阅读说明：本技术 一种以油页岩半焦基矿物/生物炭材料作为补强助剂制备橡胶的方法 (Method for preparing rubber by taking oil shale semicoke-based mineral/biochar material as reinforcing auxiliary agent ) 是由 王爱勤 许江 牟斌 朱永峰 康玉茹 于 2021-08-23 设计创作，主要内容包括：本发明公开了一种以油页岩半焦基矿物/生物炭材料作为补强助剂制备橡胶的方法,是将生胶加入混炼机塑化后,依次加入优选比例的氧化锌、硬脂酸、促进剂、硅烷偶联剂、油页岩半焦基矿物/生物炭材料、白炭黑以及硫磺后混炼得到混炼胶,再将混炼胶放置、硫化后得到橡胶产品,其中油页岩半焦基矿物/生物炭材料是油页岩半焦经酸蚀和缺氧或低氧环境下煅烧得到的。本发明将酸蚀和碳化后得到的油页岩半焦基矿物/生物炭材料作为补强助剂,制备出性能优异的橡胶产品,具有技术先进和成本可控等优势,可实现固废资源化利用和环境保护的双重效益。(The invention discloses a method for preparing rubber by taking an oil shale semicoke-based mineral/charcoal material as a reinforcing auxiliary agent, which comprises the steps of adding raw rubber into a mixing roll for plasticizing, sequentially adding zinc oxide, stearic acid, an accelerator, a silane coupling agent, an oil shale semicoke-based mineral/charcoal material, white carbon black and sulfur in an optimal proportion, mixing to obtain a mixed rubber, placing the mixed rubber, and vulcanizing to obtain a rubber product, wherein the oil shale semicoke-based mineral/charcoal material is obtained by calcining oil shale semicoke in an acid etching and oxygen-deficient or low-oxygen environment. According to the invention, the oil shale semicoke-based mineral/charcoal material obtained after acid etching and carbonization is used as a reinforcing auxiliary agent to prepare a rubber product with excellent performance, and the rubber product has the advantages of advanced technology, controllable cost and the like, and can realize double benefits of solid waste resource utilization and environmental protection.)

1. A method for preparing rubber by taking oil shale semicoke-based mineral/biochar material as a reinforcing auxiliary agent mainly comprises the following steps:

(1) preparing an oil shale semicoke-based mineral/charcoal material: crushing the oil shale semi-coke to less than 200 meshes, uniformly dispersing the crushed oil shale semi-coke into an acid solution, stirring and reacting for 2-6 h at the temperature of 60-90 ℃, and centrifuging, washing and filter-pressing to obtain an acid etching product; calcining the acid etching product in an anoxic or low-oxygen environment at 700-1000 ℃ for 2h to obtain the oil shale semicoke-based mineral/charcoal material;

(2) preparation of rubber products: adding raw rubber into a mixing roll for plasticizing, sequentially adding zinc oxide, stearic acid, an accelerator, a silane coupling agent, an oil shale semi-coke base mineral/charcoal material and white carbon black mixture and sulfur, mixing to obtain mixed rubber, placing the mixed rubber, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at the temperature of 160 ℃ under 16-17 Mpa for 0.5-1 h to obtain a rubber product; the raw materials are measured according to the following parts by mass: 100 parts of raw rubber, 3-4 parts of zinc oxide, 1-2 parts of stearic acid, 2-3 parts of an accelerant, 3-4 parts of a silane coupling agent, 50 parts of a mixture of an oil shale semicoke-based mineral/charcoal material and white carbon black, and 2-3 parts of sulfur; wherein, in the mixture of the oil shale semicoke-based mineral/charcoal material and the white carbon black, the oil shale semicoke-based mineral/charcoal material accounts for 5-20 parts.

2. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing auxiliary agent as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the acid solution is one or two of hydrochloric acid and sulfuric acid with the concentration of 0.5-2.0 mol/L.

3. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing auxiliary agent as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the oil shale semi-coke is dispersed in an acid solution according to the mass ratio of 1: 5-1: 10.

4. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing auxiliary agent as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the oxygen-deficient or low-oxygen environment is at least one of an argon atmosphere, a helium atmosphere or a nitrogen atmosphere.

5. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing auxiliary agent as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the calcination is performed in a rotary kiln, a cracking furnace, a fixed bed reactor or a fluidized bed reactor.

6. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing aid as claimed in claim 1, wherein in the step (2), the accelerator is at least one of ZDMC, TMTD and TBBS.

7. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing aid as claimed in claim 1, wherein in the step (2), the silane coupling agent is Si-69.

8. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing aid as claimed in claim 1, wherein in the step (2), the mixing temperature is 50-60 ℃, and the mixing time is 30-40 min.

9. The method for preparing rubber by using the oil shale semicoke-based mineral/biochar material as the reinforcing aid as claimed in claim 1, wherein in the step (2), the standing time of the rubber compound is 2-12 h.

Technical Field

The invention relates to a method for preparing rubber, in particular to a method for preparing rubber by taking an oil shale semicoke-based mineral/charcoal material as a reinforcing auxiliary agent, and belongs to the technical field of solid waste resource utilization and rubber deep processing.

Background

Oil shale is a sedimentary rock which is usually associated with coal and mined together, contains kerogen, minerals and moisture, and is widely applied to the aspects of shale oil refining, combustion power generation, synthetic building materials and the like. The oil shale semicoke is the main solid waste generated when the oil shale is subjected to low-temperature dry distillation to extract shale oil, and contains a large amount of mineral substances and organic matters. At present, the common disposal method of the oil shale semi-coke is stockpiling or landfill, which occupies a large amount of land and destroys ecological landscape, and leachate generated by rainwater leaching or snow melting pollutes the soil and underground water environment. Therefore, the oil shale semicoke stacking and landfill not only wastes high value-added mineral and organic matter resources, but also has potential harm to surrounding ecological and environmental quality, and the development and utilization of the oil shale semicoke from the innovative perspectives of mineralogy, materials science and the like are urgently needed.

White carbon black is a toughening and reinforcing auxiliary agent used in large scale in the rubber industry, and can provide high hardness, high tensile strength and high wear resistance for a rubber formula, but the complex preparation process and the high product price of the white carbon black lead researchers at home and abroad to use other functional materials or composite materials for substitution. Patents of Chinese inventions such as "rubber modified by oil shale ash and method thereof (CN 201110355054.6)", "method for preparing rubber filler by using modified oil shale semicoke (CN 201710134586.4)", "oil shale lime rubber inner tube modifier (CN 201710882354.7)", "natural rubber modified by shale ash and preparation method thereof (CN 201910268499.7)" and "natural rubber preparation method for rubber products by using shale ash as filler (CN 201910825736.5)" relate to the application of oil shale semicoke as filler or modifier in rubber, and show that the oil shale semicoke is gradually known and regarded as rubber additive by researchers.

From the chemical composition analysis of Jilin Wangqing, Jilin Bedian, Liaoning pacifing and Shandong Longkou oil shale carbocoal, the scholars of Wang Shujuan and the like find that the oil shale carbocoal contains a small amount of heavy metal ions such as Mn, Cu, Fe and the like except mineral substances and organic matters (see the research on the physicochemical properties of the oil shale carbocoal in different producing areas). The study of the theories of Yuan Tianyuan and the like finds that Cu²⁺、Mn²⁺And Fe³⁺The three metal ions can accelerate the aging of vulcanized rubber, so that the thermal oxidation aging resistance, ultraviolet aging resistance and ozone aging resistance of the rubber are obviously reduced (see the research on the influence of the metal ions on the aging performance of natural rubber); by studying the degradation behavior of rubber in air, the Lumingzi et al learns that Mn can lower the initial decomposition temperature of rubber, and Mn and Cu act together to have larger influence on thermal stability, which can lead to the premature degradation of rubber products (see the influence of metal ions on the thermal stability of natural rubber of different strains). On the other hand, the mass ratio of organic matters in the oil shale semicoke reaches 20-40% (mostly polycyclic aromatic hydrocarbons and phenols organic matters), and the organic matters are uniformly distributed on the surface of a mineral sheet layer or stacked gaps, so that the specific surface area of the oil shale semicoke is small, the number of stacked holes is small, and the oil shale semicoke is directly used as a rubber auxiliary agent to be not beneficial to mixing to form a cross-linked network structure; and the minerals with high added value (such as lamellar kaolinite) are not activated, so that the reaction activity is low, the filling function is realized only, and the high-value utilization is not realized. Therefore, when the oil shale semi-coke is used as a rubber reinforcing additive, the heavy metal ions and the variable valence metal ions can reduce the mechanical property and the ageing resistance of a rubber product, and the problems of how to efficiently and comprehensively utilize mineral and organic matter resources in the rubber product and the like are to be further solved.

