Polyvinyl chloride plastic floor with wear-resistant and anti-skid performance

Abstract

This invention discloses a polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties, relating to the technical fields of polymer materials and building decoration materials. The raw materials include 100 parts of PVC resin, 25-35 parts of plasticizer, 3-5 parts of composite stabilizer, 15-25 parts of wear-resistant modifier, 8-12 parts of anti-slip aggregate, 20-30 parts of filler, and processing aids. The wear-resistant modifier is an in-situ synthesized multi-layered core-shell structure, comprising a vinylsilane-activated nano-cerium dioxide core, a cross-linked polyphosphazene flame-retardant layer formed by the condensation of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone, and a fluorinated epoxy polymer shell copolymerized from hexafluorobutyl methacrylate and glycidyl methacrylate. This modifier achieves nanoscale dispersion through cross-linking with the matrix via active epoxy groups, simultaneously imparting high wear resistance, stain resistance, hydrophobicity, wet-state anti-slip properties, and synergistic flame-retardant properties to the flooring. The preparation method includes two stages: in-situ synthesis of the wear-resistant modifier and blending molding of the PVC flooring.

Description

Technical Field

[0001] This invention relates to the field of polymer materials and building decoration materials technology, and more specifically, to a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties. Background Technology

[0002] With the rapid development of the building decoration industry, polyvinyl chloride (PVC) flooring has been widely used in hospitals, schools, shopping malls, and home decoration due to its numerous advantages such as light weight, environmental friendliness, comfortable feel, and convenient construction. Existing PVC flooring is typically made from a mixture of PVC resin, plasticizers, composite stabilizers, wear-resistant modifiers, anti-slip aggregates, fillers, and various processing aids such as lubricants and antioxidants. However, facing increasingly complex usage environments and higher standards, traditional PVC flooring is gradually revealing significant shortcomings in balancing its overall performance.

[0003] Firstly, in improving the wear resistance and slip resistance of flooring, existing technologies typically employ the direct addition of traditional inorganic nanoparticles such as silica and alumina as wear-resistant agents to the polyvinyl chloride matrix. However, due to the extremely high surface energy of these inorganic nanoparticles and the lack of effective surface treatment, they are prone to agglomeration in organic polyvinyl chloride resin systems, resulting in extremely poor interfacial compatibility between the inorganic wear-resistant phase and the organic matrix. This agglomeration not only causes stress concentration within the material, leading to a sharp decline in the overall mechanical properties of the flooring and even embrittlement and fracture, but also severely sacrifices the original flexibility of the flooring in pursuit of high wear resistance, making it difficult to effectively balance wear-resistant rigidity and cushioning toughness.

[0004] Secondly, in complex real-world usage environments, the stain resistance, water resistance, and flame retardant properties of traditional PVC anti-slip flooring are often unsatisfactory. Conventional anti-slip surface designs easily trap dirt and grime, and the material's high surface energy results in poor stain and water resistance. Especially when the floor surface is wet, its anti-slip effect is severely diminished, posing a slippery safety hazard. Furthermore, indoor building materials are subject to strict fire safety regulations, and existing wear-resistant and anti-slip additives are often single-function and cannot provide additional flame retardant effects to the substrate, failing to meet the stringent requirements of modern buildings for high flame retardant performance.

[0005] Therefore, how to break through the limitations of traditional physical blending modification, fundamentally solve the technical pain point of incompatibility between the inorganic wear-resistant phase and the organic polyvinyl chloride matrix, and develop a polyvinyl chloride plastic floor that can simultaneously achieve high wear resistance, high interfacial bonding force, anti-fouling and anti-slip degradation, and excellent synergistic flame retardant properties has become an important technical problem that needs to be solved by those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies, such as poor interfacial compatibility between inorganic wear-resistant agents and the matrix, difficulty in achieving a balance between wear resistance and flexibility, degradation of anti-slip performance upon contact with water, and insufficient flame retardancy, and to provide a PVC plastic flooring with wear-resistant and anti-slip properties. This invention fundamentally solves the problem of particle agglomeration by introducing an in-situ synthesized multi-layered core-shell structure wear-resistant modifier, simultaneously endowing the flooring with high wear resistance, high interfacial bonding strength, reduced stain and anti-slip properties, and excellent synergistic flame retardant performance.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A type of polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties comprises the following components in parts by weight: 100 parts by weight of polyvinyl chloride resin, 25 to 35 parts by weight of plasticizer, 3 to 5 parts by weight of composite stabilizer, 15 to 25 parts by weight of wear-resistant modifier, 8 to 12 parts by weight of anti-slip aggregate, 20 to 30 parts by weight of filler, 1 to 2 parts by weight of lubricant, 2 to 4 parts by weight of processing aid, and 0.5 to 1 part by weight of antioxidant.

[0008] As a preferred embodiment of the present invention, the wear-resistant modifier has a multi-layer core-shell structure, including an inorganic rigid core, a cross-linked polyphosphazene flame-retardant layer coated on the surface of the inorganic rigid core, and a fluorinated epoxy polymer shell grafted on the outside of the cross-linked polyphosphazene flame-retardant layer.

[0009] As a preferred embodiment of the present invention, the inorganic rigid core is nano-cerium dioxide that has been surface-activated with vinyltriethoxysilane.

[0010] As a preferred embodiment of the present invention, the cross-linked polyphosphazene flame retardant layer is formed by a polycondensation reaction of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone.

[0011] As a preferred embodiment of the present invention, the fluorinated epoxy polymer shell is formed by polymerizing hexafluorobutyl methacrylate and glycidyl methacrylate.

