Impact-resistant wear-resistant lining plate for mining and preparation method of impact-resistant wear-resistant lining plate
By copolymerizing modified silica hollow microspheres with vinyl POSS, the problem of poor compatibility between inorganic particles and organic resins was solved, improving the mechanical strength and wear resistance of impact-resistant and wear-resistant liners used in mining, and achieving high heat resistance and good energy absorption effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUNAN HYSTER MATERIAL TECH CO
- Filing Date
- 2026-03-26
- Publication Date
- 2026-05-12
AI Technical Summary
Traditional inorganic particles have poor compatibility with organic resins and are prone to delamination, which leads to the degradation of the performance of impact-resistant and wear-resistant liners used in mining.
By modifying hollow silica microspheres with double bonds and copolymerizing them with vinyl POSS and vinyl chloride, an inorganic-organic cross-linked composite structure is formed, thereby improving the interfacial bonding force.
It significantly improves the mechanical strength and wear resistance of impact-resistant and wear-resistant liners used in mining, increases the heat resistance temperature, and the hollow structure absorbs impact energy, prevents microspheres from falling off, and enhances the interfacial bonding force.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer processing technology, specifically a mining impact-resistant and wear-resistant liner and its preparation method. Background Technology
[0002] Ultra-high molecular weight polyethylene (UHMWPE) possesses excellent wear resistance, impact resistance, chemical corrosion resistance, and low-temperature toughness, making it widely used as a thermoplastic engineering plastic. However, UHMWPE also exhibits some inherent drawbacks of polyethylene resin, such as low heat distortion temperature, poor creep resistance, high coefficient of thermal expansion, and low surface hardness, which somewhat limits its application range.
[0003] The main measures to improve the heat resistance of ultra-high molecular weight polyethylene (UHMWPE) products include: using a stretching process to orient the UHMWPE macromolecules; using silane crosslinking, peroxide crosslinking, and other methods to form a network structure of UHMWPE macromolecules to increase the heat deformation resistance of the composite material; and adding inorganic modifiers such as glass fiber, carbon fiber, and boron fiber.
[0004] Chinese patent CN102558645A discloses an impact-resistant and wear-resistant liner and its preparation method. This method uses ultra-high molecular weight polyethylene (UHMWPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), ultrafine aluminum hydroxide, diatomaceous earth, vinyltriethoxysilane, benzoic acid, and dicumyl peroxide. The formulated materials are mixed stepwise in a high-speed mixer until homogeneous, and then hot-pressed into shape on a hot press. The resulting impact-resistant and wear-resistant liner retains the excellent wear resistance, impact resistance, chemical corrosion resistance, and low-temperature toughness inherent in UHMWPE, while also exhibiting good processing performance and low material cost. However, it only involves blending inorganic fillers with UHMWPE, and the poor compatibility between inorganic particles and organic resins leads to a tendency for agglomeration. Summary of the Invention
[0005] The purpose of this invention is to provide an impact-resistant and wear-resistant liner for mining and its preparation method. The method involves modifying burr-like hollow silica microspheres with double bonds to obtain double-bond modified silica hollow microspheres, which are then copolymerized with vinyl POSS and vinyl chloride. This solves the problems of poor compatibility and easy delamination between traditional inorganic particles and organic resins. It promotes the embedding of double-bond modified silica hollow microspheres and vinyl POSS into polyvinyl chloride matrix through chemical bonds, significantly improving interfacial bonding and preventing performance degradation due to detachment during use. This results in a liner with good mechanical strength and wear resistance, as well as a high heat resistance temperature.
[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing an impact-resistant and wear-resistant liner for mining includes the following steps: Step 1: Using formaldehyde and phenol as carbon sources and ammonium dihydrogen phosphate as pore-forming agents, a phenolic resin precursor is formed through a condensation reaction. After calcination, a porous structure is formed, resulting in porous carbon microspheres.
[0007] Step 2: Using porous carbon microspheres as a carrier, hexadecyltrimethylammonium bromide as a template agent, and ammonia water as an alkaline catalytic environment, tetraethyl orthosilicate forms a silica framework through hydrolysis-condensation reaction. The template agent is removed by treatment with isopropanol and ammonium nitrate to obtain silica composite microspheres.