Disclosure of Invention

The invention aims to overcome the defects of the rubber prepared by taking the oil shale semicoke as the reinforcing additive, and provides a method for preparing the rubber by taking the oil shale semicoke-based mineral/charcoal material as the reinforcing additive.

Rubber prepared by using oil shale semicoke-based mineral/charcoal material as reinforcing auxiliary agent

The invention provides a method for preparing rubber by taking an oil shale semicoke-based mineral/biochar material as a reinforcing auxiliary agent, which mainly comprises the following steps:

(1) preparing an oil shale semicoke-based mineral/charcoal material: crushing the oil shale semi-coke to less than 200 meshes, uniformly dispersing the crushed oil shale semi-coke into an acid solution, stirring and reacting for 2-6 h at the temperature of 60-90 ℃, and centrifuging, washing and filter-pressing to obtain an acid etching product; and calcining the acid etching product in an anoxic or low-oxygen environment at 700-1000 ℃ for 2h to obtain the oil shale semicoke-based mineral/charcoal material.

The acid solution is one or two of hydrochloric acid and sulfuric acid with the concentration of 0.5-2.0 mol/L, and the oil shale semicoke is dispersed in the acid solution according to the mass ratio of 1: 5-1: 10.

The oil shale semicoke-based mineral/charcoal material is obtained by calcining in an anoxic or low-oxygen environment, wherein the anoxic or low-oxygen environment is at least one of an argon atmosphere, a helium atmosphere and a nitrogen atmosphere, and the calcining is carried out in a rotary kiln, a cracking furnace, a fixed bed reactor or a fluidized bed reactor.

(2) Preparation of rubber products: adding raw rubber into a mixing roll for plasticizing, sequentially adding zinc oxide, stearic acid, an accelerator, a silane coupling agent, an oil shale semi-coke base mineral/charcoal material and white carbon black mixture and sulfur, mixing to obtain mixed rubber, placing the mixed rubber, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at the temperature of 160 ℃ under 16-17 Mpa for 0.5-1 h to obtain a rubber product; the raw materials are measured according to the following parts by mass: 100 parts of raw rubber, 3-4 parts of zinc oxide, 1-2 parts of stearic acid, 2-3 parts of an accelerant, 3-4 parts of a silane coupling agent, 50 parts of a mixture of an oil shale semicoke-based mineral/charcoal material and white carbon black, and 2-3 parts of sulfur, wherein the mass part of the oil shale semicoke-based mineral/charcoal material in the mixture of the oil shale semicoke-based mineral/charcoal material and the white carbon black is 5-20 parts.

The accelerant is at least one of ZDMC, TMTD and TBBS; the silane coupling agent is Si-69. The mixing temperature is 50-60 ℃, and the mixing time is 30-40 min. The standing time of the rubber compound is 2-12 h.

II, structure and performance of oil shale semicoke-based mineral/charcoal material and rubber

From the comparison of the chemical composition data (Table 1) of the oil shale semicoke and the acid-etched oil shale semicoke, it can be seen that the heavy metals Cu and Mn and the iron oxide Fe in the acid-etched oil shale semicoke are treated by the acid etching process of the invention₂O₃The mass fraction is greatly reduced (only 6.5-9.8 percent of the oil shale semicoke), and the mass fractions of Cr, Zn and As with catalytic activity are also obviously reduced; FIG. 1 is SEM pictures of oil shale semicoke (left) and acid-etched oil shale semicoke (right), from which it can be clearly observed that the acid-etched oil shale semicoke still maintains an irregularly stacked lamellar structure after acid etching (right in FIG. 1), which shows that the acid etching treatment greatly erodes heavy metal iron oxides Cu, Mn and Fe which affect the performance of the rubber product₂O₃Meanwhile, the structure and the morphology of clay minerals (such as kaolinite) in the oil shale semi-coke are not damaged, and an important foundation is laid for realizing toughening and reinforcement by utilizing mineral components with high additional values subsequently.

