Functional composite material added with modified molybdenum tailing micro-powder, and preparation method and application thereof

Abstract

This application discloses a functional composite material with modified molybdenum tailings powder, its preparation method, and its application, relating to the field of rubber materials. The functional composite material with modified molybdenum tailings powder comprises the following raw materials in parts by weight: 100 parts nitrile rubber, 130-180 parts reinforcing filler, 20-25 parts plasticizer, 2-7 parts antioxidant, 1-5 parts vulcanizing agent, 1-3 parts accelerator, and 3-8 parts activator; wherein the reinforcing filler includes carbon black and modified molybdenum tailings. In the technical solution of this application, carbon black and modified molybdenum tailings are used as reinforcing fillers. The carbon black and rubber molecular network interpenetrate and support each other, forming a three-dimensional branched structure. The modified molybdenum tailings are dispersed in the three-dimensional branched structure, increasing the crosslinking density and improving the mechanical properties and aging resistance of the rubber material.

Description

Technical Field

[0001] This application relates to the field of rubber materials, and in particular to a functional composite material with modified molybdenum tailings powder, its preparation method, and its application. Background Technology

[0002] Rubber, as one of the three main polymer materials, is widely used in hoses, tapes, seals, and shock-absorbing materials due to its high elasticity. However, because rubber has weak intermolecular forces, large free volume, and weak crystallization ability, its tensile strength, modulus, wear resistance, and fatigue performance often fail to meet practical requirements. Therefore, it is necessary to add reinforcing fillers to enhance the tensile strength, hardness, and wear resistance of rubber products, while maintaining most of their elastic properties.

[0003] Silica is a widely used reinforcing agent in the rubber industry, significantly improving the mechanical properties and aging resistance of rubber materials. However, the production process of silica is not only energy-intensive but also generates waste that has a certain impact on the environment. Therefore, developing a low-cost, environmentally friendly alternative material is particularly important.

[0004] Molybdenum tailings, an industrial byproduct typically generated during molybdenum mining and smelting, contain significant amounts of silica, alumina, and other minerals, and hold promise as a rubber reinforcing agent. However, research into the applications of molybdenum tailings is still in its early stages, particularly in the rubber industry, where its potential applications have not yet been fully explored. Summary of the Invention

[0005] This application aims to solve at least one of the existing technical problems. In view of this, this application proposes a functional composite material with modified molybdenum tailings powder, its preparation method and application, using treated molybdenum tailings as raw material for reinforcing filler to obtain a rubber material with excellent mechanical properties and aging resistance.

[0006] In the first aspect, this application provides a functional composite material with added modified molybdenum tailings powder, comprising the following raw materials in parts by weight: 100 parts of nitrile rubber, 130-180 parts of reinforcing filler, 20-25 parts of plasticizer, 2-7 parts of antioxidant, 1-5 parts of vulcanizing agent, 1-3 parts of accelerator, and 3-8 parts of activator. The reinforcing filler includes carbon black and modified molybdenum tailings. The raw materials for preparing the modified molybdenum tailings include silane coupling agent, molybdenum tailings, and inorganic materials, wherein the inorganic materials are selected from at least one of calcium carbonate and kaolin.

[0007] By adopting the above technical solution, using nitrile rubber as the matrix material, carbon black and modified molybdenum tailings are added as reinforcing fillers to the nitrile rubber matrix material. Carbon black has an extremely high specific surface area and a well-developed microporous structure. Its surface is rich in aromatic rings and partially graphitized lattices, and carbon black networks are easily formed between particles. During processing, carbon black and rubber molecular networks interpenetrate and support each other, forming a three-dimensional branched structure. Modified molybdenum tailings are dispersed in the three-dimensional branched structure, playing a significant reinforcing role and effectively improving the mechanical properties and aging resistance of the rubber material.