[0008] Step 3: On the surface of silica composite microspheres, tetraethyl orthosilicate is used as the silicon source for secondary coating modification. Urea is used to regulate the microenvironment and promote uniform deposition of the silicon layer to obtain modified silica hollow microspheres with burrs. The modified silica hollow microspheres are then treated by the hydrolysis-condensation reaction of γ-methacryloyloxypropyltrimethoxysilane to obtain double bond modified silica hollow microspheres.
[0009] Step 4: Using di(2-ethylhexyl) peroxide dicarbonate and dilauroyl peroxide as composite initiators, the free radical polymerization reaction of vinyl chloride monomer is initiated. Double bond modified silica and vinyl POSS participate in polymerization through surface double bonds to form a cross-linked composite structure of inorganic and organic phases. After high temperature and high pressure hot pressing molding, the impact-resistant and wear-resistant liner for mining is obtained.
[0010] Furthermore, the specific preparation steps for the silica composite microspheres are as follows: Hexadecyltrimethylammonium bromide, porous carbon microspheres, and ammonia were added to a reaction vessel and stirred for 30-40 min at 20-25℃ and 500-600 r / min. Then, tetraethyl orthosilicate was added, and the reaction was continued for 6-7 h. After centrifugation at 8000-9000 r / min for 5-8 min, the filter cake was transferred to isopropanol and ammonium nitrate and reacted at 80-90℃ for 24 h. The mixture was then freeze-dried under vacuum at -20℃ for 12-14 h to obtain silica composite microspheres.
[0011] Furthermore, the ratio of hexadecyltrimethylammonium bromide, porous carbon microspheres, ammonia, tetraethyl orthosilicate, isopropanol, and ammonium nitrate is 30-40g: 50-60g: 2-3L: 170-180mL: 800-900mL: 14-16g.
[0012] Furthermore, the specific preparation steps of the modified silica hollow microspheres are as follows: Hexadecyltrimethylammonium bromide, urea, silica composite microspheres, and deionized water were added to a reaction vessel and stirred for 30-40 min at 20-25℃ and 500-600 r / min. Then, isopropanol and tetraethyl orthosilicate were added, and stirring was continued for another 30-40 min. The mixture was then heated to 70-80℃ and reacted for 16-18 h. After filtration, the filter cake was washed 2-4 times with deionized water and dried under vacuum at 60-80℃ for 1-2 h. The cake was then transferred to a muffle furnace and calcined at 550-600℃ for 6-8 h to obtain modified silica hollow microspheres.
[0013] Furthermore, the ratio of hexadecyltrimethylammonium bromide, urea, silica composite microspheres, deionized water, isopropanol, and tetraethyl orthosilicate is 20-22g: 12-14g: 8-10g: 450-500mL: 450-500mL: 4-5mL.
[0014] Furthermore, the specific preparation steps for double-bond modified silica hollow microspheres are as follows: Modified silica hollow microspheres, anhydrous ethanol, and deionized water were added to a reaction vessel and stirred for 10-12 min at 50-60℃ and 500-600 r / min. Then, γ-methacryloyloxypropyltrimethoxysilane was added, and the reaction was continued to be stirred for 6-8 h. After filtration, the precipitate was washed 2-4 times with deionized water and anhydrous ethanol and dried under vacuum at 60-80℃ for 1-2 h to obtain double bond modified silica hollow microspheres.
[0015] Furthermore, the ratio of modified silica hollow microspheres, anhydrous ethanol, deionized water, and γ-methacryloyloxypropyltrimethoxysilane is 15-20g: 500-600mL: 100-120mL: 12-14mL.
[0016] Furthermore, the specific preparation steps for impact-resistant and wear-resistant liners used in mining are as follows: Double-bond modified silica hollow microspheres and vinyl POSS were added to a reactor and stirred for 3-4 hours at 50-60℃ and 400-500 rpm. Then, 1,4-dioxane, di(2-ethylhexyl) peroxide dicarbonate, and dilauryl peroxide were added to the reactor. The reactor was sealed and protected with nitrogen gas. Finally, vinyl chloride was added to the reactor and stirred for 4-5 hours at 50-60℃ and 500-600 rpm. After the reaction is terminated, a methanol solution with a mass concentration of 20-22% is added. After the addition is complete, the mixture is allowed to stand for 24-29 hours, filtered, and the filter cake is washed 2-4 times with anhydrous methanol. It is then vacuum dried at 60-80℃ for 1-2 hours to obtain modified polyvinyl chloride paste resin. The modified polyvinyl chloride paste resin is then transferred to a hot press and hot-pressed at 5-10MPa and 350-390℃ for 20-30 minutes to obtain impact-resistant and wear-resistant lining plates for mining.
