阅读说明：本技术 一种煤矸石填充的橡胶组合物及其制备方法 (Coal gangue filled rubber composition and preparation method thereof ) 是由 王亮 倪建明 张俊 于 2021-03-09 设计创作，主要内容包括：本发明公开了一种改性煤矸石填充的橡胶组合物及其制备方法,制备步骤如下：S1、煤矸石预处理；S2、煤矸石粉的浸泡与干燥；S3、煤矸石粉的硫化成型；单宁酸分子中含有大量的苯环和羟基活性官能团,吸附在煤矸石表面后,能与橡胶形成无机基体-单宁酸-无机基体的结合层,降低结合层厚度,有效提升煤矸石与橡胶之间的结合力,从而提高拉伸强度、撕裂强度和最大变形,其拉伸强度可提高25.3％,撕裂强度提高13.2％,最大变形提高14.5％；减少对炭黑、白炭黑和其他矿物质填料等橡胶增强剂的依赖,节约一级能源消耗。(The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein the preparation method comprises the following steps: s1, coal gangue pretreatment; s2, soaking and drying the coal gangue powder; s3, vulcanizing and forming the coal gangue powder; the tannin molecules contain a large number of benzene rings and hydroxyl active functional groups, and after the tannin molecules are adsorbed on the surface of the coal gangue, the tannin molecules and the rubber can form a bonding layer of an inorganic matrix-tannin-inorganic matrix, the thickness of the bonding layer is reduced, and the bonding force between the coal gangue and the rubber is effectively improved, so that the tensile strength, the tearing strength and the maximum deformation are improved, wherein the tensile strength can be improved by 25.3%, the tearing strength is improved by 13.2%, and the maximum deformation is improved by 14.5%; the dependence on rubber reinforcing agents such as carbon black, white carbon black and other mineral fillers is reduced, and the first-level energy consumption is saved.)

1. A rubber composition filled with modified coal gangue and a preparation method thereof are characterized in that: the preparation steps are as follows: s1, coal gangue pretreatment; s2, soaking and drying the coal gangue powder; and S3, vulcanizing and forming the coal gangue powder.

2. The modified coal gangue filled rubber composition and the preparation method thereof as claimed in claim 1, wherein the coal gangue pretreatment in S1 comprises: grinding the crushed coal gangue raw material by using a ball mill, sieving to obtain coal gangue micro powder with the particle size of less than 100 meshes, and taking out for later use after blast drying in an environment with the temperature of 105 ℃.

3. The rubber composition filled with modified coal gangue and the preparation method thereof according to claim 1, wherein the soaking and drying of the coal gangue powder in the S2 comprises the following steps: immersing coal gangue powder into a saturated calcium hydroxide solution for 2 hours, filtering and drying, immersing into a 1% tannic acid solution for 24 hours, and blowing and drying at 80 ℃ to obtain the modified coal gangue powder.

4. The rubber composition filled with modified coal gangue and the preparation method thereof according to claim 1, wherein the vulcanization molding of the coal gangue powder in S3 comprises the following steps: taking 100 parts of natural rubber, sequentially adding 1 part of stearic acid, 1.5 parts of accelerator DM, 0.5 part of accelerator TT, 3 parts of zinc oxide, 1.5 parts of anti-aging agent, 40 parts of white carbon black and 10-30 parts of coal gangue powder mixture prepared in the S1-S2 steps, 2.3 parts of sulfur and the natural rubber, mixing uniformly by pressing with a calender, and vulcanizing and molding.

5. The modified coal gangue filled rubber composition as defined in claim 4 wherein the roller temperature of said calender is 60-70 ℃.

6. The modified coal gangue filled rubber composition and the preparation method thereof as claimed in claim 4, wherein the natural rubber can be one or more of air rubber, smoke rubber and rubber clearrubber.

7. The modified coal gangue filled rubber composition as defined in claim 3 and the preparation method thereof, wherein said tannic acid is an analytically pure reagent having a purity of 95% or more.

Technical Field

The invention belongs to the field of coal mining, and particularly relates to a rubber composition filled with modified coal gangue and a preparation method thereof.

Background

High molecular polymer materials, metal materials and inorganic materials are three basic materials in the world at present, rubber is widely applied polymer materials, mechanical properties are poor due to linear macromolecular chain structures of the rubber, reinforcing agents are generally needed to improve the wear resistance, strength, elasticity and dynamic strength of natural rubber, and carbon black, white carbon black, argil, calcium carbonate, silicate and the like are used as filling reinforcing agents of the rubber, so that the strength and the service life of rubber products can be improved, the processability of the rubber is improved, and the rubber has excellent service performance.

