A processing method for environmentally friendly resilient flooring

Abstract

This invention belongs to the field of resilient flooring technology, specifically relating to a processing method for environmentally friendly resilient flooring. This invention provides a processing method for environmentally friendly resilient flooring using polyolefins, EPDM rubber, halogen-free flame retardants, and surface-modified Ag / ZnO nanocomposite antibacterial agents as raw materials. Through processes such as mixing, extrusion, and irradiation treatment, the resulting environmentally friendly resilient flooring not only possesses excellent antibacterial and flame-retardant properties but also exhibits excellent wear resistance and aging resistance, and is environmentally friendly. This invention, through innovative research on the selection of flooring raw materials and key production technologies, has developed a functional, green, and environmentally friendly resilient flooring. This not only provides people with a healthy living environment during travel but also has significant practical implications for the industrial upgrading of high-quality flooring for my country's rail transit sector and for expanding the application fields of flooring.

Description

Technical Field

[0001] This invention belongs to the field of resilient flooring technology, and specifically relates to a processing method for environmentally friendly resilient flooring. Background Technology

[0002] As a flooring material used inside high-speed rail / light rail carriages, flooring not only needs to be aesthetically pleasing, comfortable, flame-retardant, antibacterial, and easy to maintain, but also must not emit harmful odors in the enclosed space. Currently, domestically produced flooring is mainly used in high-speed rail passenger cars, while urban rail train flooring relies heavily on imported products. Therefore, the rail transit industry has placed high demands on flooring manufacturing, making the development of a high-performance, environmentally friendly, flame-retardant, and resilient domestically produced flooring imperative.

[0003] Currently, most of the flooring used on urban rail trains in China is imported, with major brands including Gerflor, Mondo, Nora, and Yazhuo. This includes both rubber and PVC flooring, with only a few lines using domestically produced rubber flooring. Furthermore, traditional resilient flooring often uses halogenated flame retardants, which, while effective, pose problems such as the release of toxic gases during combustion, bioaccumulation, and environmental pollution. Existing halogen-free flame retardants face challenges such as high dosage requirements, deterioration of mechanical properties, and poor water resistance. Moreover, the flooring currently in use is prone to bacterial growth due to prolonged use and the accumulation of pollutants such as tea and sweat, potentially impacting human health. Currently available flooring products do not meet the environmental performance standards required for the latest high-speed trains in China. With the rapid development of my country's high-speed rail and urban rail systems and the increasing demands for safety, the need for environmentally friendly halogen-free flame-retardant flooring is becoming increasingly urgent, necessitating innovative research and development in raw material selection and key production technologies. Summary of the Invention

[0004] The purpose of this invention is to address existing problems by providing a processing method for environmentally friendly resilient flooring.

[0005] This invention is achieved through the following technical solution: A processing method for an environmentally friendly resilient flooring includes the following steps: S1. Weigh out the corresponding weight parts of polypropylene (10-20 parts), polyethylene (20-26 parts), ethylene propylene diene monomer (EPDM) rubber (60-80 parts), halogen-free flame retardant (20-30 parts), surface-modified Ag / ZnO nanocomposite antibacterial agent (18-20 parts), and anti-aging agent MB (1-2 parts) for later use. S2. The above-weighed polyolefin, EPDM rubber, halogen-free flame retardant, surface-modified Ag / ZnO nanocomposite antibacterial agent, and anti-aging agent MB are added sequentially into a mixer and mixed to obtain a mixture for later use. S3. Add the mixture obtained in step S2 into a twin-screw extruder for extrusion granulation to obtain flame-retardant and antibacterial masterbatch, and then extrude it into sheets through a T-die for later use. S4. The sheet obtained in step S3 is sent into the irradiation chamber for electron beam irradiation treatment, and then sent into the calender to be calendered into flooring substrate. After that, it is subjected to vulcanization and embossing treatment in sequence.