[0017] Furthermore, the ratio of double bond modified silica hollow microspheres, vinyl POSS, 1,4-dioxane, di(2-ethylhexyl) peroxydicarbonate, dilauroyl peroxide, vinyl chloride, and methanol solution is 10-12g: 8-10g: 120-140mL: 1-2g: 1-2g: 80-90g: 500-600mL.
[0018] The beneficial effects of this invention are: 1. The impact-resistant and wear-resistant liner for mining of the present invention is obtained by double-bonding modified silica hollow microspheres containing burrs, and then copolymerizing them with vinyl POSS and vinyl chloride. This solves the problem of poor compatibility and easy delamination between traditional inorganic particles and organic resins. It enables the double-bond modified silica hollow microspheres and vinyl POSS to be embedded into polyvinyl chloride body through chemical bonds, which significantly improves the interfacial bonding force and avoids performance degradation caused by detachment during use. It gives the liner good mechanical strength and wear resistance, and also has a high heat resistance temperature.
[0019] 2. The modified silica hollow microspheres of the present invention have a hollow structure with a burr-like shell. The hollow structure can give the impact-resistant and wear-resistant liner for mining stronger impact resistance. When the mining material hits the liner, the impact energy will drive the cavity of the hollow microsphere to undergo elastic deformation. This process will convert the impact kinetic energy into structural deformation energy, avoiding the direct transfer of energy to the polyvinyl chloride matrix, thereby reducing the cracking or damage of the matrix due to excessive instantaneous force. Compared with solid particles, the hollow structure can absorb more impact energy through deformation energy dissipation, which greatly reduces the destructive force of impact on the liner.
[0020] 3. The burr-like protrusions of the present invention can penetrate deep into the polyvinyl chloride resin matrix to form a mechanical locking structure of anchors, making the bonding force between the silica microspheres and the resin interface far greater than that of ordinary smooth particles. When impacted, this anchoring effect can prevent the microspheres from falling off the matrix, avoid gaps or cracks at the interface, and ensure that the impact energy can be effectively transmitted and dispersed through the interface, rather than concentrated in a local area, leading to interface peeling failure. Detailed Implementation
[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0022] Example 1: A method for preparing an impact-resistant and wear-resistant liner for mining, comprising the following steps: S1: 70 mL of 30% formaldehyde solution, 12 g of ammonium dihydrogen phosphate, 80 g of phenol, and 500 mL of deionized water were added to a reaction vessel and stirred at 55 °C and 500 r / min for 1 h. Then, 10 mL of 1% sodium hydroxide solution was added, and the reaction continued for 1 h. The mixture was heated at 90 °C for 1 h, and the product was cooled to 60 °C. The pH was adjusted to neutral with 1 mol / L hydrochloric acid solution, and the product was dehydrated by vacuum distillation at 0.092 MPa. The product was placed in a mixed solution of 1 mL Tween 80, 40 mL of n-pentane, and 4 mL of concentrated sulfuric acid and stirred at 3000 r / min for 20 min. The mixture was transferred to a mold, foamed and cured at 60 °C for 20 h, and then transferred to a muffle furnace and calcined at 550 °C for 2 h under nitrogen protection to obtain porous carbon microspheres.
[0023] S2: Add 30g hexadecyltrimethylammonium bromide, 50g porous carbon microspheres and 2L ammonia water to a reaction vessel, stir for 30min at 20℃ and 500r / min, then add 170mL tetraethyl orthosilicate, continue the reaction for 6h, centrifuge at 8000r / min for 5min, transfer the filter cake to 800mL isopropanol and 14g ammonium nitrate, react at 80℃ for 24h, and freeze-dry under vacuum at -20℃ for 12h to obtain silica composite microspheres.
[0024] S3: Add 20g hexadecyltrimethylammonium bromide, 12g urea, 8g silica composite microspheres and 450mL deionized water to a reaction vessel, stir for 30min at 20℃ and 500r / min, then add 450mL isopropanol and 4mL tetraethyl orthosilicate, continue stirring for 30min, heat to 70℃, continue the reaction for 16h, filter, wash the filter cake twice with deionized water, vacuum dry at 60℃ for 1h, transfer to a muffle furnace, heat to 550℃ and calcine for 6h to obtain modified silica hollow microspheres.