[0008] Silane coupling agents can improve the dispersion and flowability of molybdenum tailings in nitrile rubber matrices. If the inorganic material includes kaolin, the molybdenum tailings contain a large amount of metal oxides such as silica and alumina. These metal oxides can combine with the carrier framework formed by kaolin through solid-phase ion exchange / diffusion, regulating the crystal phase reconstruction of kaolin. The resulting modified molybdenum tailings are dispersed in the three-dimensional branched structure formed by carbon black, effectively increasing the crosslinking density and forming more stable branched aggregates, significantly improving the mechanical properties and aging resistance of the rubber material.

[0009] If the inorganic material includes calcium carbonate, the calcium carbonate is preferably light calcium carbonate. Light calcium carbonate has a fine particle size and good flowability. When added, it can reduce the viscosity of the rubber compound and improve its flowability. Calcium carbonate and molybdenum tailings complement each other. The resulting modified molybdenum tailings are dispersed in the three-dimensional branched structure formed by carbon black, which helps to increase the crosslinking density and improve the mechanical properties and aging resistance of the rubber material.

[0010] In this application, carbon black and modified molybdenum tailings are used as reinforcing fillers for rubber. The carbon black and rubber molecular network interpenetrate and support each other, forming a three-dimensional branched structure. The modified molybdenum tailings are dispersed in the three-dimensional branched structure, effectively increasing the crosslinking density and improving the mechanical properties and aging resistance of the rubber material. Plasticizers can increase the degree of freedom of chain segments, achieving significant improvements in the material's softness, elasticity, processability, and impact toughness.

[0011] Preferably, the reinforcing filler is in the form of 145 to 160 parts by weight.

[0012] Optionally, the weight ratio of the carbon black to the modified molybdenum tailings is (40~50):(95~105).

[0013] By adopting the above technical solution and controlling the ratio of carbon black to modified molybdenum tailings, the mechanical properties and aging resistance of rubber materials can be effectively improved.

[0014] Optionally, the weight ratio of the silane coupling agent, the molybdenum tailings, and the inorganic matter is 2.7:30:80.

[0015] By adopting the above technical solution and using molybdenum tailings as a raw material for reinforcing filler, the resource utilization of molybdenum tailings can be realized, and production costs can be reduced. Modified molybdenum tailings prepared by using silane coupling agents, molybdenum tailings, and inorganic substances are dispersed in the three-dimensional branched structure formed by carbon black, which effectively increases the crosslinking density, forms more stable branched aggregates, and significantly improves the hardness and mechanical properties of rubber materials.

[0016] Optionally, the inorganic material is kaolin, and the method for preparing the modified molybdenum tailings includes: (1) The kaolin is roasted, and the kaolin obtained from roasting is added to an alkaline solution and stirred in a constant temperature water bath. It is then taken out and left to stand at room temperature. It is placed in a thermostat, taken out and subjected to solid-liquid separation, washing and drying to obtain activated kaolin. (2) The molybdenum tailings were mixed with the kaolin obtained in step (1) and reacted under heating conditions to obtain a complex. (3) The complex obtained in step (2) is added to the silane coupling agent solution, stirred and reacted, and then separated into solid and liquid, washed and dried to obtain modified molybdenum tailings.

[0017] By employing the above technical solution, kaolin is calcined at 700-800℃ and then added to an alkaline solution to obtain activated kaolin, which possesses strong ion exchange capacity. When mixed with molybdenum tailings, the metal oxides in the molybdenum tailings can combine with the carrier framework formed by the kaolin through solid-phase ion exchange / diffusion, thus regulating the crystal phase reconstruction of the kaolin. A silane coupling agent is used to modify the composite of molybdenum tailings and kaolin to improve the dispersion and fluidity of the modified molybdenum tailings in the matrix.

[0018] Optionally, the alkaline solution in step (1) is a sodium hydroxide solution with a concentration of 8~15wt%, the temperature of the constant temperature water bath is 70~85℃, and the temperature in the thermostat is set to 70~90℃.

[0019] Optionally, the heating conditions in step (2) are as follows: the mixture is reacted at 300~400℃ for 1h, heated to 400~600℃ at a heating rate of 10~20℃ / min, held at this temperature for 3h, taken out and cooled to 20~30℃ at a cooling rate of 60~100℃ / min.

