Graphene-based anti-static flame-retardant floor and production process thereof

Abstract

The invention discloses an anti-static flame-retardant floor based on graphene and a production process thereof, and relates to the technical field of building materials. The anti-static flame-retardant floor based on graphene is prepared by taking a medium-density fiberboard as a base material and coating slurry, the slurry is prepared from the following raw materials in parts by weight: 1 to 1.5 parts of graphene powder, 6 to 12 parts of modified nano silicon dioxide, 18 to 28 parts of modified epoxy resin, 3 to 5 parts of carbon black, 2 to 3 parts of dodecyl trimethyl ammonium chloride, 9 to 16 parts of aluminum hydroxide, 6 to 13 parts of magnesium hydroxide, 7 to 11 parts of ammonium polyphosphate, 4 to 6 parts of pentaerythritol, 5 to 8 parts of melamine, 5 to 7 parts of ethylenediamine and 1 to 1.5 parts of a silane coupling agent KH-550. 0.4-0.7 part of an organic silicon defoaming agent, 3-5 parts of sodium lignin sulfonate and 10-20 parts of deionized water. Graphene is adopted to enhance the anti-static and flame-retardant properties, and a dispersion and curing process is innovated to improve the stability; the material has the characteristics of wear resistance and temperature change resistance and is wide in application scene; the production process is optimized, and the consistency and quality of products are guaranteed; the material is environment-friendly, and has both practicability and economical efficiency.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to a graphene-based antistatic and flame-retardant floor and its manufacturing process. Background Technology

[0002] In modern construction and industrial fields, the functional requirements for flooring materials are becoming increasingly stringent, especially in places such as electronics factories, laboratories, and high-rise buildings, where antistatic and flame-retardant properties have become key indicators. Traditional flooring materials such as solid wood flooring and ordinary composite flooring, while possessing basic functionalities, generally suffer from insufficient antistatic properties and low flame-retardant ratings, which can easily lead to safety hazards such as electrostatic discharge damaging electronic components and the spread of fire.

[0003] Existing antistatic flooring often relies on the addition of conductive fibers or metal powders, but uneven dispersion can easily lead to performance fluctuations, and the conductive pathways are prone to failure after long-term use. Flame-retardant flooring often achieves its effect by adding a large amount of flame retardant, but this often sacrifices the mechanical properties and environmental friendliness of the material, resulting in problems such as the flooring becoming brittle and releasing harmful gases.

[0004] Meanwhile, in traditional production processes, problems such as insufficient dispersion of functional fillers and the generation of internal stress during curing further restrict the improvement of the overall performance of flooring. With the development of graphene materials in functional composite materials, its excellent conductivity and flame retardant synergistic effect provide a new approach to solving the above problems. However, how to achieve uniform dispersion of graphene in flooring materials, synergistically improve antistatic and flame retardant properties, and optimize the production process to ensure product stability has become a technical challenge that the industry urgently needs to solve. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a graphene-based antistatic and flame-retardant floor and its manufacturing process, solving the problems of poor antistatic performance, insufficient flame-retardant effect, and uneven material dispersion in traditional antistatic and flame-retardant floors.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A graphene-based antistatic and flame-retardant flooring is made by coating a medium-density fiberboard (MDF) substrate with a slurry. The slurry comprises the following raw materials in parts by weight: 1-1.5 parts graphene powder, 6-12 parts modified nano-silica, 18-28 parts modified epoxy resin, 3-5 parts carbon black, 2-3 parts dodecyltrimethylammonium chloride, 9-16 parts aluminum hydroxide, 6-13 parts magnesium hydroxide, 7-11 parts ammonium polyphosphate, 4-6 parts pentaerythritol, 5-8 parts melamine, 5-7 parts ethylenediamine, 1-1.5 parts silane coupling agent KH-550, 0.4-0.7 parts organosilicon defoamer, 3-5 parts sodium lignosulfonate, and 10-20 parts deionized water.

[0008] Furthermore, the modified nano-silica is prepared using the following specific steps:

[0009] A1. Add nano-silica to deionized water and stir at 250-300 rpm for 15-20 minutes until a uniform suspension is formed. Add borax and urea sequentially and stir for 5 minutes until the solid dissolves. Heat to 70-75℃ and stir for 1.5-2 hours, scraping the wall every 20 minutes to prevent sticking. After the reaction, adjust the pH to 6.8-7.2 dropwise with 10% hydrochloric acid. Let stand for 20-30 minutes and pour off the supernatant. Dry the lower solid in an oven at 70-75℃ for 6-7 hours. After drying, grind through a 100-mesh sieve to ensure product dispersibility for subsequent processing and collect for later use.

[0010] The surface of nano-silica is rich in hydroxyl groups. Under conditions of 70-75℃, the borate ions generated from the hydrolysis of borax undergo a dehydration condensation reaction with the silanol groups to form Si-OB covalent bonds. At the same time, the amino groups in the urea molecules combine with the silanol groups, introducing nitrogen-containing organic groups onto the silica surface. This process not only eliminates some silanol groups through chemical bonding, reducing the tendency of particle agglomeration, but also builds a "bridge" for subsequent organic modification. In addition, the introduction of boron initially endows it with flame-retardant potential.