[0006] More preferably, the preparation of the halogen-free flame retardant includes the following steps: (1) Disperse ammonium polyphosphate in anhydrous ethanol by ultrasonication. After the dispersion is uniform, add 4-5 wt% KH-550, heat to 80-90℃, stir at 200-300 rpm for 3-4 h, filter, and vacuum dry at 60-70℃ for 10-12 h to obtain modified ammonium polyphosphate. (2) Disperse sodium-based montmorillonite in deionized water by ultrasonication. After the dispersion is uniform, add it to a four-necked flask. Heat the flask to 70-80°C and add hexadecyltrimethylammonium bromide. React at 200-300 rpm and 70-80°C for 2-3 hours. Then add phytic acid solution and continue stirring for 1-2 hours. Filter the mixture and wash it with deionized water by centrifugation 3-5 times. Dry it under vacuum at 60-70°C for 6-8 hours to obtain the initial modified montmorillonite. (3) The modified montmorillonite is ultrasonically dispersed in deionized water, and 30-40% of the mass of the modified montmorillonite is added with tannic acid. After stirring and mixing, the pH is adjusted to 8-9 with NaOH solution, the temperature is raised to 60-70℃, and the reaction is continued for 4-5 hours. After filtration, the modified montmorillonite is washed 3-5 times with deionized water by centrifugation and then vacuum dried at 60-70℃ for 12 hours. (4) Weigh 20-30 parts of modified ammonium polyphosphate, 7-10 parts of hydroxyapatite nanowires and 18-20 parts of modified montmorillonite and add them to a high-speed mixer in sequence. Then add deionized water, stir at 400-600 rpm for 5-7 min, and then stir at 5000-6000 rpm for 10-15 min to obtain a slurry. (4) After vacuum drying the obtained slurry at 60~70℃ for 6~8h, it can be granulated and extruded.

[0007] More preferably, the mass-to-volume ratio of sodium-based montmorillonite to deionized water in step (2) is 1g:8~10mL; The mass ratio of sodium montmorillonite to hexadecyltrimethylammonium bromide is 1:2~2.6; The pH value of phytic acid solution is 2~3.

[0008] More preferably, in step (4), the solid-liquid ratio is controlled to be 1:8~10 when adding deionized water.

[0009] More preferably, the preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent includes the following steps: 1) Disperse nano zinc oxide in anhydrous ethanol using ultrasonication. After uniform ultrasonic dispersion, heat to 78-86℃. Under constant temperature conditions, add 0.3-0.5 times the amount of propylene methyl dimethoxysilane to nano zinc oxide while stirring at 100-200 rpm. Continue stirring at constant temperature for 8-10 hours. Cool to room temperature, filter, and then wash 3-5 times with anhydrous ethanol by centrifugation. Finally, vacuum dry at 60-70℃ for 6-8 hours to obtain modified nano zinc oxide for later use. 2) The obtained modified nano zinc oxide was ultrasonically dispersed in deionized water to obtain a modified nano zinc oxide aqueous dispersion. Then, 0.1 to 0.2 times the mass of modified nano zinc oxide silver nitrate was added to deionized water and stirred to dissolve to obtain a silver nitrate solution. The silver nitrate solution was added to the modified nano zinc oxide aqueous dispersion and stirred for another 2 to 3 hours. After vacuum drying at 60 to 70°C for 6 to 8 hours, the mixture was pulverized to obtain Ag / ZnO nanocomposite antibacterial agent. 3) Place the Ag / ZnO nanocomposite antibacterial agent obtained in step 2) in a plasma reaction chamber, introduce argon gas, treat with 3~4kW for 2~4min, then ultrasonically disperse it in anhydrous ethanol. After uniform dispersion, add bifunctional ionic liquid, heat to 60~70℃, stir at 180~200rpm for 8~10h, filter, wash 3~5 times with anhydrous ethanol, and vacuum dry at 60~70℃ for 10~14h.

[0010] More preferably, the preparation method of the bifunctional ionic liquid in step 3) is as follows: 1-Butyl-3-methylimidazolium chloride and lithium bis(trifluoromethanesulfonyl)imide are dissolved in acetonitrile at a molar ratio of 1:1. After stirring at room temperature for 10-12 hours, a primary product is obtained. Then, sodium cyanoborogen is added, and stirring is continued for 6-8 hours. The solvent is removed by vacuum distillation to obtain the bifunctional ionic liquid. The molar ratio of the primary product to sodium cyanoborogen is 1:0.2-0.3.

[0011] More preferably, the temperature of the mixing process in step S2 is 160~180℃, and the mixing time is 10~20min.

[0012] More preferably, the temperature during extrusion granulation in step S3 is 180~200℃.

[0013] More preferably, the irradiation dose in step S4 is 10~20 kGy; The vulcanization treatment is carried out at a temperature of 160~180℃, a pressure of 8~10MPa, and a vulcanization time of 20~30min.