[0020] Optionally, the inorganic material is calcium carbonate, and the method for preparing the modified molybdenum tailings includes: (1) Dry the calcium carbonate and molybdenum tailings separately to obtain dried calcium carbonate and molybdenum tailings; (2) Add the silane coupling agent to the ethanol solution and adjust the pH to 3.5~5.5 to obtain the modified solution; (3) Add the dried calcium carbonate and molybdenum tailings from step (1) to the modified liquid obtained in step (2), stir and react, separate the solid and liquid, wash and dry to obtain modified molybdenum tailings.

[0021] By adopting the above technical solution, the calcium carbonate is preferably light calcium carbonate, which has good fluidity. Calcium carbonate and molybdenum tailings complement each other. After modification with silane coupling agent, the modified molybdenum tailings are dispersed in the three-dimensional branched structure formed by carbon black, which helps to increase the crosslinking density and improve the mechanical properties and aging resistance of rubber materials.

[0022] Optionally, the inorganic material is calcium carbonate and kaolin, wherein the weight ratio of calcium carbonate to kaolin is 1:1, and the method for preparing the modified molybdenum tailings includes: (1) The kaolin is roasted, and the kaolin obtained from roasting is added to an alkaline solution and stirred in a constant temperature water bath. It is then taken out and left to stand at room temperature. It is placed in a thermostat, taken out and subjected to solid-liquid separation, washing and drying to obtain activated kaolin. (2) Molybdenum tailings, calcium carbonate and kaolin obtained in step (1) are mixed and reacted under heating conditions to obtain a complex; (3) The complex obtained in step (2) is added to the silane coupling agent solution, stirred and reacted, and then separated into solid and liquid, washed and dried to obtain modified molybdenum tailings.

[0023] By employing the above-mentioned technical solution, kaolin is subjected to high-temperature calcination and then added to an alkaline solution to obtain activated kaolin, which at this point possesses a strong ion exchange capacity. When mixed with molybdenum tailings and calcium carbonate, the metal oxides in the molybdenum tailings can combine with the carrier framework formed by the kaolin through solid-phase ion exchange / diffusion. Calcium carbonate can also be embedded within the kaolin. The resulting modified molybdenum tailings are dispersed within the three-dimensional branched structure formed by carbon black, effectively increasing the crosslinking density and improving the material's mechanical properties and aging resistance.

[0024] Understandably, after mixing molybdenum tailings, calcium carbonate, and kaolin, the heating conditions are as follows: the mixture is reacted at 300~400℃ for 1 hour, heated to 400~600℃ at a heating rate of 10~20℃ / min, held at this temperature for 3 hours, and then taken out and cooled to 20~30℃ at a cooling rate of 60~100℃ / min.

[0025] Optionally, the molybdenum tailings comprises the following chemical composition by mass percentage: SiO2 60-80%, Al2O3 10-16%, K2O 3-6%, Na2O 1-2%, MgO 2-4%, with the balance being other components.

[0026] By adopting the above technical solution, molybdenum tailings, an industrial waste, are transformed into a valuable resource. This application makes full use of the large amount of metal oxides contained in molybdenum tailings and modifies them to effectively reinforce rubber.

[0027] Optionally, the plasticizer includes dioctyl phthalate; and / or, the vulcanizing agent is sulfur.

[0028] By adopting the above technical solution, the addition of dioctyl phthalate to the rubber matrix can increase the degree of freedom of the chain segments, thereby significantly improving the material's softness, elasticity, processability, and impact toughness.

[0029] Optionally, the activator includes stearic acid and nano zinc oxide, and the mass ratio of stearic acid to nano zinc oxide is 1:(1.5~2.5).

[0030] Optionally, the silane coupling agent includes silane coupling agent KH-550, silane coupling agent KH-560, or silane coupling agent Si-69. Other types of silane coupling agents may also be used according to production needs, and this application does not impose any restrictions.

[0031] Secondly, this application provides a method for preparing a functional composite material with modified molybdenum tailings powder as described in any of the above claims, comprising the following steps: S1. Mix nitrile rubber, reinforcing filler, plasticizer, antioxidant and activator, and then perform intensive mixing to obtain a compound rubber. S2. Add the vulcanizing agent and accelerator to the first-stage compound obtained in step S1, and perform intensive mixing to obtain the second-stage compound. S3. The two-stage compound obtained in step S2 is subjected to open milling and sheeting to obtain a functional composite material with added modified molybdenum tailings powder.