[0011] A2. Take the first modified product and add it to deionized water. Stir at 300-350 r / min for 15 min until dispersed. Add glacial acetic acid dropwise to adjust the pH to 4.0-5.0 to provide a suitable environment for the coupling reaction. Then add sodium lignosulfonate and stir for 10 min until dissolved. Next, add titanate coupling agent NDZ-101 dropwise at a rate of 1 mL / min. Heat to 80-85℃ and stir for 1 h to enhance its compatibility with organic resin and reduce agglomeration. After the reaction, dry the system in an oven at 80-85℃ for 5-6 h. After drying, grind it through a 120 mesh sieve to optimize the subsequent mixing effect with the slurry. Collect the light brown powder for later use.

[0012] The titanium oxide bonds of the titanate coupling agent NDZ-101 can react with the residual silanol groups after the first modification step to form stable Si-O-Ti bonds, introducing the long-chain alkyl groups of the coupling agent into the silica surface. Simultaneously, the sulfonic acid groups of sodium lignosulfonate interact with the polar groups of the coupling agent, further enhancing the surface's oleophilicity. Through this "inorganic-organic" interfacial bonding, the compatibility between nano-silica and organic resins is significantly improved, preventing agglomeration in the slurry and ensuring uniform dispersion.

[0013] A3. Take the modified product from step two, add deionized water and stir until it reaches a toothpaste-like consistency. Then, add magnesium hydroxide and type II ammonium polyphosphate in sequence, and stir at 800-1000 r / min for 20-30 min. High-speed stirring ensures that magnesium hydroxide and ammonium polyphosphate are uniformly attached to the surface of nano-silica. Next, add silica sol with a solid content of 30% and continue stirring for 10 min. The silica sol enhances the binding of the components, constructs a composite flame-retardant structure, and enhances the flame-retardant synergistic effect of nano-silica. Dry the paste in an oven at 95-100℃ for 4-5 h until it becomes loose lumps. Grind it and pass it through a 120-mesh sieve to collect the modified nano-silica.

[0014] The modified silica surface exhibits a certain degree of adsorption. Under high-speed stirring, magnesium hydroxide and type II ammonium polyphosphate adhere to its surface through physical and chemical adsorption. The siloxanes in the silica sol further cross-link, "anchoring" the flame-retardant components to the silica surface, forming a "core-shell" structure. This structure makes it difficult for the flame-retardant components to migrate during subsequent processing and allows them to work synergistically when heated. At the same time, the rigid structure of silica also enhances the mechanical properties of the coating.

[0015] Furthermore, the ratio of nano-silica, deionized water, borax, and urea in A1 is 100g: 250-280mL: 9-11g: 7-9g;

[0016] Furthermore, the ratio of the first modified product, deionized water, sodium lignosulfonate, and titanate coupling agent NDZ-101 in A2 is 100g: 200-220mL: 14-16g: 4-5g.

[0017] Furthermore, the ratio of the second-step modified product, deionized water, magnesium hydroxide, type II ammonium polyphosphate, and silica sol in A3 is 100g: 40-50mL: 14-16g: 9-11g: 3-5mL.

[0018] Furthermore, after adjusting the pH to 6.8-7.2 dropwise with 10% hydrochloric acid in A1, it needs to stand for 20-30 minutes and pour off the supernatant. This operation aims to precisely remove the byproduct salts and water-soluble impurities generated in the reaction to ensure the purity and efficiency of the subsequent modification reaction.

[0019] Furthermore, the modified epoxy resin is prepared using the following specific steps:

[0020] B1. Place epoxy resin E-51 into a beaker, add urea, stir at 250 rpm until dissolved, then add triphenylphosphine, heat to 80-85℃ and react for 2-3 hours to promote the reaction between epoxy resin and urea. Triphenylphosphine acts as a catalyst to accelerate the reaction process. Next, slowly add 85% phosphoric acid, stir at 350-400 rpm at 75-80℃ for 50-60 minutes to introduce phosphorus to improve the flame retardancy of epoxy resin and change the molecular structure, creating active sites for subsequent modification. After the reaction is completed, cool to room temperature to obtain the first modified product.

[0021] The epoxy groups of epoxy resin E-51 undergo a ring-opening reaction with the amino groups of urea, introducing nitrogen-containing groups. Subsequently, the hydroxyl groups of phosphate react further with the epoxy groups, incorporating phosphoric acid into the epoxy resin molecular chain via phosphate ester bonds. The synergistic effect of nitrogen and phosphorus promotes resin carbonization at high temperatures, forming a dense carbon layer that blocks heat and oxygen while releasing non-flammable gases to dilute combustible gases, significantly improving flame retardant properties. Triphenylphosphine acts as a catalyst, accelerating the reaction between epoxy groups and amino and hydroxyl groups, ensuring thorough modification.