Table 2 and FIG. 2 show the specific surface area, surface potential data and N of the oil shale semicoke and oil shale semicoke-based mineral/biochar materials, respectively, in accordance with the present invention₂The specific surface area of the oil shale semicoke-based mineral/charcoal material is more than 4 times of that of the oil shale semicoke by an absorption/desorption curve, N₂The adsorption capacity is obviously improved, and the increase of the pore volume and the reduction of the pore diameter indicate that the number of pseudo pores formed by stacking is increased, which is favorable for the adsorption of formula components such as rubber molecules, silane coupling agents and the like in the mixing processThe surface of the mineral/biochar material or the mineral/biochar material enters a lamellar structure to improve the mechanical property and stability of the composite rubber product. Meanwhile, as can be seen from the Zeta potential data of the oil shale semicoke and the oil shale semicoke-based mineral/charcoal material, the electronegativity of the surface of the oil shale semicoke-based mineral/charcoal material is obviously increased (the Zeta potential value is-35.4), and the particle size reduction and the dispersibility increase of the oil shale semicoke-based mineral/charcoal material are further proved to be realized through the acid etching and calcining processes.

FIG. 3 is an infrared spectrum of oil shale semicoke and oil shale semicoke-based mineral/biochar materials, which shows 3686cm in comparison to oil shale semicoke^-1And 3619cm^-1The decrease in the-OH peak intensity of the kaolinite indicates that the kaolinite is converted into metakaolinite with high activity (especially, the activity is higher when calcined at 700-1000 ℃) after high-temperature calcination, and the metakaolinite is combined with the Si-O group, the Al-Al-OH group and the Fe-O group or the Fe₂O₃Corresponding 1036cm^-1、918cm^-1And 534cm^-1The decrease in peak intensity also again demonstrates that the acid etching treatment erodes the metal ions in the oil shale char.

Meanwhile, the dispersibility of the rubber reinforcing aid is one of the key factors influencing the toughening and reinforcing performance of the rubber reinforcing aid, and the more uniform the rubber reinforcing aid is dispersed in the matrix, the more favorable the rubber reinforcing aid is for forming a compact cross-linked network structure and improving the mechanical performance and the ageing resistance of the product. Respectively adding 50mL of water and 50mL of ethanol into equal mass (0.25 g) of oil shale semicoke or oil shale semicoke-based mineral/charcoal material&In the mixed solution of silane coupling agent (50 mL of water +2g of silane coupling agent Si-69), the mixture was stirred at a high speed of 6000rpm/min for 5 minutes, and the dispersion conditions in different systems are shown in FIG. 4, which shows that the silane coupling agent and the ethanol were uniformly dispersed in water and ethanol after the mixture was dispersed at a high speed&Standing the oil shale semi-coke in a silane coupling agent system for 1 minute in a water system and ethanol&Obvious sedimentation appears in the mixed solution of the silane coupling agent, the mixed solution is accumulated at the bottom of the container after 5 minutes, and the oil shale semicoke-based mineral/biochar material is dispersed in a water system or ethanol&The silane coupling agent system still keeps a uniform dispersion state after being stood for a long time, which strongly proves that the oil shale semicoke-based mineral/biochar material can contain organic rubberThe uniform dispersion of the rubber molecules, the silane coupling agent and the stearic acid in the mixed system is realized, the intercalation and the crosslinking reaction are conveniently carried out in the mixing process to improve the mechanical property of the rubber product, which is further proved by the mechanical property data (table 3) of the rubber prepared by the embodiment of the invention, and the composite rubber product (MSC-SR-X) The tensile strength of the rubber product (RB) is higher than that of a rubber product (RB) prepared without adding modified oil shale semi-coke and white carbon black as a reinforcing auxiliary agent, and particularly the maximum breaking elongation index lifting amplitude can reach 14.10 percent.

In conclusion, compared with the prior art, the rubber preparation method provided by the invention has the following advantages:

1. on the basis of fully knowing the chemical composition and structural characteristics of the oil shale semicoke and the preparation process of the rubber product, the invention obtains the oil shale semicoke-based mineral/biochar material through the acid etching and calcining two-step process after condition optimization, wherein heavy metal ions (Cu) in the mineral/biochar material²⁺、Mn²⁺And Fe³⁺) Valence-variable metal ion (Fe)²⁺) The rubber reinforcing agent has the characteristics of extremely low content of soluble salt and the like, large specific surface area, pore volume, good dispersibility in an oil phase system or a water phase system and the like, and is used as a rubber reinforcing auxiliary agent to prepare a rubber product with excellent mechanical property and stability by utilizing the mineralogy and physicochemical characteristics of the materials.