[0014] The present invention has the following advantages over the prior art: This invention provides a processing method for environmentally friendly resilient flooring. Using polyolefins, EPDM rubber, halogen-free flame retardants, and surface-modified Ag / ZnO nanocomposite antibacterial agents as raw materials, the method involves processes such as mixing, extrusion, and irradiation. The resulting environmentally friendly resilient flooring not only possesses excellent antibacterial and flame-retardant properties but also exhibits excellent wear resistance and aging resistance, and is environmentally friendly. This invention, through innovative research on the selection of flooring raw materials and key production technologies, has developed a functional, green, and environmentally friendly resilient flooring. This not only provides a healthy living environment for people during their travels but also has significant practical implications for the industrial upgrading of high-quality flooring used in my country's rail transit sector and for expanding the application fields of flooring.

[0015] First, this invention modifies ammonium polyphosphate with a silane coupling agent to obtain modified ammonium polyphosphate. This modification treatment improves its hydrolysis resistance and compatibility with polymers. Montmorillonite is then modified with quaternary ammonium salts followed by phytic acid intercalation. Phytic acid provides a phosphorus source, and the layered structure of montmorillonite slows gas diffusion, synergistically inhibiting combustion. At this stage, the montmorillonite has a large interlayer spacing. Tannic acid is then intercalated into the interlayer, and its polyphenolic structure coordinates with the metal ions in the initially modified montmorillonite layers, forming a stable complex. The resulting modified ammonium polyphosphate, hydroxyapatite nanowires, and modified montmorillonite are mixed using variable-speed stirring to obtain a homogeneous halogen-free flame retardant. When used in the processing of environmentally friendly resilient flooring, it exhibits excellent compatibility with polymers, imparting superior flame retardancy to the resilient flooring.

[0016] Secondly, the surface of nano-zinc oxide is modified with allylmethyldimethoxysilane. The methoxy groups on allylmethyldimethoxysilane react with the hydroxyl groups on the surface of nano-zinc oxide, improving dispersibility and preventing aggregation. Simultaneously, the double bonds can participate in subsequent cross-linking. Then, silver is doped into the modified nano-zinc oxide to prepare an Ag / ZnO nanocomposite antibacterial agent with superior antibacterial properties. At this point, high-energy particles and active groups in plasma interact with the surface of the nano-antibacterial agent, introducing a large number of active groups onto the surface of the Ag / ZnO nano-antibacterial agent, thereby enhancing its interaction with bacteria and further improving its antibacterial performance. Finally, the Ag / ZnO nano-antibacterial agent is further modified using a bifunctional ionic liquid. The amino groups in the ionic liquid bind to ZnO through coordination bonds, and hydrophobic chains (such as long alkyl chains) enhance compatibility with the polymer matrix, while simultaneously releasing antibacterial ions (such as BH3). - ) and Ag + The synergistic effect further enhances the antibacterial properties of the antibacterial agent. Furthermore, the ionic liquid is biodegradable, avoiding the environmental pollution caused by traditional organic solvents, making it more environmentally friendly.

[0017] Finally, irradiation promotes cross-linking. The cross-linked network structure of polyolefins formed by irradiation curing helps to isolate the formation of carbon layers during combustion, further enhancing the flame retardant properties of the composite material. At the same time, through irradiation, it promotes the formation of a stable whole with excellent mechanical properties.

[0018] This invention not only provides a method for processing environmentally friendly resilient flooring, but also provides a highly efficient flame retardant and antibacterial agent for the chemical industry. Detailed Implementation