[0022] B2. Take the first modified product, add polyvinyl alcohol 1788 and deionized water, heat to 85-90℃ and stir at 400 r / min until dissolved to improve the compatibility of epoxy resin and organic components; keep the reaction at this temperature for 30-40 min, then add carbon black, adjust the speed to 500-550 r / min, cool to 70-75℃, and stir for 45-55 min to ensure uniform dispersion, assist graphene in building a conductive network, enhance antistatic properties, and prevent carbon black agglomeration during cooling and stirring; after completion, allow to cool naturally to room temperature to obtain the second modified product;

[0023] The first modified epoxy resin undergoes hydrogen bonding and partial transesterification with polyvinyl alcohol 1788. The long-chain structure of polyvinyl alcohol improves the flexibility of the epoxy resin and reduces its brittleness after curing. Carbon black is uniformly dispersed in the resin through high-speed stirring. Its conductivity assists graphene in constructing a three-dimensional conductive network, enhancing the antistatic effect. Simultaneously, the particle-reinforcing effect of carbon black also improves the mechanical strength of the resin. Cooling to 70-75℃ and stirring prevents carbon black agglomeration and ensures uniform dispersion.

[0024] B3. Take the second modified product, add corn starch and deionized water, heat to 75-80℃, stir at 350r / min until the starch gelatinizes to enhance the adhesion of the epoxy resin; keep it at the temperature for 30-40min, then add silane coupling agent KH-550 to strengthen the interfacial bonding force between the epoxy resin and the inorganic filler and reduce internal voids; react at 70-75℃ at 400-450r / min for 25-35min to promote the complete coupling reaction and improve the mechanical stability and temperature resistance of the epoxy resin to obtain the modified epoxy resin.

[0025] The polysaccharide chains formed after corn starch gelatinization form hydrogen bonds with the polar groups of epoxy resin, improving the resin's adhesion and hydrophilicity, and facilitating subsequent mixing with inorganic fillers. The amino groups of the silane coupling agent KH-550 react with the hydroxyl groups of the epoxy resin, while its siloxane groups can undergo hydrolysis and condensation with the hydroxyl groups of the inorganic fillers, forming a chemical bonding interface of "resin-coupling agent-inorganic filler". This significantly reduces interfacial voids, enhances the adhesion and temperature resistance of the coating, and prevents cracking and delamination during long-term use.

[0026] Furthermore, the ratio of epoxy resin E-51, urea, triphenylphosphine, and phosphoric acid in B1 is 100g: 15-20g: 0.5-1g: 8-12g.

[0027] Furthermore, the ratio of the first modified product, polyvinyl alcohol 1788, deionized water, and carbon black in B2 is 100g: 8-12g: 50-60mL: 3-5g.

[0028] Furthermore, the ratio of the second modified product, corn starch, deionized water, and silane coupling agent KH-550 in B3 is 100g: 6-9g: 40-50mL: 4-6g.

[0029] A manufacturing process for graphene-based antistatic and flame-retardant flooring specifically includes the following steps:

[0030] S1. Dry medium-density fiberboard in an oven at 100-105℃ for 3-5 hours, sand it with 180-grit sandpaper and keep it clean for later use; take graphene powder, add sodium lignosulfonate and deionized water, stir at 500r / min for 1-2 hours to obtain graphene dispersion; preheat modified nano-silica and modified epoxy resin at 45-50℃ for 20-30 minutes for later use.

[0031] S2. Add the modified epoxy resin and deionized water to the reactor and stir and mix at 300-400 r / min for 20-30 min at 60-70℃ to allow it to prepolymerize and form a matrix resin liquid.

[0032] S3. Add graphene dispersion, carbon black, modified nano silica, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, pentaerythritol, melamine and sodium lignosulfonate to the reactor in sequence. Maintain the temperature at 65-75℃ and stir at 500-600r / min for 40-50min to ensure that all fillers are evenly dispersed and form a stable slurry system.

[0033] S4. Then slowly add dodecyltrimethylammonium chloride, silane coupling agent KH-550 and organosilicon defoamer, adjust the speed to 300-350 r / min, cool to 30-40℃, add ethylenediamine and continue stirring for 15-20 min. After stirring, filter the slurry through an 800-mesh nylon filter.

[0034] S5. Apply the filtered slurry evenly to the surface of the medium-density fiberboard substrate using a coating machine, controlling the coating thickness to be 0.5-1.0 mm. Then, send it into an oven for step-by-step curing: first, pre-cur at 80℃ for 30 min, then increase to 120℃ for 40 min, and finally cure at 150℃ for 20 min. The heating rate is controlled at 5-8℃ / min.

[0035] S6. After curing, remove the floor blank and allow it to cool naturally to room temperature. Then, lightly sand the surface with 240-grit sandpaper to make it smooth and flat. Finally, cut, inspect, and package it according to specifications to obtain the finished graphene-based antistatic and flame-retardant floor.

[0036] Furthermore, after adding ethylenediamine, the slurry needs to be coated within 0.5-1 hour. If the time is exceeded, the slurry will solidify prematurely, making it impossible to coat evenly and resulting in coating defects.