2. According to the invention, a combined process of acid etching and carbonization is adopted, so that the comprehensive utilization of mineral and organic matter resources in the oil shale semicoke solid waste is realized, the oil shale semicoke-based mineral/charcoal material which is high in product yield (more than 70%) and has a pore structure and a lamellar morphology is obtained by controlling the process conditions such as acid etching conditions, carbonization conditions and the like, and the rubber product which is high in tensile strength (more than 16.50 MPa) and high in elongation at break (623%) is obtained by further regulating and controlling key parameters such as a rubber mixing formula and the addition amount of the mineral/charcoal material.

3. The oil shale semicoke solid waste used in the invention has the characteristics of easily obtained raw materials, stable supply, low price and the like, the two-step treatment process is reasonable and efficient, the acid liquor and the gas generated in the carbonization process can be recycled, the process belongs to a green chemical and low-carbon preparation process, the reinforcing effect of white carbon black and carbon black double components can be realized by using the lamellar minerals and the biochar in the mineral/biochar material in the rubber formula, the cost advantage and the economic benefit are obvious compared with the white carbon black, and the industrial production is favorable for the resource utilization of the solid waste and the environmental protection.

Drawings

FIG. 1 is SEM pictures of oil shale semicoke (left) and acid etched oil shale semicoke (right);

FIG. 2 is a graph of oil shale semicoke and N for oil shale semicoke-based mineral/biochar materials₂Adsorption-desorption curves;

FIG. 3 is an infrared spectrum of oil shale semicoke and oil shale semicoke-based mineral/biochar materials;

fig. 4 is a digital photograph of oil shale semicoke and oil shale semicoke-based mineral/biochar materials dispersed in a water system and an ethanol & silane coupling agent system.

Detailed Description

The preparation method and properties of the oil shale semicoke-based mineral/biochar material reinforcing additive and the composite rubber product of the invention are further explained by the following specific examples.

Example 1

(1) Acid etching of oil shale semicoke: weighing 500g of oil shale semi-coke powder (crushed and less than 200 meshes), dispersing the oil shale semi-coke powder into 2.5L and 2M hydrochloric acid solution, stirring and reacting for 6 hours at 90 ℃, centrifuging, washing for 3 times by deionized water, and performing filter pressing and drying to obtain acid etched oil shale semi-coke;

(2) preparation of rubber products: 100 parts of styrene butadiene rubber raw rubber (mass parts, the same below) are added into a mixing roll for plasticizing for 10 minutes, then 4 parts of zinc oxide, 2 parts of stearic acid, 3 parts of accelerator (ZDMC), Si-693.5 parts of silane coupling agent, 10 parts of acid-etched oil shale semi-coke, 40 parts of white carbon black and 3 parts of sulfur are sequentially added, mixing is carried out for 0.5h at the temperature of 60 ℃, and the roll spacing is adjusted to carry out multiple times of cutting knife in the mixing process to obtain mixed rubber; and then placing the mixed rubber for 12h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing the mixed rubber at the temperature of 160 ℃ under 17Mpa for 0.5h to obtain a rubber product which is marked as ASC-RB-1. The mechanical property data of the compounded rubber product are shown in Table 3.

Example 2

(1) Preparing an oil shale semicoke-based mineral/charcoal material: weighing 500g of oil shale semicoke powder, dispersing into 5L of 0.5M hydrochloric acid solution, stirring and reacting for 6h at 90 ℃, centrifuging, washing for 3 times by deionized water and performing filter pressing to obtain acid-etched oil shale semicoke; adding the acid-etched oil shale semicoke into a rotary kiln, and calcining for 2 hours at 700 ℃ under the protection of argon atmosphere to obtain an oil shale semicoke-based mineral/charcoal material;

(2) preparation of rubber products: adding 100 parts of styrene butadiene rubber raw rubber into a mixing roll for plasticizing for 10 minutes, sequentially adding 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an accelerator (TBBS), Si-692 parts of a silane coupling agent, 5 parts of an oil shale semi-coke base mineral/charcoal material, 45 parts of white carbon black and 2 parts of sulfur, mixing for 0.5h at 55 ℃, adjusting the roll spacing in the mixing process, and performing multiple times of cutting to obtain rubber compound; and then placing the mixed rubber for 12h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at the temperature of 16Mpa and 160 ℃ for 0.5h to obtain a rubber product, which is marked as MSC-RB-2. The mechanical property data of the compounded rubber product are shown in Table 3.