[0019] The technical solution 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1 A processing method for an environmentally friendly resilient flooring includes the following steps: S1. Weigh out the corresponding weight parts of polypropylene (10 parts), polyethylene (20 parts), ethylene propylene diene monomer (EPDM) rubber (60 parts), halogen-free flame retardant (20 parts), surface-modified Ag / ZnO nanocomposite antibacterial agent (18 parts), and anti-aging agent MB (1 part) for later use. S2. The above-weighed polyolefin, EPDM rubber, halogen-free flame retardant, surface-modified Ag / ZnO nanocomposite antibacterial agent, and anti-aging agent MB are added sequentially into a mixer and mixed at 160°C for 10-20 minutes to obtain a mixture for later use. S3. Add the mixture obtained in step S2 into a twin-screw extruder and extrude and granulate at 180°C to obtain flame-retardant and antibacterial masterbatch, and then extrude sheet material through a T-die for later use. S4. The sheet obtained in step S3 is sent into the irradiation chamber for electron beam irradiation treatment, and then sent into the calender to be calendered into floor substrate. After calendering, it is vulcanized at 160°C and 8MPa for 20 minutes, and then embossed. The irradiation dose was 10 kGy; The preparation of the halogen-free flame retardant includes the following steps: (1) Ammonium polyphosphate was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, 4wt% KH-550 was added, the temperature was raised to 80℃, stirred at 200rpm for 3h, filtered, and vacuum dried at 60℃ for 10h to obtain modified ammonium polyphosphate. (2) Sodium montmorillonite was ultrasonically dispersed in deionized water at a mass-to-volume ratio of 1 g: 8 mL. After being dispersed evenly, it was added to a four-necked flask. After heating to 70°C, cetyltrimethylammonium bromide with a mass of 2 times that of sodium montmorillonite was added. The mixture was reacted at 70°C for 2 hours at 200 rpm. Phytic acid solution (pH 2) was added. After stirring for 1 hour, the mixture was filtered. The mixture was then washed three times by centrifugation with deionized water and dried under vacuum at 60°C for 6 hours to obtain the initial modified montmorillonite. (3) The modified montmorillonite was ultrasonically dispersed in deionized water, and tannic acid of 30% of the mass of the modified montmorillonite was added. After stirring and mixing, the pH was adjusted to 8 with NaOH solution, the temperature was raised to 60℃, and the reaction was continued for 4 hours. After filtration, the modified montmorillonite was obtained by centrifugation and washing three times with deionized water and vacuum drying at 60℃ for 12 hours. (4) Weigh 20-3 parts of modified ammonium polyphosphate, 7 parts of hydroxyapatite nanowires and 18 parts of modified montmorillonite and add them to a high-speed mixer in sequence. Then add deionized water and control the solid-liquid ratio to 1:8. Stir at 400 rpm for 5 min and then at 5000 rpm for 10 min to obtain a slurry. (4) The obtained slurry is vacuum dried at 60°C for 6 hours and then granulated by extrusion granulation. The preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent includes the following steps: 1) Disperse nano zinc oxide in anhydrous ethanol by ultrasonication. After the ultrasonic dispersion is uniform, heat to 78°C. Under constant temperature conditions, add 0.3 times the amount of nano zinc oxide in propenylmethyldimethoxysilane while stirring at 100 rpm. Continue stirring at constant temperature for 8 hours, cool to room temperature, filter, and then wash three times by centrifugation with anhydrous ethanol. After drying under vacuum at 60°C for 6 hours, obtain modified nano zinc oxide for later use. 2) The obtained modified nano zinc oxide was ultrasonically dispersed in deionized water to obtain a modified nano zinc oxide aqueous dispersion. Then, silver nitrate at 0.1 times the mass of the modified nano zinc oxide was added to the deionized water and stirred to dissolve to obtain a silver nitrate solution. The silver nitrate solution was added to the modified nano zinc oxide aqueous dispersion, and the reaction was continued to be stirred for 2 hours. After vacuum drying at 60°C for 6 hours, it was pulverized to obtain Ag / ZnO nanocomposite antibacterial agent. 3) The Ag / ZnO nanocomposite antibacterial agent obtained in step 2) was placed in a plasma reaction chamber, argon gas was introduced, and after treatment at 3kW for 2 min, it was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, a bifunctional ionic liquid was added, the temperature was raised to 60℃, and the reaction was stirred at 180rpm for 8 h. After filtration, the mixture was washed 3 times with anhydrous ethanol and then vacuum dried at 60℃ for 10 h. The preparation method of the bifunctional ionic liquid is as follows: 1-Butyl-3-methylimidazolium chloride and lithium bis(trifluoromethanesulfonyl)imide are dissolved in acetonitrile at a molar ratio of 1:1. After stirring at room temperature for 10 h, a primary product is obtained. Then, sodium cyanoborogen is added, and stirring is continued for 6 h. The solvent is removed by vacuum distillation to obtain the bifunctional ionic liquid. The molar ratio of the primary product to sodium cyanoborogen is 1:0.2.