[0032] By employing the above technical solution, nitrile rubber, reinforcing fillers, plasticizers, antioxidants, and activators are mixed and internally mixed to improve the dispersibility of the raw materials, resulting in a first-stage compound. A vulcanizing agent and vulcanization accelerator are then added to the first-stage compound, and the mixture is internally mixed again to ensure that the vulcanizing agent and vulcanization accelerator are sufficiently dispersed in the rubber compound, laying the groundwork for subsequent full vulcanization. The functional composite material with modified molybdenum tailings powder is then vulcanized at 170℃ for 6 minutes to obtain a rubber material with excellent mechanical properties and aging resistance.

[0033] Thirdly, this application provides the application of a functional composite material with added modified molybdenum tailings powder as described in any of the above claims in hoses, tapes, seals, and shock-absorbing materials.

[0034] By adopting the above technical solution, the functional composite material with added modified molybdenum tailings powder provided in this application has excellent mechanical properties and aging resistance after vulcanization treatment. It has excellent comprehensive performance and can better meet the needs of practical applications. It can be applied to hoses, tapes, seals and shock-absorbing materials, etc.

[0035] In summary, this application includes at least one of the following beneficial technical effects: 1. In the technical solution of this application, carbon black and modified molybdenum tailings are used as rubber reinforcing fillers. The carbon black and rubber molecular network permeate and support each other to form a three-dimensional branch structure. The modified molybdenum tailings are dispersed in the three-dimensional branch structure, which effectively improves the crosslinking density and improves the mechanical properties and aging resistance of the rubber material.

[0036] 2. Silane coupling agents can improve the dispersion and flowability of molybdenum tailings in nitrile rubber matrices. If the inorganic material includes kaolin, the molybdenum tailings contain a large amount of metal oxides such as silica and alumina. These metal oxides can combine with the carrier skeleton formed by kaolin through solid-phase ion exchange / diffusion, regulating the crystal phase reconstruction of kaolin. The resulting modified molybdenum tailings are dispersed in the three-dimensional branched structure formed by carbon black, effectively increasing the crosslinking density and forming more stable branched aggregates, significantly improving the mechanical properties and aging resistance of the rubber material. Molybdenum tailings are an industrial waste. This application transforms "waste" into "treasure," fully utilizing the large amount of metal oxides contained in molybdenum tailings and cleverly loading them onto kaolin as a reinforcing filler. It is then compounded with carbon black and calcium carbonate to effectively reinforce the rubber and can completely replace silica, reducing production costs. Detailed Implementation

[0037] The present application will be further described in detail below with reference to the embodiments. Preparation Example 1

[0038] A method for preparing modified molybdenum tailings includes the following steps: (1) 80 parts by weight of kaolin (Shanghai Maclean Biochemical Technology Co., Ltd., particle size of 1250 mesh) was calcined in a muffle furnace at 750℃ for 2h. It was taken out and cooled to 50℃ at a cooling rate of 50℃ / min. It was then naturally cooled to room temperature (25℃). The cooled kaolin was mixed with 10wt% sodium hydroxide solution at a mass ratio of 1:18. The mixture was placed in a constant temperature water bath at 80℃ and stirred at a stirring rate of 300rpm for 2h. It was taken out and allowed to stand at room temperature (25℃) for 25min. It was then placed in a constant temperature container at 80℃ for 3h. After solid-liquid separation, it was washed with deionized water and dried at 110℃ for 2h to obtain activated kaolin.

[0039] (2) Dry 30 parts by weight of molybdenum tailings at 120°C for 2 hours. Mix the dried molybdenum tailings with the activated kaolin obtained in step (1) and stir at a stirring rate of 200 rpm for 20 minutes to obtain a mixture. React the mixture at 350°C for 1 hour and raise the temperature to 500°C at a heating rate of 15°C / min. Maintain this temperature for 3 hours, take it out and cool it to 25°C at a cooling rate of 100°C / min to obtain a molybdenum tailings-kaolin composite.