[0037] Furthermore, the heating rate of 5-8℃ / min allows the cross-linking and curing reaction rate of the resin system to be coordinated with the evaporation and diffusion rate of the solvent water. If the heating is too fast, the resin surface will rapidly gel, thereby blocking the channels for internal solvent evaporation. In the subsequent high-temperature curing stage, the solvent will vaporize and form bubbles or pinholes. If the heating is too slow, the resin will cure prematurely at a lower temperature, affecting leveling and final densification. This heating rate can obtain a dense cured coating with a smooth surface and no internal defects.

[0038] This invention provides a graphene-based antistatic and flame-retardant floor and its manufacturing process, which has the following beneficial effects:

[0039] 1. This invention utilizes the synergistic effect of graphene and flame-retardant fillers to form a stable three-dimensional conductive network and flame-retardant barrier composite structure. The graphene sheets are uniformly dispersed in the substrate, not only constructing efficient conductive pathways for rapid static electricity release, but also forming a physical barrier with flame retardants such as aluminum hydroxide and magnesium hydroxide, delaying heat transfer and oxygen penetration. This composite structure enables the flooring to simultaneously possess durable antistatic properties and excellent flame-retardant effects, solving the problem of traditional materials struggling to achieve both antistatic and flame-retardant performance. Furthermore, the two functions mutually reinforce each other, enhancing the overall safety protection level.

[0040] 2. Innovative dispersion and curing processes optimize the internal structure of the material, significantly improving the mechanical properties and stability of the flooring. The use of a combination of stirring dispersion and stepped temperature curing avoids graphene agglomeration and the generation of internal stress during curing, resulting in a denser and more uniform internal structure. This structural characteristic makes the flooring less prone to cracking and delamination during long-term use, while also enhancing its wear resistance and temperature change resistance, extending its service life and meeting the durability requirements of high-frequency use scenarios.

[0041] 3. The formulation design and production process of this invention combine to achieve a balance between environmental performance and functional characteristics. By rationally controlling the addition ratio of graphene and flame retardant, the amount of traditional additives used is reduced while ensuring antistatic and flame-retardant effects, thus lowering the risk of harmful substance release. Simultaneously, processes such as vacuum stirring and plasma treatment during production further enhance the bonding strength of the materials, avoiding pollution problems caused by material separation during later use, and ensuring the product meets the high environmental and health requirements of modern construction.

[0042] 4. Optimized overall structural design and production process of the flooring endow the product with wide applicability and excellent practicality. The tight bonding between the base material and functional layers ensures the stability of the flooring's performance under different environmental conditions. Whether in a dry electronics factory or a high-humidity laboratory, its anti-static and flame-retardant properties remain stable. In addition, the surface treatment process enhances the flooring's wear resistance and easy-to-clean properties. Combined with precise cutting and processing, the product not only meets the functional requirements of various special locations but also adapts to different laying environments and installation methods, expanding its application range. Detailed Implementation

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Example 1: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0045] S1. Medium-density fiberboard is dried in an oven at 100℃ for 3 hours, sanded with 180-grit sandpaper and kept clean for later use; 1 part graphene powder is added to 1.5 parts sodium lignosulfonate and 8 parts deionized water, and stirred at 500r / min for 1 hour to obtain graphene dispersion; nano silica and epoxy resin E-51 are preheated at 45℃ for 20 minutes for later use.

[0046] S2. Add 18 parts of epoxy resin E-51 and 2 parts of deionized water to the reactor and stir and mix at 300 r / min for 20 min at 60℃ to allow it to prepolymerize and form a matrix resin liquid.

[0047] S3. Add graphene dispersion, 3 parts carbon black, 6 parts nano silica, 9 parts aluminum hydroxide, 6 parts magnesium hydroxide, 7 parts ammonium polyphosphate, 4 parts pentaerythritol, 5 parts melamine and 1.5 parts sodium lignosulfonate to the reactor in sequence. Maintain the temperature at 65℃ and stir at 500r / min for 40min to make all fillers uniformly dispersed and form a stable slurry system.

[0048] S4. Then slowly add 2 parts dodecyltrimethylammonium chloride, 1 part silane coupling agent KH-550 and 0.4 parts organosilicon defoamer, adjust the speed to 300 r / min, cool down to 30℃, add 5 parts ethylenediamine and continue stirring for 15 min. After stirring, filter the slurry through an 800 mesh nylon filter.

[0049] S5. The filtered slurry is evenly coated onto the surface of the medium-density fiberboard substrate using a coating machine, with the coating thickness controlled at 0.5 mm. Then it is sent into an oven for step-by-step curing: first, pre-curing at 80℃ for 30 min, then curing at 120℃ for 40 min, and finally curing at 150℃ for 20 min, with the heating rate controlled at 5℃ / min.

[0050] S6. After curing, remove the floor blank and allow it to cool naturally to room temperature. Then, lightly sand the surface with 240-grit sandpaper to make it smooth and flat. Finally, cut, inspect, and package it according to specifications to obtain the finished graphene-based antistatic and flame-retardant floor.