[0025] S4: Add 15g of modified silica hollow microspheres, 500mL of anhydrous ethanol and 100mL of deionized water to a reaction vessel, stir for 10min at 50℃ and 500r / min, then add 12mL of γ-methacryloyloxypropyltrimethoxysilane, continue stirring for 6h, filter, wash the precipitate twice with deionized water and anhydrous ethanol, and dry under vacuum at 60℃ for 1h to obtain double bond modified silica hollow microspheres.
[0026] S5: Add 10g of double-bond modified silica hollow microspheres and 8g of vinyl POSS to a reactor and stir for 3h at 50℃ and 400r / min. Add 120mL of 1,4-dioxane, 1g of initiator di(2-ethylhexyl) peroxide dicarbonate and 1g of dilauryl peroxide to the reactor, seal, and purge with nitrogen. Then add 80g of vinyl chloride to the reactor and stir for 4h at 50℃ and 500r / min. After the reaction is terminated, add 500mL of 20% methanol solution. After the addition is complete, let stand for 24h, filter, wash the filter cake twice with anhydrous methanol, and vacuum dry at 60℃ for 1h to obtain modified polyvinyl chloride paste resin. Then transfer the modified polyvinyl chloride paste resin to a hot press and hot press at 5MPa and 350℃ for 20min to obtain an impact-resistant and wear-resistant liner for mining.
[0027] Example 2: A method for preparing an impact-resistant and wear-resistant liner for mining, comprising the following steps: S1: Add 75 mL of 31% formaldehyde solution, 13 g of ammonium dihydrogen phosphate, 85 g of phenol, and 550 mL of deionized water to a reaction vessel. Stir at 57.5 °C and 550 r / min for 1.5 h. Then add 11 mL of 1.5% sodium hydroxide solution and continue the reaction for 1.5 h. Heat at 92.5 °C for 1.5 h. Cool the product to 65 °C and adjust the temperature with 1.5 mol / L hydrochloric acid solution. The pH was adjusted to neutral, and the mixture was dehydrated by vacuum distillation at 0.0935 MPa. The product was then placed in a mixed solution of 1.5 mL Tween 80, 42.5 mL n-pentane, and 4.5 mL concentrated sulfuric acid and stirred at 3100 r / min for 25 min. The mixture was then transferred to a mold, foamed and cured at 65 °C for 22 h, and then transferred to a muffle furnace and calcined at 555 °C for 2.5 h under nitrogen protection to obtain porous carbon microspheres.
[0028] S2: Add 35g hexadecyltrimethylammonium bromide, 55g porous carbon microspheres and 2.5L ammonia water to a reaction vessel, stir for 35min at 22.5℃ and 550r / min, then add 175mL tetraethyl orthosilicate, continue the reaction for 6.5h, centrifuge at 8500r / min for 6.5min, transfer the filter cake to 850mL isopropanol and 15g ammonium nitrate, react at 85℃ for 24h, and freeze-dry under vacuum at -20℃ for 13h to obtain silica composite microspheres.
[0029] S3: 21g hexadecyltrimethylammonium bromide, 13g urea, 9g silica composite microspheres and 475mL deionized water were added to a reaction vessel and stirred for 35min at 22.5℃ and 550r / min. Then 475mL isopropanol and 4.5mL tetraethyl orthosilicate were added and stirred for another 35min. The mixture was heated to 75℃ and reacted for 17h. The mixture was filtered, and the filter cake was washed three times with deionized water and dried under vacuum at 70℃ for 1.5h. The cake was then transferred to a muffle furnace and calcined at 575℃ for 7h to obtain modified silica hollow microspheres.
[0030] S4: 17.5 g of modified silica hollow microspheres, 550 mL of anhydrous ethanol and 110 mL of deionized water were added to a reaction vessel and stirred for 11 min at 55 °C and 550 r / min. Then, 13 mL of γ-methacryloyloxypropyltrimethoxysilane was added and the reaction was continued to be stirred for 7 h. After filtration, the precipitate was washed three times with deionized water and anhydrous ethanol and dried under vacuum at 70 °C for 1.5 h to obtain double bond modified silica hollow microspheres.
