan.
10. The preparation method of the modified white carbon black filler for the rubber material of the non-pneumatic tire as claimed in claim 9, is characterized in that: the method comprises the following steps:
(1) dissolving chitosan in 2-4% acetic acid water solution to obtain chitosan solution, adding white carbon black, mixing, and adding K5-10% of chitosan2S2O8Reacting for 2-4h at 60-70 ℃, and drying to obtain a chitosan-loaded white carbon black solution; the molar ratio of the chitosan to the acetic acid is 1: (2-3);
(2) adding multi-or single-walled carbon nanotubes to HNO3/H2SO4Preparing 0.02-0.05g/mL carbon nanotube solution in the mixed acid solution, heating the solution to boiling state, refluxing for 40-70min, filtering with a filter membrane, washing with deionized water to weak acidity, and vacuum drying at 60-80 deg.C for 40-60 h; HNO3And H2SO4The mass of (2-4) to 1;
(3) dissolving the carbon nano tube acidified in the step (2) in deionized water, performing ultrasonic dispersion to prepare a carbon nano tube solution with the concentration of 6-15mg/mL, adding the carbon nano tube solution into the chitosan-loaded white carbon black solution in the step (1), and performing ultrasonic dispersion to obtain modified white carbon black;
wherein, the mass of the chitosan is 30-50% of the mass of the white carbon black, and the mass of the carbon nano tube is 40-60% of the mass of the chitosan.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117467234A (en) * | 2023-11-23 | 2024-01-30 | 广东东大科技有限公司 | Low-compression permanent deformation styrene thermoplastic elastomer and preparation method thereof |
| CN117487263A (en) * | 2023-07-17 | 2024-02-02 | 曲靖市马龙区天龙橡胶制品有限公司 | Regenerated rubber prepared from waste tires and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117487263A (en) * | 2023-07-17 | 2024-02-02 | 曲靖市马龙区天龙橡胶制品有限公司 | Regenerated rubber prepared from waste tires and preparation method thereof |
| CN117467234A (en) * | 2023-11-23 | 2024-01-30 | 广东东大科技有限公司 | Low-compression permanent deformation styrene thermoplastic elastomer and preparation method thereof |
| CN117467234B (en) * | 2023-11-23 | 2024-04-16 | 广东东大科技有限公司 | Low-compression permanent deformation styrene thermoplastic elastomer and preparation method thereof |
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