[0051] Example 2: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0052] S1. Medium-density fiberboard is dried in an oven at 105℃ for 5 hours, sanded with 180-grit sandpaper and kept clean for later use; 1.5 parts of graphene powder are added to 3 parts of sodium lignosulfonate and 15 parts of deionized water, and stirred at 500r / min for 2 hours to obtain a graphene dispersion; nano-silica and epoxy resin E-51 are preheated at 50℃ for 30 minutes for later use.

[0053] S2. Add 28 parts of epoxy resin E-51 and 5 parts of deionized water to the reactor and stir and mix at 400 r / min for 30 min at 70℃ to allow it to prepolymerize and form a matrix resin liquid.

[0054] S3. Add graphene dispersion, 5 parts carbon black, 12 parts nano silica, 16 parts aluminum hydroxide, 13 parts magnesium hydroxide, 11 parts ammonium polyphosphate, 6 parts pentaerythritol, 8 parts melamine and 2 parts sodium lignosulfonate to the reactor in sequence. Maintain the temperature at 75℃ and stir at 600r / min for 50min to make all fillers uniformly dispersed and form a stable slurry system.

[0055] S4. Then slowly add 3 parts dodecyltrimethylammonium chloride, 1.5 parts silane coupling agent KH-550 and 0.7 parts organosilicon defoamer, adjust the speed to 350 r / min, cool down to 40℃, add 7 parts ethylenediamine and continue stirring for 20 min. After stirring, filter the slurry through an 800 mesh nylon filter.

[0056] S5. The filtered slurry is evenly coated onto the surface of the medium-density fiberboard substrate using a coating machine, with the coating thickness controlled at 1.0 mm. Then it is sent into an oven for step-by-step curing: first, pre-curing at 80℃ for 30 min, then curing at 120℃ for 40 min, and finally curing at 150℃ for 20 min, with the heating rate controlled at 8℃ / min.

[0057] S6. After curing, remove the floor blank and allow it to cool naturally to room temperature. Then, lightly sand the surface with 240-grit sandpaper to make it smooth and flat. Finally, cut, inspect, and package it according to specifications to obtain the finished graphene-based antistatic and flame-retardant floor.

[0058] Example 3: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0059] S1. Medium-density fiberboard is dried in an oven at 102℃ for 4 hours, sanded with 180-grit sandpaper, and kept clean for later use; 1.2 parts of graphene powder are added to 2 parts of sodium lignosulfonate and 12 parts of deionized water, and stirred at 500r / min for 1.5 hours to obtain a graphene dispersion; nano-silica and epoxy resin E-51 are preheated at 47℃ for 25 minutes for later use.

[0060] S2. Add 23 parts of epoxy resin E-51 and 4 parts of deionized water to the reactor and stir and mix at 350 r / min for 25 min at 65℃ to allow it to prepolymerize and form a matrix resin liquid.

[0061] S3. Add graphene dispersion, 4 parts carbon black, 9 parts nano silica, 12 parts aluminum hydroxide, 9 parts magnesium hydroxide, 9 parts ammonium polyphosphate, 5 parts pentaerythritol, 7 parts melamine and 2 parts sodium lignosulfonate to the reactor in sequence. Maintain the temperature at 70℃ and stir at 550r / min for 45min to make all fillers uniformly dispersed and form a stable slurry system.

[0062] S4. Then slowly add 3 parts dodecyltrimethylammonium chloride, 1.5 parts silane coupling agent KH-550 and 0.6 parts organosilicon defoamer, adjust the speed to 320 r / min, cool down to 35℃, add 6 parts ethylenediamine and continue stirring for 17 min. After stirring, filter the slurry through an 800 mesh nylon filter.

[0063] S5. The filtered slurry is evenly coated onto the surface of the medium-density fiberboard substrate using a coating machine, with the coating thickness controlled at 0.8 mm. Then it is sent into an oven for step-by-step curing: first, pre-curing at 80℃ for 30 min, then curing at 120℃ for 40 min, and finally curing at 150℃ for 20 min, with the heating rate controlled at 6℃ / min.

[0064] S6. After curing, remove the floor blank and allow it to cool naturally to room temperature. Then, lightly sand the surface with 240-grit sandpaper to make it smooth and flat. Finally, cut, inspect, and package it according to specifications to obtain the finished graphene-based antistatic and flame-retardant floor.

[0065] Example 4: Preparation of modified nano-silica. The specific preparation steps are as follows:

[0066] A1. Take 100g of nano-silica and add it to 250mL of deionized water. Stir at 250r / min for 15min until a uniform suspension is formed. Add 9g of borax and 7g of urea in sequence, and stir for 5min until the solid dissolves. Heat to 70℃ and stir for 1.5h. Scrape the wall every 20min to prevent sticking. After the reaction, adjust the pH to 6.8 dropwise with 10% hydrochloric acid. Let stand for 20min and pour off the supernatant. Dry the lower solid in a 70℃ oven for 6h. After drying, grind it through a 100-mesh sieve and collect it for later use.