[0021] Example 2 A processing method for an environmentally friendly resilient flooring includes the following steps: S1. Weigh out the corresponding weight parts of polypropylene (15 parts), polyethylene (23 parts), ethylene propylene diene monomer (EPDM) rubber (70 parts), halogen-free flame retardant (25 parts), surface-modified Ag / ZnO nanocomposite antibacterial agent (19 parts), and anti-aging agent MB (1.5 parts) for later use. S2. The above-weighed polyolefin, EPDM rubber, halogen-free flame retardant, surface-modified Ag / ZnO nanocomposite antibacterial agent, and anti-aging agent MB are added to the internal mixer in sequence and mixed at 170°C for 15 minutes to obtain a mixture for later use. S3. Add the mixture obtained in step S2 into a twin-screw extruder and extrude and granulate at 190°C to obtain flame-retardant and antibacterial masterbatch, and then extrude sheet material through a T-die for later use. S4. The sheet obtained in step S3 is sent into the irradiation chamber for electron beam irradiation treatment, and then sent into the calender to be calendered into floor substrate. After calendering, it is vulcanized at 170°C and 9MPa for 25 minutes, and then embossed. The irradiation dose was 15 kGy; The preparation of the halogen-free flame retardant includes the following steps: (1) Ammonium polyphosphate was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, 4.5wt% KH-550 was added, the temperature was raised to 85℃, and the mixture was stirred at 250rpm for 3.5h. After filtration, the mixture was vacuum dried at 65℃ for 11h to obtain modified ammonium polyphosphate. (2) Sodium montmorillonite was ultrasonically dispersed in deionized water at a mass-to-volume ratio of 1 g: 9 mL. After being dispersed evenly, it was added to a four-necked flask. After heating to 75°C, cetyltrimethylammonium bromide was added at 2.3 times the mass of sodium montmorillonite. The mixture was reacted at 250 rpm and 75°C for 2.5 h. Phytic acid solution (pH 2.5) was added and the mixture was stirred for another 1.5 h. After filtration, the mixture was washed four times by centrifugation with deionized water and then dried under vacuum at 65°C for 7 h to obtain the initial modified montmorillonite. (3) The modified montmorillonite was ultrasonically dispersed in deionized water, and tannic acid of 35% of the mass of the modified montmorillonite was added. After stirring and mixing, the pH was adjusted to 8.5 with NaOH solution, the temperature was raised to 65℃, and the reaction was continued for 4.5h. After filtration, the modified montmorillonite was obtained by centrifugation and washing 4 times with deionized water and vacuum drying at 65℃ for 12h. (4) Weigh 25 parts of modified ammonium polyphosphate, 8 parts of hydroxyapatite nanowires and 19 parts of modified montmorillonite and add them to a high-speed mixer in sequence. Then add deionized water and control the solid-liquid ratio to 1:9. Stir at 500 rpm for 6 min and then at 5500 rpm for 12 min to obtain a slurry. (4) The obtained slurry is vacuum dried at 65°C for 7 hours and then granulated and extruded. The preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent includes the following steps: 1) Disperse nano zinc oxide in anhydrous ethanol by ultrasonication. After the ultrasonic dispersion is uniform, heat to 82°C. Under constant temperature conditions, add 0.4 times the amount of nano zinc oxide in propenylmethyldimethoxysilane while stirring at 150 rpm. Continue stirring at constant temperature for 9 hours, cool to room temperature, filter, and then wash 4 times by centrifugation with anhydrous ethanol. Dry under vacuum at 65°C for 7 hours to obtain modified nano zinc oxide for later use. 2) The obtained modified nano zinc oxide was ultrasonically dispersed in deionized water to obtain a modified nano zinc oxide aqueous dispersion. Then, silver nitrate at 0.5 times the mass of the modified nano zinc oxide was added to the deionized water and stirred to dissolve to obtain a silver nitrate solution. The silver nitrate solution was added to the modified nano zinc oxide aqueous dispersion, and the reaction was continued to be stirred for 2.5 h. After vacuum drying at 65℃ for 7 h, the Ag / ZnO nanocomposite antibacterial agent was obtained by pulverization. 3) The Ag / ZnO nanocomposite antibacterial agent obtained in step 2) was placed in a plasma reaction chamber, argon gas was introduced, and after treatment at 3.5kW for 3 min, it was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, a bifunctional ionic liquid was added, the temperature was raised to 65℃, and the reaction was stirred at 190rpm for 9 h. After filtration, it was washed 4 times with anhydrous ethanol and then vacuum dried at 65℃ for 12 h. The preparation method of the bifunctional ionic liquid is as follows: 1-Butyl-3-methylimidazolium chloride and lithium bis(trifluoromethanesulfonyl)imide are dissolved in acetonitrile at a molar ratio of 1:1. After stirring at room temperature for 11 hours, a primary product is obtained. Then, sodium cyanoborogen is added, and stirring is continued for 7 hours. The solvent is removed by vacuum distillation to obtain the bifunctional ionic liquid. The molar ratio of the primary product to sodium cyanoborogen is 1:0.25.