[0040] (3) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (obtained by mixing 10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol) and reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH value of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The molybdenum tailings-kaolin complex obtained in step (2) was added to the silane coupling agent solution at a rate of 5 parts by weight / min and stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and solid-liquid separation was performed. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified molybdenum tailings.

[0041] In step (2), the average particle size of the molybdenum tailings before drying is 5 μm. The chemical composition of the molybdenum tailings is: SiO2 73.01wt%, Al2O3 15.0wt%, K2O 4.35wt%, Na2O 1.21wt%, MgO 3.48wt%, CaO 1.82wt%, with the remainder being other components. Preparation Example 2

[0042] A method for preparing modified molybdenum tailings includes the following steps: (1) 30 parts by weight of molybdenum tailings and 80 parts by weight of light calcium carbonate (average particle size of 2 μm) were dried at 120℃ for 2 h to obtain dried calcium carbonate and dried molybdenum tailings for later use.

[0043] (2) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol), and reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH value of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The dried molybdenum tailings and dried light calcium carbonate obtained in step (1) were added to the silane coupling agent solution at a rate of 5 parts by weight / min, and stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and subjected to solid-liquid separation. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified molybdenum tailings.

[0044] In step (1), the average particle size of the molybdenum tailings before drying is 5 μm. The chemical composition of the molybdenum tailings is: SiO2 73.01wt%, Al2O3 15.0wt%, K2O 4.35wt%, Na2O 1.21wt%, MgO 3.48wt%, CaO 1.82wt%, with the remainder being other components. Preparation Example 3

[0045] A method for preparing modified molybdenum tailings includes the following steps: (1) 40 parts by weight of kaolin (Shanghai Maclean Biochemical Technology Co., Ltd., particle size of 1250 mesh) were calcined in a muffle furnace at 750℃ for 2h. The kaolin was taken out and cooled to 50℃ at a cooling rate of 50℃ / min. It was then naturally cooled to room temperature (25℃). The cooled kaolin was mixed with 10wt% sodium hydroxide solution at a mass ratio of 1:18. The mixture was placed in a constant temperature water bath at 80℃ and stirred at a stirring rate of 300rpm for 2h. The mixture was taken out and allowed to stand at room temperature (25℃) for 25min. It was then placed in a constant temperature container at 80℃ for 3h. The mixture was then removed and subjected to solid-liquid separation. It was washed with deionized water and dried at 110℃ for 2h to obtain activated kaolin.

[0046] (2) 30 parts by weight of molybdenum tailings and 40 parts by weight of light calcium carbonate (average particle size of 2 μm) were dried at 120°C for 2 h. The dried molybdenum tailings, calcium carbonate and activated kaolin obtained in step (1) were mixed and stirred at a stirring rate of 200 rpm for 20 min to obtain a mixture. The mixture was reacted at 350°C for 1 h and heated to 500°C at a heating rate of 15°C / min. The temperature was maintained at this temperature for 3 h. The mixture was then taken out and cooled to 25°C at a cooling rate of 100°C / min to obtain a composite of molybdenum tailings-kaolin-calcium carbonate.

[0047] (3) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol) and reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH value of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The molybdenum tailings-kaolin-calcium carbonate composite obtained in step (2) was added to the silane coupling agent solution at a rate of 5 parts by weight / min and stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and subjected to solid-liquid separation. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified molybdenum tailings.

[0048] The average particle size of the molybdenum tailings before drying was 5 μm. The chemical composition of the molybdenum tailings was: SiO2 73.01 wt%, Al2O3 15.0 wt%, K2O 4.35 wt%, Na2O 1.21 wt%, MgO 3.48 wt%, CaO 1.82 wt%, with the balance being other components. Preparation of Comparative Example 1

[0049] A method for preparing modified calcium carbonate includes the following steps: (1) 80 parts by weight of light calcium carbonate (average particle size of 2 μm) were dried at 120℃ for 2 h to obtain dried calcium carbonate for later use.