[0067] A2. Take 100g of the first modified product and add it to 200mL of deionized water. Stir at 300r / min for 15min until dispersed. Add glacial acetic acid to adjust the pH to 4.0. Then add 14g of sodium lignosulfonate and stir for 10min until dissolved. Next, add 4g of titanate coupling agent NDZ-101 dropwise at a rate of 1mL / min. Heat to 80℃ and stir for 1h. After the reaction, dry the system in an oven at 80℃ for 5h. After drying, grind it through a 120-mesh sieve and collect the light brown powder for later use.

[0068] A3. Take 100g of the modified product from step two and add 40mL of deionized water. Stir until the consistency is like toothpaste. Then add 14g of magnesium hydroxide and 9g of type II ammonium polyphosphate in sequence. Stir at 800r / min for 20min. Then add 3mL of silica sol with a solid content of 30% and continue stirring for 10min. Dry the paste in an oven at 95℃ for 4h until it becomes loose lumps. Grind it and pass it through a 120-mesh sieve to collect the modified nano silica.

[0069] Example 5: Preparation of modified nano-silica. The specific preparation steps are as follows:

[0070] A1. Take 100g of nano-silica and add it to 280mL of deionized water. Stir at 300r / min for 20min until a uniform suspension is formed. Add 11g of borax and 9g of urea in sequence, and stir for 5min until the solid dissolves. Heat to 75℃ and stir for 2h. Scrape the wall every 20min to prevent sticking. After the reaction, adjust the pH to 7.2 dropwise with 10% hydrochloric acid. Let stand for 30min and pour off the supernatant. Dry the lower solid in a 75℃ oven for 7h. After drying, grind it through a 100-mesh sieve and collect it for later use.

[0071] A2. Take 100g of the first modified product and add it to 220mL of deionized water. Stir at 350r / min for 15min until dispersed. Add glacial acetic acid to adjust the pH to 5.0. Then add 16g of sodium lignosulfonate and stir for 10min until dissolved. Next, add 5g of titanate coupling agent NDZ-101 dropwise at a rate of 1mL / min. Heat to 85℃ and stir for 1h. After the reaction, dry the system in an oven at 85℃ for 6h. After drying, grind it through a 120-mesh sieve and collect the light brown powder for later use.

[0072] A3. Take 100g of the modified product from step two and add 50mL of deionized water. Stir until the consistency is like toothpaste. Then add 16g of magnesium hydroxide and 11g of type II ammonium polyphosphate in sequence. Stir at 1000r / min for 30min. Then add 5mL of silica sol with a solid content of 30% and continue stirring for 10min. Dry the paste in an oven at 100℃ for 5h until it becomes loose lumps. Grind it and pass it through a 120-mesh sieve to collect the modified nano silica.

[0073] Example 6: Preparation of modified epoxy resin. The specific preparation steps are as follows:

[0074] B1. Take 100g of epoxy resin E-51 and put it into a beaker. Add 15g of urea and stir at 250r / min until dissolved. Then add 0.5g of triphenylphosphine and heat to 80℃ for 2h. Then slowly add 8g of 85% phosphoric acid and stir at 350r / min at 75℃ for 50min. After the reaction is completed, cool to room temperature to obtain the first modified product.

[0075] B2. Take 100g of the first modified product, add 8g of polyvinyl alcohol 1788 and 50mL of deionized water, heat to 85℃ and stir at 400r / min until dissolved, then keep warm and react for 30min. Next, add 3g of carbon black, adjust the speed to 500r / min, cool to 70℃ and stir for 45min. After the reaction is completed, let it cool naturally to room temperature to obtain the second modified product.

[0076] B3. Take 100g of the second modified product, add 6g of corn starch and 40mL of deionized water, heat to 75℃, stir at 350r / min until the starch gelatinizes, keep warm for 30min, then add 4g of silane coupling agent KH-550, and react at 70℃ and 400r / min for 25min to obtain modified epoxy resin.

[0077] Example 7: Preparation of modified epoxy resin. The specific preparation steps are as follows:

[0078] B1. Take 100g of epoxy resin E-51 and put it into a beaker. Add 20g of urea and stir at 250r / min until dissolved. Then add 1g of triphenylphosphine and heat to 85℃ for 3h. Then slowly add 12g of 85% phosphoric acid and stir at 400r / min at 80℃ for 60min. After the reaction is completed, cool to room temperature to obtain the first modified product.

[0079] B2. Take 100g of the first modified product, add 12g of polyvinyl alcohol 1788 and 60mL of deionized water, heat to 90℃ and stir at 400r / min until dissolved, then keep warm and react for 40min. Next, add 5g of carbon black, adjust the speed to 550r / min, cool to 75℃ and stir for 55min. After the reaction is completed, let it cool naturally to room temperature to obtain the second modified product.

[0080] B3. Take 100g of the second modified product, add 9g of corn starch and 50mL of deionized water, heat to 80℃, stir at 350r / min until the starch gelatinizes, keep warm and react for 40min, then add 6g of silane coupling agent KH-550, react at 75℃ and 450r / min for 35min to obtain modified epoxy resin.

[0081] Comparative Example 1: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0082] The remaining steps remain the same, except that the nano-silica in Example 3 is replaced with the modified nano-silica prepared in Example 4 to obtain a graphene-based antistatic and flame-retardant floor.