The coal gangue is the carbonaceous rock and rock discharged in the processes of shaft building, development and tunneling, coal mining and coal washing of coal mines, is a general name of solid waste discharged in the processes of coal mine construction and coal production, is one of the solid waste with the largest discharge amount in China, can solve the disposal problem and reduce the material cost and realize the sustainable utilization of resources by recycling, can be used for producing cement, being used as concrete aggregate, manufacturing sintered bricks, producing soil fertilizer, being used as low-calorific-value fuel, being used as a roadbed cushion layer, filling material for underground backfilling and the like at present, can reduce the physical and mechanical properties and the ageing resistance of rubber by partially replacing carbon black with the coal gangue after being processed by superfine grinding, and can improve the compatibility between the inorganic mineral powder coal gangue and the organic high molecular polymer due to the lower compatibility between the inorganic mineral powder coal gangue and the organic high molecular polymer as the main material, the surface of the coal gangue is modified to increase the hydroxyl active points on the surface of the coal gangue, the silane coupling agent is firmly combined with the coal gangue through hydrolysis reaction to form organic groups which are subjected to covalent reaction with rubber macromolecules, the organic groups improve the compatibility of coal gangue powder and a rubber matrix, and further improve the mechanical property of rubber, but the silane coupling agent has severe storage conditions, volatility and toxicity and is not beneficial to industrial application.

Disclosure of Invention

The invention aims to solve the technical problem of improving the compatibility between the coal gangue and rubber by using the tannic acid modified coal gangue, effectively utilizing the waste coal gangue residues, saving resources, protecting the environment, reducing the use of mineral fillers such as white carbon black and the like and reducing the production cost.

In order to achieve the purpose, the invention adopts the technical scheme that: a rubber composition filled with modified coal gangue and a preparation method thereof are disclosed, the preparation steps are as follows: s1, coal gangue pretreatment; s2, soaking and drying the coal gangue powder; and S3, vulcanizing and forming the coal gangue powder.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein the coal gangue pretreatment in S1 comprises the following steps: grinding the crushed coal gangue raw material by using a ball mill, sieving to obtain coal gangue micro powder with the particle size of less than 100 meshes, and taking out for later use after blast drying in an environment with the temperature of 105 ℃.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein the soaking and drying of the coal gangue powder in S2 comprises the following steps: immersing coal gangue powder into a saturated calcium hydroxide solution for 2 hours, filtering and drying, immersing into a 1% tannic acid solution for 24 hours, and blowing and drying at 80 ℃ to obtain the modified coal gangue powder.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein the vulcanization molding of the coal gangue powder in S3 comprises the following steps: taking 100 parts of natural rubber, sequentially adding 1 part of stearic acid, 1.5 parts of accelerator DM, 0.5 part of accelerator TT, 3 parts of zinc oxide, 1.5 parts of anti-aging agent, 40 parts of white carbon black and 10-30 parts of coal gangue powder mixture prepared in the S1-S2 steps, 2.3 parts of sulfur and the natural rubber, mixing uniformly by pressing with a calender, and vulcanizing and molding.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein the roller temperature of a calender is 60-70 ℃.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof.

The invention discloses a rubber composition filled with modified coal gangue and a preparation method thereof, wherein tannic acid is an analytically pure reagent with the purity of more than or equal to 95%.

The technical scheme adopted by the invention is as follows: compared with the prior art, the invention has the beneficial effects that: tannin (C76H52O46) is a polyphenol compound, and has low cost, no toxicity and no harm. The plant extract is widely existed in tea, coffee, leaves, barks and immature fruits, is one of main components of plants, and has the characteristics of low price, wide sources, no toxicity, no harm and the like; the tannin molecules contain a large number of benzene rings and hydroxyl active functional groups, and after the tannin molecules are adsorbed on the surface of the coal gangue, the tannin molecules and the rubber can form a bonding layer of an inorganic matrix-tannin-inorganic matrix, the thickness of the bonding layer is reduced, and the bonding force between the coal gangue and the rubber is effectively improved, so that the tensile strength, the tearing strength and the maximum deformation are improved, wherein the tensile strength can be improved by 25.3%, the tearing strength is improved by 13.2%, and the maximum deformation is improved by 14.5%; the dependence on rubber reinforcing agents such as carbon black, white carbon black and other mineral fillers is reduced, and the first-level energy consumption is saved; the coal gangue waste residue can be effectively utilized, the comprehensive utilization is enlarged, the utilization rate is increased, the emission of solid waste is reduced, the pollution of occupied land to the atmosphere, soil, water resources and vegetation is further avoided, and the sustainable development is facilitated; the tannic acid solution has no corrosivity and irritation, is beneficial to industrial application, and the waste liquid is harmless and can be directly discharged.

The present invention will be described in more detail with reference to the following examples.

Detailed Description

The following embodiments are provided to describe the embodiments of the present invention, such as the shapes and structures of the components, the mutual positions and connection relationships among the components, the functions and working principles of the components, the manufacturing processes and the operation and use methods of the components, and the like, in further detail, so as to help those skilled in the art to more completely, accurately and deeply understand the inventive concept and technical solutions of the present invention.