[0050] (2) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol). The mixture was reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The light calcium carbonate obtained in step (1) was added to the silane coupling agent solution at a rate of 5 parts by weight / min. The mixture was stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and subjected to solid-liquid separation. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified calcium carbonate. Preparation of Comparative Example 2

[0051] A method for preparing modified molybdenum tailings includes the following steps: (1) Dry 30 parts by weight of molybdenum tailings at 120°C for 2 hours to obtain dried molybdenum tailings for later use.

[0052] (2) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol). The mixture was reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The molybdenum tailings obtained in step (1) were added to the silane coupling agent solution at a rate of 5 parts by weight / min. The mixture was stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and solid-liquid separation was performed. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified molybdenum tailings.

[0053] In step (1), the average particle size of the molybdenum tailings before drying is 5 μm. The chemical composition of the molybdenum tailings is: SiO2 73.01wt%, Al2O3 15.0wt%, K2O 4.35wt%, Na2O 1.21wt%, MgO 3.48wt%, CaO 1.82wt%, with the remainder being other components. Preparation of Comparative Example 3

[0054] A method for preparing modified kaolin includes the following steps: (1) 80 parts by weight of kaolin (Shanghai Maclean Biochemical Technology Co., Ltd., particle size of 1250 mesh) were dried at 120℃ for 2 hours to obtain dried kaolin and dried molybdenum tailings for later use.

[0055] (2) 2.7 parts by weight of silane coupling agent Si-69 were added dropwise to an ethanol solution (10.8 parts by weight of deionized water and 80 parts by weight of anhydrous ethanol). The mixture was reacted at 30°C for 30 min to obtain a silane coupling agent solution. The pH of the silane coupling agent solution was adjusted to 4.5 with glacial acetic acid. The kaolin obtained by drying in step (1) was added to the silane coupling agent solution at a rate of 5 parts by weight / min. The mixture was stirred at a stirring rate of 500 rpm for 30 min. The stirred and dispersed mixture was placed at 25°C and 50% relative humidity and stirred at a stirring rate of 100 rpm for 2 h. The mixture was then removed and solid-liquid separation was performed. The separated solid was washed with deionized water and dried at 110°C for 2 h to obtain modified kaolin. Examples 1-6

[0056] Examples 1-6 provide a functional composite material with modified molybdenum tailings powder. The raw material composition and content are shown in Table 1 below. The specific preparation method includes the following steps: S1. Add nitrile rubber, reinforcing filler, plasticizer, antioxidant and activator into a mixer and mix at 60 rpm for 5 minutes to obtain a compound. S2. Add sulfur and accelerator to the first-stage compound obtained in step S1, mix at 60 rpm for 5 minutes, and control the discharge temperature at 90℃ to obtain the second-stage compound. S3. Add the two-stage compound obtained in step S2 into the open mill, sheet it out, and obtain the compounded rubber material. S4. The mixed rubber material obtained in step S3 is vulcanized at 170°C for 6 minutes to obtain the rubber test sample material.

[0057] In step S1, the nitrile rubber was purchased from Guangzhou Liben Rubber Raw Material Trading Co., Ltd., and its product name was nitrile rubber 3305E; the reinforcing filler was obtained by mixing 45 parts by weight of carbon black N330 and 100 parts by weight of modified molybdenum tailings prepared in Preparation Example 1; the plasticizer was dioctyl phthalate; the antioxidant was obtained by mixing antioxidant AW and antioxidant 4010NA in a mass ratio of 1:1; the activator was obtained by mixing nano zinc oxide and stearic acid 1801 in a mass ratio of 2:1; and the accelerator was obtained by mixing N,N-dicyclohexyl-2-benzothiazole sulfenamide and ethylene thiourea in a mass ratio of 0.6:1.

[0058] Table 1. Raw materials and their usage for rubber materials (unit: parts by weight) Examples 7-8

[0059] Examples 7 and 8 are based on Example 3, the difference being that in step S1, the total mass of the reinforcing filler remains constant, but the amount of its components changes; the other steps are the same as in Example 3. Specifically, In Example 7, the reinforcing filler was obtained by mixing 40 parts by weight of carbon black N330 and 105 parts by weight of modified molybdenum tailings prepared in Preparation Example 1.