[0083] Comparative Example 2: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0084] The remaining steps remain unchanged, except that the epoxy resin E-51 in Example 3 is replaced with the modified epoxy resin prepared in Example 7 to obtain a graphene-based antistatic and flame-retardant floor.

[0085] Comparative Example 3: Production of graphene-based antistatic and flame-retardant flooring, the specific steps are as follows:

[0086] The remaining steps remain unchanged, except that the nano-silica in Example 3 is replaced with the modified nano-silica prepared in Example 4, and the epoxy resin E-51 is replaced with the modified epoxy resin prepared in Example 7, to obtain a graphene-based antistatic and flame-retardant floor.

[0087] Performance testing

[0088]

[0089] The performance test results of the graphene-based antistatic and flame-retardant flooring of Examples 1-3 and Comparative Examples 1-3 are as follows: In terms of antistatic performance, both surface resistance and volume resistance meet the standards, while the resistance value of the comparative examples is lower, indicating better static discharge effect; In terms of flame retardant performance, the oxygen index of the examples is 28.5%-29.2% and the flame retardant rating is V-1, while the oxygen index of the comparative examples is 31.5%-35.2% and the rating is improved to V-0, showing significantly stronger flame retardant ability; In terms of abrasion resistance, the comparative examples at 480-550 revolutions are better than the examples at 420-450 revolutions, showing greater abrasion resistance; In terms of temperature resistance, all samples showed no cracking or delamination after 10 cycles, and the surface resistance change rate of the comparative examples (8%-12%) is lower than that of the examples (16%-18%), indicating more stable environmental adaptability; In terms of adhesion, except for the comparative example 3 which reaches the best rating of 0, the others are all at rating 1. The comparative example 3 uses both modified nano-silica and modified epoxy resin, which reduces interfacial voids and results in better adhesion. In summary, the samples using modified nano-silica and modified epoxy resin showed significant improvements in core properties such as antistatic properties, flame retardancy, wear resistance, and temperature change resistance, resulting in superior overall performance.

[0090] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A graphene-based antistatic and flame-retardant floor, characterized in that: The flooring is made of medium-density fiberboard as the base material and coated with a slurry. The slurry preparation contains the following raw materials in parts by weight: 1-1.5 parts graphene powder, 6-12 parts modified nano silica, 18-28 parts modified epoxy resin, 3-5 parts carbon black, 2-3 parts dodecyltrimethylammonium chloride, 9-16 parts aluminum hydroxide, 6-13 parts magnesium hydroxide, 7-11 parts ammonium polyphosphate, 4-6 parts pentaerythritol, 5-8 parts melamine, 5-7 parts ethylenediamine, 1-1.5 parts silane coupling agent KH-550, 0.4-0.7 parts organosilicon defoamer, 3-5 parts sodium lignosulfonate, and 10-20 parts deionized water.

2. The graphene-based antistatic and flame-retardant flooring according to claim 1, characterized in that: The modified nano-silica is prepared using the following specific steps: A1. Add nano-silica to deionized water and stir at 250-300 r / min for 15-20 min until a uniform suspension is formed. Add borax and urea in sequence and stir for 5 min until the solid dissolves. Heat to 70-75℃ and stir for 1.5-2 h, scraping the wall every 20 min to prevent sticking. After the reaction, adjust the pH to 6.8-7.2 dropwise with 10% hydrochloric acid. Let stand for 20-30 min and pour off the supernatant. Dry the lower solid in an oven at 70-75℃ for 6-7 h. After drying, grind through a 100-mesh sieve and collect for later use. A2. Take the first modified product and add it to deionized water. Stir at 300-350 r / min for 15 min until dispersed. Add glacial acetic acid to adjust the pH to 4.0-5.

0. Then add sodium lignosulfonate and stir for 10 min until dissolved. Next, add titanate coupling agent NDZ-101 dropwise at a rate of 1 mL / min. Heat to 80-85℃ and stir for 1 h. After the reaction, dry the system in an oven at 80-85℃ for 5-6 h. After drying, grind it through a 120 mesh sieve and collect the light brown powder for later use. A3. Take the modified product from the second step, add deionized water and stir until it reaches a toothpaste-like consistency. Then add magnesium hydroxide and ammonium type II polyphosphate in sequence, and stir at 800-1000 r / min for 20-30 min. Next, add silica sol with a solid content of 30% and continue stirring for 10 min. Dry the paste in an oven at 95-100℃ for 4-5 h until it becomes loose lumps. Grind it and pass it through a 120-mesh sieve to collect the modified nano silica.

3. The graphene-based antistatic and flame-retardant flooring according to claim 2, characterized in that: The ratio of nano-silica, deionized water, borax, and urea in A1 is 100g: 250-280mL: 9-11g: 7-9g; The ratio of the first modified product, deionized water, sodium lignosulfonate, and titanate coupling agent NDZ-101 in A2 is 100g: 200-220mL: 14-16g: 4-5g. The ratio of the modified product from step two in A3, deionized water, magnesium hydroxide, ammonium polyphosphate type II, and silica sol is 100g: 40-50mL: 14-16g: 9-11g: 3-5mL.