[0022] Example 3 A processing method for an environmentally friendly resilient flooring includes the following steps: S1. Weigh out the corresponding weight parts of polypropylene 20 parts, polyethylene 26 parts, EPDM rubber 80 parts, halogen-free flame retardant 30 parts, surface-modified Ag / ZnO nanocomposite antibacterial agent 20 parts, and anti-aging agent MB 2 parts for later use. S2. The above-weighed polyolefin, EPDM rubber, halogen-free flame retardant, surface-modified Ag / ZnO nanocomposite antibacterial agent, and anti-aging agent MB are added to the internal mixer in sequence and mixed at 180°C for 20 minutes to obtain a mixture for later use. S3. Add the mixture obtained in step S2 into a twin-screw extruder and extrude and granulate at 200°C to obtain flame-retardant and antibacterial masterbatch, and then extrude sheet material through a T-die for later use. S4. The sheet obtained in step S3 is sent into the irradiation chamber for electron beam irradiation treatment, and then sent into the calender to be calendered into floor substrate. After calendering, it is vulcanized at 180°C and 10MPa for 30 minutes, and then embossed. The irradiation dose was 20 kGy; The preparation of the halogen-free flame retardant includes the following steps: (1) Ammonium polyphosphate was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, 5 wt% KH-550 was added, the temperature was raised to 90℃, and the mixture was stirred at 300 rpm for 4 h. After filtration, the mixture was vacuum dried at 70℃ for 12 h to obtain modified ammonium polyphosphate. (2) Sodium montmorillonite was ultrasonically dispersed in deionized water at a mass-volume ratio of 1 g to 10 mL. After being dispersed evenly, it was added to a four-necked flask. After heating to 80°C, cetyltrimethylammonium bromide was added at 2.6 times the mass of sodium montmorillonite. The mixture was reacted at 300 rpm and 80°C for 3 h. Phytic acid solution (pH 3) was added and stirred for another 2 h. The mixture was then filtered. After washing with deionized water by centrifugation 5 times, the mixture was dried under vacuum at 70°C for 8 h to obtain the initial modified montmorillonite. (3) The modified montmorillonite was ultrasonically dispersed in deionized water, and 40% of the mass of the modified montmorillonite was added with tannic acid. After stirring and mixing, the pH was adjusted to 9 with NaOH solution, the temperature was raised to 70℃, and the reaction was continued for 5 hours. After filtration, the modified montmorillonite was obtained by centrifugation and washing with deionized water 5 times and vacuum drying at 70℃ for 12 hours. (4) Weigh out 30 parts of modified ammonium polyphosphate, 10 parts of hydroxyapatite nanowires and 20 parts of modified montmorillonite and add them to a high-speed mixer in sequence. Then add deionized water and control the solid-liquid ratio to 1:10. Stir at 600 rpm for 7 min and then at 6000 rpm for 15 min to obtain a slurry. (4) The obtained slurry is vacuum dried at 70°C for 8 hours and then granulated by extrusion granulation. The preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent includes the following steps: 1) Disperse nano zinc oxide in anhydrous ethanol by ultrasonication. After the ultrasonic dispersion is uniform, heat to 86°C. Under constant temperature conditions, add 0.5 times the amount of nano zinc oxide in propenylmethyldimethoxysilane while stirring at 200 rpm. Continue stirring at constant temperature for 10 h, cool to room temperature, filter, and then wash 5 times with anhydrous ethanol by centrifugation. Dry under vacuum at 70°C for 8 h to obtain modified nano zinc oxide for later use. 2) The obtained modified nano zinc oxide was ultrasonically dispersed in deionized water to obtain a modified nano zinc oxide aqueous dispersion. Then, 0.2 times the mass of the modified nano zinc oxide was added to the deionized water and stirred to dissolve to obtain a silver nitrate solution. The silver nitrate solution was added to the modified nano zinc oxide aqueous dispersion and stirred for another 3 hours. After vacuum drying at 70°C for 8 hours, the mixture was pulverized to obtain Ag / ZnO nanocomposite antibacterial agent. 3) The Ag / ZnO nanocomposite antibacterial agent obtained in step 2) was placed in a plasma reaction chamber, argon gas was introduced, and after treatment at 4kW for 4 min, it was ultrasonically dispersed in anhydrous ethanol. After uniform dispersion, a bifunctional ionic liquid was added, the temperature was raised to 70℃, and the reaction was stirred at 200rpm for 10 h. After filtration, it was washed 5 times with anhydrous ethanol and then vacuum dried at 70℃ for 14 h. The preparation method of the bifunctional ionic liquid is as follows: 1-Butyl-3-methylimidazolium chloride and lithium bis(trifluoromethanesulfonyl)imide are dissolved in acetonitrile at a molar ratio of 1:1. After stirring at room temperature for 12 hours, a primary product is obtained. Then, sodium cyanoborogen is added, and stirring is continued for 8 hours. The solvent is removed by vacuum distillation to obtain the bifunctional ionic liquid. The molar ratio of the primary product to sodium cyanoborogen is 1:0.3.