Example 1

The formula is as follows: 100 parts of natural rubber, 1 part of stearic acid, 1.5 parts of an accelerator DM, 0.5 part of an accelerator TT, 3 parts of zinc oxide, 1.5 parts of an anti-aging agent, 40 parts of white carbon black and 2.3 parts of sulfur.

Mixing 100 parts by mass of natural rubber and 1 part by mass of stearic acid, using a calender to fully fuse the stearic acid and the rubber, adding 1.5 parts by mass of an accelerator DM, repeating the steps until all materials and the rubber are fully and uniformly fused, and finally vulcanizing and molding.

Example 2

The formula is as follows: 100 parts of natural rubber, 1 part of stearic acid, 1.5 parts of an accelerator DM, 0.5 part of an accelerator TT, 3 parts of zinc oxide, 1.5 parts of an anti-aging agent, 40 parts of white carbon black, 20 parts of coal gangue micropowder and 2.3 parts of sulfur.

Mixing 100 parts by mass of natural rubber and 1 part by mass of stearic acid, using a calender to fully fuse the stearic acid and the rubber, adding 1.5 parts by mass of an accelerator DM, repeating the steps until all materials and the rubber are fully and uniformly fused, and finally vulcanizing and molding.

Example 3

The formula is as follows: 100 parts of natural rubber, 1 part of stearic acid, 1.5 parts of an accelerator DM, 0.5 part of an accelerator TT, 3 parts of zinc oxide, 1.5 parts of an anti-aging agent, 40 parts of white carbon black, 10 parts of modified coal gangue micropowder and 2.3 parts of sulfur.

Mixing 100 parts by mass of natural rubber and 1 part by mass of stearic acid, using a calender to fully fuse the stearic acid and the rubber, adding 1.5 parts by mass of an accelerator DM, repeating the steps until all materials and the rubber are fully and uniformly fused, and finally vulcanizing and molding.

Example 4

The formula is as follows: 100 parts of natural rubber, 1 part of stearic acid, 1.5 parts of an accelerator DM, 0.5 part of an accelerator TT, 3 parts of zinc oxide, 1.5 parts of an anti-aging agent, 40 parts of white carbon black, 20 parts of modified coal gangue micropowder and 2.3 parts of sulfur.

Mixing 100 parts by mass of natural rubber and 1 part by mass of stearic acid, using a calender to fully fuse the stearic acid and the rubber, adding 1.5 parts by mass of an accelerator DM, repeating the steps until all materials and the rubber are fully and uniformly fused, and finally vulcanizing and molding.

Example 5

The formula is as follows: 100 parts of natural rubber, 1 part of stearic acid, 1.5 parts of an accelerator DM, 0.5 part of an accelerator TT, 3 parts of zinc oxide, 1.5 parts of an anti-aging agent, 40 parts of white carbon black, 30 parts of modified coal gangue micropowder and 2.3 parts of sulfur.

Mixing 100 parts by mass of natural rubber and 1 part by mass of stearic acid, using a calender to fully fuse the stearic acid and the rubber, adding 1.5 parts by mass of an accelerator DM, repeating the steps until all materials and the rubber are fully and uniformly fused, and finally vulcanizing and molding.

The table below shows that the binding force between the coal gangue and the rubber is effectively improved by adopting the modified coal gangue of the tannic acid and the calcium hydroxide solution, so that the tensile strength, the tearing strength and the maximum deformation are improved.

The technical scheme adopted by the invention is as follows: compared with the prior art, the invention has the beneficial effects that: tannin (C76H52O46) is a polyphenol compound, and has low cost, no toxicity and no harm. The plant extract is widely existed in tea, coffee, leaves, barks and immature fruits, is one of main components of plants, and has the characteristics of low price, wide sources, no toxicity, no harm and the like; the tannin molecules contain a large number of benzene rings and hydroxyl active functional groups, and after the tannin molecules are adsorbed on the surface of the coal gangue, the tannin molecules and the rubber can form a bonding layer of an inorganic matrix-tannin-inorganic matrix, the thickness of the bonding layer is reduced, and the bonding force between the coal gangue and the rubber is effectively improved, so that the tensile strength, the tearing strength and the maximum deformation are improved, wherein the tensile strength can be improved by 25.3%, the tearing strength is improved by 13.2%, and the maximum deformation is improved by 14.5%; the dependence on rubber reinforcing agents such as carbon black, white carbon black and other mineral fillers is reduced, and the first-level energy consumption is saved; the coal gangue waste residue can be effectively utilized, the comprehensive utilization is enlarged, the utilization rate is increased, the emission of solid waste is reduced, the pollution of occupied land to the atmosphere, soil, water resources and vegetation is further avoided, and the sustainable development is facilitated; the tannic acid solution has no corrosivity and irritation, is beneficial to industrial application, and the waste liquid is harmless and can be directly discharged.

The invention has been described in an illustrative manner, and it is to be understood that the invention is not limited to the precise form disclosed, and that various insubstantial modifications of the inventive concepts and solutions, or their direct application to other applications without such modifications, are intended to be covered by the scope of the invention.