[0060] In Example 8, the reinforcing filler was obtained by mixing 50 parts by weight of carbon black N330 and 95 parts by weight of modified molybdenum tailings prepared in Preparation Example 1. Examples 9-10

[0061] Examples 9 and 10 are based on Example 3, the difference being that the source of the modified molybdenum tailings is different in step S1, while the other steps remain the same as in Example 3. Specifically, In Example 9, the modified molybdenum tailings prepared in Preparation Example 2 were used in equal parts by weight to replace the modified molybdenum tailings prepared in Preparation Example 1.

[0062] In Example 10, the modified molybdenum tailings prepared in Preparation Example 3 were used in equal parts by weight to replace the modified molybdenum tailings prepared in Preparation Example 1. Comparative Example 1

[0063] This comparative example is based on Example 1, except that the modified calcium carbonate prepared in Comparative Example 1 is used in equal parts by weight to replace the modified molybdenum tailings prepared in Example 1. Comparative Example 2

[0064] This comparative example is based on Example 1, except that the modified molybdenum tailings prepared in Comparative Example 2 are used in equal parts by weight to replace the modified molybdenum tailings prepared in Example 1. Comparative Example 3

[0065] This comparative example is based on Example 1, except that the modified kaolin prepared in Comparative Example 3 is used in equal parts by weight to replace the modified molybdenum tailings prepared in Example 1. Comparative Example 4

[0066] This comparative example is based on Example 1, except that the amount of reinforcing filler component in step S1 has changed, and the amount of reinforcing filler has changed accordingly; the other steps remain the same as in Example 1. Specifically, In this comparative example, the reinforcing filler was obtained by mixing 45 parts by weight of carbon black N330 and 80 parts by weight of modified molybdenum tailings. The amount of reinforcing filler used in this comparative example was 125 parts by weight. Comparative Example 5

[0067] This comparative example is based on Example 1, except that the composition of the reinforcing filler changed in step S1, while the other steps remained the same as in Example 1. Specifically, In this comparative example, the reinforcing filler was obtained by mixing 45 parts by weight of carbon black N330 and 100 parts by weight of silica (fumed silica from Jiangsu Congzhong Chemical Co., Ltd.). Performance testing

[0068] The rubber materials prepared in Examples 1-10 and Comparative Examples 1-5 were subjected to hardness tests, tensile strength tests, elongation at break tests, and aging resistance tests. The experimental results are shown in Table 2 below.

[0069] The hardness test was conducted according to GB / T 531.1-2008 for Shore A hardness testing; the tensile strength and elongation at break tests were conducted according to GB / T 528-2009. The samples were aged according to GB / T 3512-2001, which describes the method of accelerated aging of vulcanized rubber or thermoplastic rubber in hot air. The aging conditions were 100℃ for 72 hours. After aging, the samples were tested for Shore A hardness, tensile strength and elongation at break according to the test methods before aging.

[0070] Table 2 Experimental results of rubber material performance

[0071] As shown in Table 2, the experimental results indicate that this application uses carbon black and modified molybdenum tailings in a specific ratio. The carbon black and rubber molecular network permeate and support each other to form a three-dimensional branched structure. The modified molybdenum tailings are dispersed in the three-dimensional branched structure, which increases the crosslinking density and improves the mechanical properties and aging resistance of the rubber material.

[0072] The embodiments described in this specific implementation are preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the principles of this application should be covered within the scope of protection of this application.

Claims

1. A functional composite material with added modified molybdenum tailings powder, characterized in that, The raw materials include the following parts by weight: 100 parts of nitrile rubber, 130-180 parts of reinforcing filler, 20-25 parts of plasticizer, 2-7 parts of antioxidant, 1-5 parts of vulcanizing agent, 1-3 parts of accelerator, and 3-8 parts of activator. The reinforcing filler includes carbon black and modified molybdenum tailings. The raw materials for preparing the modified molybdenum tailings include silane coupling agent, molybdenum tailings, and inorganic materials, wherein the inorganic materials are selected from at least one of calcium carbonate and kaolin.