[0031] S5: Add 11g of double-bond modified silica hollow microspheres and 9g of vinyl POSS to the reactor, stir for 3.5h at 55℃ and 450r / min, and then add 130mL of the mixture. 1,4-Dioxane, 1.5g of initiator di(2-ethylhexyl) peroxide dicarbonate, and 1.5g of dilauryl peroxide were added to a reaction vessel, sealed, and protected with nitrogen gas. Then, 85g of vinyl chloride was added to the reaction vessel, and the mixture was stirred at 55℃ and 550r / min for 4.5h. After the reaction was terminated, 550mL of 21% methanol solution was added dropwise. After the addition was complete, the mixture was allowed to stand for 26.5h, filtered, and the filter cake was washed three times with anhydrous methanol and vacuum dried at 70℃ for 1.5h to obtain modified polyvinyl chloride paste resin. The modified polyvinyl chloride paste resin was then transferred to a hot press and hot-pressed at 7.5MPa and 370℃ for 25min to obtain an impact-resistant and wear-resistant liner for mining.
[0032] Example 3: A method for preparing an impact-resistant and wear-resistant liner for mining, comprising the following steps: S1: 80 mL of 32% formaldehyde solution, 14 g of ammonium dihydrogen phosphate, 90 g of phenol, and 600 mL of deionized water were added to a reaction vessel and stirred at 60 °C and 600 r / min for 2 h. Then, 12 mL of 2% sodium hydroxide solution was added, and the reaction continued for 2 h. The mixture was heated at 95 °C for 2 h, and the product was cooled to 70 °C. The pH was adjusted to neutral with 2 mol / L hydrochloric acid solution, and the product was dehydrated by vacuum distillation at 0.095 MPa. The product was placed in a mixed solution of 2 mL Tween 80, 45 mL of n-pentane, and 5 mL of concentrated sulfuric acid and stirred at 3200 r / min for 30 min. The mixture was transferred to a mold, foamed and cured at 70 °C for 24 h, and then transferred to a muffle furnace and calcined at 560 °C for 3 h under nitrogen protection to obtain porous carbon microspheres.
[0033] S2: Add 40g hexadecyltrimethylammonium bromide, 60g porous carbon microspheres and 3L ammonia water to a reaction vessel, stir for 40min at 25℃ and 600r / min, then add 180mL tetraethyl orthosilicate, continue the reaction for 7h, centrifuge at 9000r / min for 8min, transfer the filter cake to 900mL isopropanol and 16g ammonium nitrate, react at 90℃ for 24h, and freeze-dry under vacuum at -20℃ for 14h to obtain silica composite microspheres.
[0034] S3: 22g hexadecyltrimethylammonium bromide, 14g urea, 10g silica composite microspheres and 500mL deionized water were added to a reaction vessel and stirred for 40min at 25℃ and 600r / min. Then 500mL isopropanol and 5mL tetraethyl orthosilicate were added and stirred for another 40min. The mixture was heated to 80℃ and reacted for another 18h. The mixture was filtered, and the filter cake was washed four times with deionized water and dried under vacuum at 80℃ for 2h. The cake was then transferred to a muffle furnace and calcined at 600℃ for 8h to obtain modified silica hollow microspheres.
[0035] S4: Add 20g of modified silica hollow microspheres, 600mL of anhydrous ethanol and 120mL of deionized water to a reaction vessel, stir for 12min at 60℃ and 600r / min, then add 14mL of γ-methacryloyloxypropyltrimethoxysilane, continue stirring for 8h, filter, wash the precipitate 4 times with deionized water and anhydrous ethanol, and dry under vacuum at 80℃ for 2h to obtain double bond modified silica hollow microspheres.
[0036] S5: 12g of double-bond modified silica hollow microspheres and 10g of vinyl POSS were added to a reaction vessel and stirred for 4h at 60℃ and 500r / min. 140mL of 1,4-dioxane, 2g of initiator di(2-ethylhexyl) peroxide dicarbonate and 2g of dilauryl peroxide were added to the reaction vessel, which was then sealed and protected with nitrogen. 90g of vinyl chloride was then added to the reaction vessel and stirred for 5h at 60℃ and 600r / min. After the reaction was terminated, 600mL of 22% methanol solution was added dropwise. After the addition was complete, the mixture was allowed to stand for 29h, filtered, and the filter cake was washed four times with anhydrous methanol and vacuum dried at 80℃ for 2h to obtain modified polyvinyl chloride paste resin. The modified polyvinyl chloride paste resin was then transferred to a hot press and hot-pressed at 10MPa and 390℃ for 30min to obtain an impact-resistant and wear-resistant liner for mining.