[0023] Comparative Example 1 Based on Example 2, the halogen-free flame retardant was replaced with untreated sodium montmorillonite, while the rest of the technical solutions remained the same as those in Example 2.

[0024] Comparative Example 2 Based on Example 2, step 3) is omitted in the preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent, and the rest of the technical solutions are consistent with those in Example 2.

[0025] Comparative Example 3 Based on Example 2, the surface-modified Ag / ZnO nanocomposite antibacterial agent was replaced with untreated nano zinc oxide, while the rest of the technical solutions remained the same as those in Example 2.

[0026] Comparative Example 4 Based on Example 2, no irradiation treatment is performed in step S4, and the remaining technical solutions are consistent with those in Example 2.

[0027] Performance testing 1. Antibacterial performance test The materials of each embodiment and comparative example were pulverized into powder with a particle size of less than 150 μm. The same mass was taken, and the inhibition rate of each group of resilient flooring against Staphylococcus aureus and Escherichia coli was tested according to the Quine test method. The test results are shown in Table 1 below.

[0028] Table 1

[0029] As can be seen from Table 1 above, the environmentally friendly resilient flooring prepared by the present invention has excellent antibacterial properties. Comparing Comparative Examples 1-3 with Example 2, it was found that the antibacterial rate of Example 2 was significantly better than that of the comparative examples, indicating that the treatment of montmorillonite and the treatment of nano zinc oxide in the present invention can improve the antibacterial properties of the environmentally friendly resilient flooring.

[0030] 2. Critical thermal radiation flux detection for resilient flooring Test methods The test was conducted according to GB / T 11785-2005 "Determination of Combustion Performance of Flooring Materials by Radiant Heat Source Method". During the test, two samples perpendicular to a certain direction were tested first. The test was repeated twice in the direction with the lowest test value. The result was the average of the test results of three samples in the same direction.

[0031] Test sample For each example and comparative example, six specimens with dimensions of (1050±5) mm × (230±5) mm were prepared. Three specimens were prepared in one direction and three specimens were prepared in the direction perpendicular to that direction.

[0032] According to the requirements of GB 8624-2012 "Fire Performance Rating of Building Materials and Products", the rating standards are shown in Table 2 below.

[0033] Table 2

[0034] The test results are shown in Table 2 below.

[0035] Table 2

[0036] As can be seen from Table 3 above, the environmentally friendly resilient flooring prepared by this invention can achieve a combustion performance of B1 (B-S1) level, which is a flame-retardant material with good flame retardant effect, is not prone to flame spread, and has good safety in use.

[0037] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A processing method for an environmentally friendly resilient floor, characterized in that, Includes the following steps: S1. Weigh out the corresponding weight parts of polypropylene (10-20 parts), polyethylene (20-26 parts), ethylene propylene diene monomer (EPDM) rubber (60-80 parts), halogen-free flame retardant (20-30 parts), surface-modified Ag / ZnO nanocomposite antibacterial agent (18-20 parts), and anti-aging agent MB (1-2 parts) for later use. S2. The above-weighed polyolefin, EPDM rubber, halogen-free flame retardant, surface-modified Ag / ZnO nanocomposite antibacterial agent, and anti-aging agent MB are added sequentially into a mixer and mixed to obtain a mixture for later use. S3. Add the mixture obtained in step S2 into a twin-screw extruder for extrusion granulation to obtain flame-retardant and antibacterial masterbatch, and then extrude it into sheets through a T-die for later use. S4. The sheet obtained in step S3 is sent into the irradiation chamber for electron beam irradiation treatment, and then sent into the calender to be calendered into flooring substrate. After that, it is subjected to vulcanization and embossing treatment in sequence.