2. The functional composite material with added modified molybdenum tailings powder according to claim 1, characterized in that, The weight ratio of the carbon black to the modified molybdenum tailings is (40~50):(95~105).

3. The functional composite material with added modified molybdenum tailings powder according to claim 1, characterized in that, The weight ratio of the silane coupling agent, the molybdenum tailings, and the inorganic matter is 2.7:30:

80.

4. The functional composite material with added modified molybdenum tailings powder according to claim 3, characterized in that, The inorganic material is kaolin, and the method for preparing the modified molybdenum tailings includes: (1) The kaolin is roasted, and the kaolin obtained from roasting is added to an alkaline solution and stirred in a constant temperature water bath. It is then taken out and left to stand at room temperature. It is placed in a thermostat, taken out and subjected to solid-liquid separation, washing and drying to obtain activated kaolin. (2) The molybdenum tailings were mixed with the kaolin obtained in step (1) and reacted under heating conditions to obtain a complex. (3) The complex obtained in step (2) is added to the silane coupling agent solution, stirred and reacted, and then separated into solid and liquid, washed and dried to obtain modified molybdenum tailings.

5. The functional composite material with added modified molybdenum tailings powder according to claim 3, characterized in that, The inorganic substance is calcium carbonate, and the method for preparing the modified molybdenum tailings includes: (1) Dry the calcium carbonate and molybdenum tailings separately to obtain dried calcium carbonate and molybdenum tailings; (2) Add the silane coupling agent to the ethanol solution and adjust the pH to 3.5~5.5 to obtain the modified solution; (3) Add the dried calcium carbonate and molybdenum tailings from step (1) to the modified liquid obtained in step (2), stir and react, separate the solid and liquid, wash and dry to obtain modified molybdenum tailings.

6. The functional composite material with added modified molybdenum tailings powder according to claim 3, characterized in that, The inorganic materials are calcium carbonate and kaolin, with a weight ratio of calcium carbonate to kaolin of 1:

1. The method for preparing the modified molybdenum tailings includes: (1) The kaolin is roasted, and the kaolin obtained from roasting is added to an alkaline solution and stirred in a constant temperature water bath. It is then taken out and left to stand at room temperature. It is placed in a thermostat, taken out and subjected to solid-liquid separation, washing and drying to obtain activated kaolin. (2) Molybdenum tailings, calcium carbonate and kaolin obtained in step (1) are mixed and reacted under heating conditions to obtain a complex; (3) The complex obtained in step (2) is added to the silane coupling agent solution, stirred and reacted, and then separated into solid and liquid, washed and dried to obtain modified molybdenum tailings.

7. The functional composite material with added modified molybdenum tailings powder according to claim 1, characterized in that, The molybdenum tailings comprise the following chemical composition by mass percentage: SiO2 60-80%, Al2O3 10-16%, K2O 3-6%, Na2O 1-2%, MgO 2-4%, with the balance being other components.

8. The functional composite material with added modified molybdenum tailings powder according to claim 1, characterized in that, The plasticizer includes dioctyl phthalate; and / or, The activator comprises stearic acid and nano-zinc oxide, and the weight ratio of stearic acid to nano-zinc oxide is 1:(1.5~2.5); and / or, The vulcanizing agent is sulfur.

9. A method for preparing a functional composite material with added modified molybdenum tailings powder as described in any one of claims 1 to 8, characterized in that, Includes the following steps: S1. Mix nitrile rubber, reinforcing filler, plasticizer, antioxidant and activator, and then perform intensive mixing to obtain a compound rubber. S2. Add the vulcanizing agent and accelerator to the first-stage compound obtained in step S1, and perform intensive mixing to obtain the second-stage compound. S3. The two-stage compound obtained in step S2 is subjected to open milling and sheeting to obtain a functional composite material with added modified molybdenum tailings powder.

10. The application of a functional composite material with added modified molybdenum tailings powder as described in any one of claims 1 to 8 in hoses, belts, seals and shock-absorbing materials.

Images