[0037] Comparative Example 1: Based on Example 3, the porous carbon microspheres in step S2 were omitted.
[0038] Comparative Example 2: Based on Example 3, the modified silica hollow microspheres in step S4 were replaced with silica composite microspheres in step S2.
[0039] Comparative Example 3: Based on Example 3, the double bond modified silica hollow microspheres in step S5 were replaced with the modified silica hollow microspheres in step S3.
[0040] The performance of the impact-resistant and wear-resistant liners for mining obtained in Examples 1-3 and Comparative Examples 1-3 was tested, and the results are shown in Table 1: Table 1
[0041] As can be seen from Table 1, in Comparative Example 1, the porous carbon microspheres in step S2 were omitted, resulting in a significant decrease in impact resistance. The hollow structure could not effectively absorb impact energy through deformation, the matrix was prone to cracking, the mechanical strength was insufficient, and the reinforcing effect of the porous carbon core was lacking. The load-bearing capacity of the composite system decreased, the tensile elongation at break decreased simultaneously, the thermal stability deteriorated, the high thermal stability of porous carbon could not be utilized, the liner was prone to softening and deformation under high-temperature conditions in the mine, the wear resistance decreased, and the insufficient structural stability caused the microspheres to fall off easily, thus failing to continuously exert the wear-resistant reinforcing effect.
[0042] Comparative Example 2 replaced the modified silica hollow microspheres with silica composite microspheres. The interfacial bonding was weak, and there was no anchoring effect of burr-like protrusions. The microspheres and polyvinyl chloride matrix were prone to delamination and detachment, resulting in a decrease in tensile strength and impact strength, as well as a decrease in wear resistance. The smooth surface of the microspheres had low frictional resistance with the matrix, which could not effectively prevent material wear. Furthermore, wear channels were easily formed due to interfacial peeling. The heat distortion temperature was low, and the dense silica layer of the secondary coating was not formed. The thermal conductivity and structural stability of the system were insufficient, and deformation was prone to occur at high temperatures.
[0043] Comparative Example 3 replaced the double bond modified silica hollow microspheres with modified silica hollow microspheres. The compatibility was extremely poor. The microspheres and polyvinyl chloride matrix were prone to delamination. Impact energy could not be transferred through the interface, the notched impact strength decreased, the wear resistance was the worst, the microspheres were easy to detach from the matrix during friction, the thermal stability was the worst, the weak interfacial bonding led to uneven heat transfer, and local overheating and softening was easy. It could not adapt to the high temperature and high load conditions of mining. The tensile elongation at break was the lowest. The interfacial delamination led to stress concentration, and the matrix was prone to brittle fracture during tensile process. It could not withstand repeated pulling of mining materials.
[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims
1. A method for preparing an impact-resistant and wear-resistant liner for mining, characterized in that, Includes the following steps: Step 1: Using formaldehyde and phenol as carbon sources and ammonium dihydrogen phosphate as pore-forming agents, a phenolic resin precursor is formed through a condensation reaction. After calcination, a porous structure is formed, resulting in porous carbon microspheres. Step 2: Using porous carbon microspheres as a carrier, hexadecyltrimethylammonium bromide as a template agent, and ammonia water as an alkaline catalytic environment, tetraethyl orthosilicate forms a silica framework through hydrolysis-condensation reaction. The template agent is removed by treatment with isopropanol and ammonium nitrate to obtain silica composite microspheres. Step 3: On the surface of silica composite microspheres, tetraethyl orthosilicate is used as the silicon source for secondary coating modification. Urea is used to regulate the microenvironment and promote uniform deposition of the silicon layer to obtain modified silica hollow microspheres with burrs. The modified silica hollow microspheres are then treated by the hydrolysis-condensation reaction of γ-methacryloyloxypropyltrimethoxysilane to obtain double bond modified silica hollow microspheres. Step 4: Using di(2-ethylhexyl) peroxide and dilauroyl peroxide as composite initiators, a free radical polymerization reaction is initiated on vinyl chloride monomer. Double-bond modified silica and vinyl POSS participate in the polymerization through surface double bonds, forming a cross-linked composite structure of inorganic and organic phases. After high-temperature and high-pressure hot pressing, an impact-resistant and wear-resistant liner for mining is obtained.
2. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 1, characterized in that, The specific preparation steps for the silica composite microspheres are as follows: Hexadecyltrimethylammonium bromide, porous carbon microspheres, and ammonia were added to a reaction vessel and stirred for 30-40 min at 20-25℃ and 500-600 r / min. Then, tetraethyl orthosilicate was added, and the reaction was continued for 6-7 h. After centrifugation at 8000-9000 r / min for 5-8 min, the filter cake was transferred to isopropanol and ammonium nitrate and reacted at 80-90℃ for 24 h. The mixture was then freeze-dried under vacuum at -20℃ for 12-14 h to obtain silica composite microspheres.
3. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 2, characterized in that, The ratio of hexadecyltrimethylammonium bromide, porous carbon microspheres, ammonia, tetraethyl orthosilicate, isopropanol, and ammonium nitrate is 30-40g: 50-60g: 2-3L: 170-180mL: 800-900mL: 14-16g.
4. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 1, characterized in that, The specific preparation steps of the modified silica hollow microspheres are as follows: Hexadecyltrimethylammonium bromide, urea, silica composite microspheres, and deionized water were added to a reaction vessel and stirred for 30-40 min at 20-25℃ and 500-600 r / min. Then, isopropanol and tetraethyl orthosilicate were added, and stirring was continued for another 30-40 min. The mixture was then heated to 70-80℃ and reacted for 16-18 h. After filtration, the filter cake was washed 2-4 times with deionized water and dried under vacuum at 60-80℃ for 1-2 h. The cake was then transferred to a muffle furnace and calcined at 550-600℃ for 6-8 h to obtain modified silica hollow microspheres.
5. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 4, characterized in that, The ratio of hexadecyltrimethylammonium bromide, urea, silica composite microspheres, deionized water, isopropanol and tetraethyl orthosilicate is 20-22g: 12-14g: 8-10g: 450-500mL: 450-500mL: 4-5mL.
6. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 1, characterized in that, The specific preparation steps for the double-bond modified silica hollow microspheres are as follows: Modified silica hollow microspheres, anhydrous ethanol, and deionized water were added to a reaction vessel and stirred for 10-12 min at 50-60℃ and 500-600 r / min. Then, γ-methacryloyloxypropyltrimethoxysilane was added, and the reaction was continued to be stirred for 6-8 h. After filtration, the precipitate was washed 2-4 times with deionized water and anhydrous ethanol and dried under vacuum at 60-80℃ for 1-2 h to obtain double bond modified silica hollow microspheres.
7. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 6, characterized in that, The ratio of the modified silica hollow microspheres, anhydrous ethanol, deionized water and γ-methacryloxypropyltrimethoxysilane is 15-20g: 500-600mL: 100-120mL: 12-14mL.
8. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 1, characterized in that, The specific preparation steps for the impact-resistant and wear-resistant liner plate used in mining are as follows: Double-bond modified silica hollow microspheres and vinyl POSS were added to a reactor and stirred for 3-4 hours at 50-60℃ and 400-500 rpm. Then, 1,4-dioxane, di(2-ethylhexyl) peroxide dicarbonate, and dilauryl peroxide were added to the reactor. The reactor was sealed and protected with nitrogen gas. Finally, vinyl chloride was added to the reactor and stirred for 4-5 hours at 50-60℃ and 500-600 rpm. After the reaction is terminated, a methanol solution with a mass concentration of 20-22% is added. After the addition is complete, the mixture is allowed to stand for 24-29 hours, filtered, and the filter cake is washed 2-4 times with anhydrous methanol. It is then vacuum dried at 60-80℃ for 1-2 hours to obtain modified polyvinyl chloride paste resin. The modified polyvinyl chloride paste resin is then transferred to a hot press and hot-pressed at 5-10MPa and 350-390℃ for 20-30 minutes to obtain impact-resistant and wear-resistant lining plates for mining.
9. The method for preparing an impact-resistant and wear-resistant liner for mining according to claim 8, characterized in that, The ratio of the double bond modified silica hollow microspheres, vinyl POSS, 1,4-dioxane, di(2-ethylhexyl) peroxydicarbonate, dilauroyl peroxide, vinyl chloride, and methanol solution is 10-12g: 8-10g: 120-140mL: 1-2g: 1-2g: 80-90g: 500-600mL.
10. A type of impact-resistant and wear-resistant liner for mining, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.