2. The processing method of the environmentally friendly resilient flooring according to claim 1, characterized in that, The preparation of the halogen-free flame retardant includes the following steps: (1) Disperse ammonium polyphosphate in anhydrous ethanol by ultrasonication. After the dispersion is uniform, add 4-5 wt% KH-550, heat to 80-90℃, stir at 200-300 rpm for 3-4 h, filter, and vacuum dry at 60-70℃ for 10-12 h to obtain modified ammonium polyphosphate. (2) Disperse sodium-based montmorillonite in deionized water by ultrasonication. After the dispersion is uniform, add it to a four-necked flask. Heat the flask to 70-80°C and add hexadecyltrimethylammonium bromide. React at 200-300 rpm and 70-80°C for 2-3 hours. Then add phytic acid solution and continue stirring for 1-2 hours. Filter the mixture and wash it with deionized water by centrifugation 3-5 times. Dry it under vacuum at 60-70°C for 6-8 hours to obtain the initial modified montmorillonite. (3) The modified montmorillonite is ultrasonically dispersed in deionized water, and 30-40% of the mass of the modified montmorillonite is added with tannic acid. After stirring and mixing, the pH is adjusted to 8-9 with NaOH solution, the temperature is raised to 60-70℃, and the reaction is continued for 4-5 hours. After filtration, the modified montmorillonite is washed 3-5 times with deionized water by centrifugation and then vacuum dried at 60-70℃ for 12 hours. (4) Weigh 20-30 parts of modified ammonium polyphosphate, 7-10 parts of hydroxyapatite nanowires and 18-20 parts of modified montmorillonite and add them to a high-speed mixer in sequence. Then add deionized water, stir at 400-600 rpm for 5-7 min, and then stir at 5000-6000 rpm for 10-15 min to obtain a slurry. (4) After vacuum drying the obtained slurry at 60~70℃ for 6~8h, it can be granulated and extruded.

3. The processing method for an environmentally friendly resilient flooring according to claim 2, characterized in that, The mass-to-volume ratio of sodium-based montmorillonite to deionized water in step (2) is 1 g: 8~10 mL; The mass ratio of sodium montmorillonite to hexadecyltrimethylammonium bromide is 1:2~2.6; The pH value of phytic acid solution is 2~3.

4. The processing method of an environmentally friendly resilient flooring according to claim 2, characterized in that, When adding deionized water in step (4), the solid-liquid ratio should be controlled to be 1:8~10.

5. The processing method of an environmentally friendly resilient flooring according to claim 1, characterized in that, The preparation of the surface-modified Ag / ZnO nanocomposite antibacterial agent includes the following steps: 1) Disperse nano zinc oxide in anhydrous ethanol using ultrasonication. After uniform ultrasonic dispersion, heat to 78-86℃. Under constant temperature conditions, add 0.3-0.5 times the amount of propylene methyl dimethoxysilane to nano zinc oxide while stirring at 100-200 rpm. Continue stirring at constant temperature for 8-10 hours. Cool to room temperature, filter, and then wash 3-5 times with anhydrous ethanol by centrifugation. Finally, vacuum dry at 60-70℃ for 6-8 hours to obtain modified nano zinc oxide for later use. 2) The obtained modified nano zinc oxide was ultrasonically dispersed in deionized water to obtain a modified nano zinc oxide aqueous dispersion. Then, 0.1 to 0.2 times the mass of modified nano zinc oxide silver nitrate was added to deionized water and stirred to dissolve to obtain a silver nitrate solution. The silver nitrate solution was added to the modified nano zinc oxide aqueous dispersion and stirred for another 2 to 3 hours. After vacuum drying at 60 to 70°C for 6 to 8 hours, the mixture was pulverized to obtain Ag / ZnO nanocomposite antibacterial agent. 3) Place the Ag / ZnO nanocomposite antibacterial agent obtained in step 2) in a plasma reaction chamber, introduce argon gas, treat with 3~4kW for 2~4min, then ultrasonically disperse it in anhydrous ethanol. After uniform dispersion, add bifunctional ionic liquid, heat to 60~70℃, stir at 180~200rpm for 8~10h, filter, wash 3~5 times with anhydrous ethanol, and vacuum dry at 60~70℃ for 10~14h.

6. The processing method of an environmentally friendly resilient flooring according to claim 5, characterized in that, The preparation method of the bifunctional ionic liquid described in step 3) is as follows: 1-Butyl-3-methylimidazolium chloride and lithium bis(trifluoromethanesulfonyl)imide are dissolved in acetonitrile at a molar ratio of 1:

1. After stirring at room temperature for 10-12 h, a primary product is obtained. Then, sodium cyanoborogen is added, and stirring is continued for 6-8 h. The solvent is removed by vacuum distillation to obtain the bifunctional ionic liquid. The molar ratio of the primary product to sodium cyanoborogen is 1:0.2-0.

3.

7. The processing method of an environmentally friendly resilient flooring according to claim 1, characterized in that, The mixing temperature in step S2 is 160~180℃, and the mixing time is 10~20min.

8. The processing method of an environmentally friendly resilient flooring according to claim 1, characterized in that, The temperature during extrusion granulation in step S3 is 180~200℃.

9. The processing method of an environmentally friendly resilient flooring according to claim 1, characterized in that, The irradiation dose described in step S4 is 10~20 kGy; The vulcanization treatment is carried out at a temperature of 160~180℃, a pressure of 8~10MPa, and a vulcanization time of 20~30min.

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