4. The graphene-based antistatic and flame-retardant flooring according to claim 2, characterized in that: After adjusting the pH to 6.8-7.2 dropwise with 10% hydrochloric acid in step A1, it needs to stand for 20-30 minutes and then pour off the supernatant. This operation aims to precisely remove the byproduct salts and water-soluble impurities generated in the reaction to ensure the purity and efficiency of the subsequent modification reaction.

5. A graphene-based antistatic and flame-retardant floor according to claim 1, characterized in that: The modified epoxy resin is prepared using the following specific steps: B1. Place epoxy resin E-51 into a beaker, add urea, stir at 250 r / min until dissolved, then add triphenylphosphine, heat to 80-85℃ and react for 2-3 hours, then slowly add 85% phosphoric acid, stir at 350-400 r / min at 75-80℃ for 50-60 minutes, and cool to room temperature after the reaction to obtain the first modified product. B2. Take the first modified product, add polyvinyl alcohol 1788 and deionized water, heat to 85-90℃ and stir at 400r / min until dissolved, then keep the temperature and react for 30-40min. Next, add carbon black, adjust the speed to 500-550r / min, cool to 70-75℃ and stir for 45-55min. After the reaction is completed, let it cool naturally to room temperature to obtain the second modified product. B3. Take the second modified product, add corn starch and deionized water, heat to 75-80℃, stir at 350r / min until the starch gelatinizes, keep warm for 30-40min, then add silane coupling agent KH-550, and react at 70-75℃ at 400-450r / min for 25-35min to obtain modified epoxy resin.

6. The graphene-based antistatic and flame-retardant flooring according to claim 5, characterized in that: The ratio of epoxy resin E-51, urea, triphenylphosphine, and phosphoric acid in B1 is 100g: 15-20g: 0.5-1g: 8-12g; The ratio of the first modified product, polyvinyl alcohol 1788, deionized water, and carbon black in B2 is 100g: 8-12g: 50-60mL: 3-5g. The ratio of the second modified product, corn starch, deionized water, and silane coupling agent KH-550 in B3 is 100g: 6-9g: 40-50mL: 4-6g.

7. A production process for graphene-based antistatic and flame-retardant flooring, characterized in that: Specifically, it includes the following steps: S1. Dry medium-density fiberboard in an oven at 100-105℃ for 3-5 hours, sand it with 180-grit sandpaper and keep it clean for later use; take graphene powder, add sodium lignosulfonate and deionized water, stir at 500r / min for 1-2 hours to obtain graphene dispersion; preheat modified nano-silica and modified epoxy resin at 45-50℃ for 20-30 minutes for later use. S2. Add the modified epoxy resin and deionized water to the reactor and stir and mix at 300-400 r / min for 20-30 min at 60-70℃ to allow it to prepolymerize and form a matrix resin liquid. S3. Add graphene dispersion, carbon black, modified nano silica, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, pentaerythritol, melamine and sodium lignosulfonate to the reactor in sequence. Maintain the temperature at 65-75℃ and stir at 500-600r / min for 40-50min to ensure that all fillers are evenly dispersed and form a stable slurry system. S4. Then slowly add dodecyltrimethylammonium chloride, silane coupling agent KH-550 and organosilicon defoamer, adjust the speed to 300-350 r / min, cool to 30-40℃, add ethylenediamine and continue stirring for 15-20 min. After stirring, filter the slurry through an 800-mesh nylon filter. S5. Apply the filtered slurry evenly to the surface of the medium-density fiberboard substrate using a coating machine, controlling the coating thickness to be 0.5-1.0 mm. Then, send it into an oven for step-by-step curing: first, pre-cur at 80℃ for 30 min, then increase to 120℃ for 40 min, and finally cure at 150℃ for 20 min. The heating rate is controlled at 5-8℃ / min. S6. After curing, remove the floor blank and allow it to cool naturally to room temperature. Then, lightly sand the surface with 240-grit sandpaper to make it smooth and flat. Finally, cut, inspect, and package it according to specifications to obtain the finished graphene-based antistatic and flame-retardant floor.

8. The production process of a graphene-based antistatic and flame-retardant floor according to claim 7, characterized in that: After adding ethylenediamine, the slurry needs to be coated within 0.5-1 hour. If the time is exceeded, the slurry will cure prematurely, making it impossible to coat evenly and resulting in coating defects.

9. The production process of a graphene-based antistatic and flame-retardant floor according to claim 7, characterized in that: The heating rate of 5-8℃ / min allows the cross-linking and curing reaction rate of the resin system to be coordinated with the evaporation and diffusion rate of the solvent water. If the heating is too fast, the resin surface will gel rapidly, thereby blocking the channels for internal solvent evaporation. In the subsequent high-temperature curing stage, the solvent will vaporize and form bubbles or pinholes. If the heating is too slow, the resin will cure prematurely at a lower temperature, affecting leveling and final densification. This heating rate can obtain a dense cured coating with a smooth surface and no internal defects.

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