Example 3

(1) Preparing an oil shale semicoke-based mineral/charcoal material: weighing 500g of oil shale semicoke powder, dispersing into 5L of 1M sulfuric acid solution, stirring and reacting for 4h at 90 ℃, centrifuging, washing for 3 times by deionized water and performing filter pressing to obtain acid-etched oil shale semicoke; adding the acid-etched oil shale semicoke into a cracking furnace, and calcining for 2 hours at 800 ℃ under the protection of helium atmosphere to obtain an oil shale semicoke-based mineral/charcoal material;

(2) preparation of rubber products: adding 100 parts of butadiene styrene rubber raw rubber into a mixing roll for plasticizing for 10 minutes, sequentially adding 3.5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an accelerant (TMTD), silane coupling agent Si-693 parts, 5 parts of oil shale semi-coke based mineral/charcoal material, 45 parts of white carbon black and 2 parts of sulfur, mixing for 0.5h at the temperature of 60 ℃, adjusting the roll spacing in the mixing process, and carrying out multiple times of cutting to obtain mixed rubber; and then placing the mixed rubber for 2h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at 17Mpa and 160 ℃ for 40min to obtain a rubber product which is marked as MSC-RB-3. The mechanical property data of the compounded rubber product are shown in Table 3.

Example 4

(1) Preparing an oil shale semicoke-based mineral/charcoal material: weighing 500g of oil shale semicoke powder, dispersing into 4L of 2M hydrochloric acid solution, stirring and reacting for 6h at 90 ℃, centrifuging, washing for 3 times by using deionized water, and performing filter pressing to obtain acid-etched oil shale semicoke; adding the acid-etched oil shale semicoke into a fluidized bed reactor, and calcining for 2 hours at 900 ℃ under the protection of nitrogen atmosphere to obtain an oil shale semicoke-based mineral/charcoal material;

(2) preparation of rubber products: adding 100 parts of styrene butadiene rubber raw rubber into a mixing roll for plasticizing for 10 minutes, sequentially adding 4 parts of zinc oxide, 2.5 parts of stearic acid, 3 parts of an accelerant (TBBS), a silane coupling agent Si-694, 10 parts of an oil shale semi-coke based mineral/charcoal material, 40 parts of white carbon black and 3 parts of sulfur, mixing for 40 minutes at 60 ℃, and adjusting the roll spacing to perform multiple times of cutting in the mixing process to obtain rubber compound; and then placing the mixed rubber for 6h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at the temperature of 16Mpa and 160 ℃ for 40min to obtain a rubber product which is marked as MSC-RB-4. The mechanical property data of the compounded rubber product are shown in Table 3.

Example 5

(1) Preparing an oil shale semicoke-based mineral/charcoal material: weighing 500g of oil shale semicoke powder, dispersing into 4L of 1M hydrochloric acid solution, stirring and reacting for 6h at 90 ℃, centrifuging, washing for 3 times by using deionized water, and performing filter pressing to obtain acid-etched oil shale semicoke; adding the acid-etched oil shale semicoke into a fixed bed reactor, and calcining for 2 hours at 1000 ℃ under the protection of nitrogen atmosphere to obtain an oil shale semicoke-based mineral/charcoal material;

(2) preparation of rubber products: adding 100 parts of styrene butadiene rubber raw rubber into a mixing roll for plasticizing for 10 minutes, sequentially adding 4 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an accelerant (TMTD), a silane coupling agent Si-694, 10 parts of an oil shale semi-coke based mineral/charcoal material, 40 parts of white carbon black and 3 parts of sulfur, mixing for 0.5h at 55 ℃, adjusting a roll gap in the mixing process, and performing multiple times of cutting to obtain rubber compound; and then placing the mixed rubber for 12h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at 16Mpa and 160 ℃ for 40min to obtain a rubber product, which is marked as MSC-RB-5. The mechanical property data of the compounded rubber product are shown in Table 3.

Comparative example

The white carbon black is used as a reinforcing auxiliary agent to prepare the rubber, and the main steps are as follows: 100 parts of raw butadiene styrene rubber is added into a mixing roll for plasticizing for 10 minutes, then 3.5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of accelerator (ZDMC), Si-694 parts of silane coupling agent, 50 parts of white carbon black and 3 parts of sulfur are added in sequence, mixing is carried out for 0.5h at the temperature of 60 ℃, and the roll spacing is adjusted to carry out multiple times of cutting knife in the mixing process to obtain mixed rubber; and then placing the mixed rubber for 12h, adding the mixed rubber into a flat vulcanizing machine, and vulcanizing at 17Mpa and 160 ℃ for 40min to obtain a rubber product marked as RB. The mechanical property data of the compounded rubber product are shown in Table 3.