[0012] As a preferred embodiment of the present invention, the polyvinyl chloride resin is selected from one or more of the suspension general-purpose polyvinyl chloride resin SG-3 and suspension general-purpose polyvinyl chloride resin SG-5.

[0013] As a preferred embodiment of the present invention, the plasticizer is selected from one or more of dioctyl phthalate, dibutyl phthalate, dioctyl terephthalate, and epoxidized soybean oil.

[0014] As a preferred embodiment of the present invention, the composite stabilizer is selected from one or more of calcium-zinc composite stabilizers, barium-zinc composite stabilizers, rare earth composite stabilizers, and organotin stabilizers.

[0015] As a preferred embodiment of the present invention, the anti-slip aggregate is selected from one or more of quartz sand, corundum, silicon carbide particles, and glass microspheres.

[0016] As a preferred embodiment of the present invention, the filler is selected from one or more of calcium carbonate powder, ultrafine talc powder, calcined kaolin, and wollastonite powder.

[0017] As a preferred embodiment of the present invention, the lubricant is selected from one or more of stearic acid, calcium stearate, polyethylene wax, and oxidized polyethylene wax.

[0018] As a preferred embodiment of the present invention, the processing aid is selected from one or more of the following: acrylate copolymer ACR-201, acrylate copolymer ACR-401, and acrylate copolymer ACR-503.

[0019] As a preferred embodiment of the present invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and triphenyl phosphite.

[0020] This invention also provides a method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties, comprising the following steps: In the first stage, the in-situ synthesis of the wear-resistant modifier: Nano-cerium dioxide was dispersed in anhydrous acetonitrile, ultrasonically treated, and then vinyltriethoxysilane was added for stirring and reflux reaction. After separation and drying, vinylized nano-cerium dioxide was obtained. The vinylized nano-cerium dioxide was redispersed in tetrahydrofuran, and hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone were added. After slowly adding an acid-binding agent, the temperature was raised to carry out the reaction, and a core-shell intermediate with residual vinyl groups on the surface was obtained. The core-shell intermediate was dispersed in deionized water, and sodium dodecyl sulfate was added for emulsification. After introducing a protective gas and raising the temperature, hexafluorobutyl methacrylate, glycidyl methacrylate, and potassium persulfate aqueous solution were added dropwise for isothermal reaction. After demulsification, washing with water, and drying, the wear-resistant modifier with the multi-layered core-shell structure was obtained. The second stage involves the blending and molding of PVC plastic flooring: Weighed PVC resin, plasticizer, composite stabilizer, filler, lubricant, processing aid, antioxidant, and the aforementioned wear-resistant modifier are added to a mixer for hot mixing; subsequently, the mixture is discharged into a cold mixer for cooling; the cold-mixed material is then mixed evenly with anti-slip aggregate, fed into a twin-screw extruder for melt extrusion plasticization, pressed into sheets by calendering equipment, cooled, drawn, and cut to obtain the PVC plastic flooring with wear-resistant and anti-slip properties.

[0021] As a preferred technical solution of the present invention, the specific process for obtaining vinylated nano-cerium dioxide is as follows: 30 to 40 parts by weight of nano-cerium dioxide with a particle size of 20 to 100 mesh are dispersed in 200 parts by weight of anhydrous acetonitrile, ultrasonically treated for 30 minutes, 2 to 3 parts by weight of vinyltriethoxysilane are added, and the mixture is stirred and refluxed at 65 degrees Celsius for 4 hours, centrifuged, washed and dried.

[0022] As a preferred technical solution of the present invention, the specific process for obtaining the core-shell intermediate with residual vinyl groups on the surface is as follows: the vinylized nano-cerium dioxide is redispersed in 300 parts by weight of tetrahydrofuran, 10 to 15 parts by weight of hexachlorocyclotriphosphazene and 12 to 18 parts by weight of 4,4'-dihydroxydiphenyl sulfone are added sequentially, and 8 to 10 parts by weight of triethylamine are slowly added dropwise under an ice bath; after the addition is completed, the temperature is raised to 55 degrees Celsius and the reaction is carried out for 12 hours.

[0023] As a preferred technical solution of the present invention, the specific process for obtaining the wear-resistant modifier with the multi-layer core-shell structure is as follows: the core-shell intermediate is dispersed in 400 parts by weight of deionized water, and 1.5 to 2.5 parts by weight of sodium dodecyl sulfate is added for emulsification for 30 minutes; nitrogen gas is introduced for protection, the temperature is raised to 75 degrees Celsius, and 15 to 20 parts by weight of hexafluorobutyl methacrylate, 8 to 12 parts by weight of glycidyl methacrylate and 0.5 to 1 part by weight of potassium persulfate aqueous solution are added dropwise to the reaction system at a uniform rate, the dropwise addition time is controlled at 2 hours, and the reaction is continued at a constant temperature for 6 hours; after the reaction is completed, the mixture is demulsified, washed with water, and freeze-dried under vacuum.

[0024] As a preferred technical solution of the present invention, the specific process of hot mixing and cold mixing in the second stage is as follows: polyvinyl chloride resin, plasticizer, composite stabilizer, filler, lubricant, processing aid, antioxidant and wear-resistant modifier are put into a high-speed mixer and hot-mixed at high speed for 10 to 15 minutes at 110 to 120 degrees Celsius; then discharged into a cold mixer and cooled to 40 to 50 degrees Celsius.

[0025] As a preferred technical solution of the present invention, the specific process of extrusion and molding in the second stage is as follows: the cold-mixed material is mixed evenly with the anti-slip aggregate, fed into a twin-screw extruder, and melt-extruded and plasticized in a temperature range of 160 to 180 degrees Celsius. The material is then pressed into sheets by a calendering molding equipment, and cooled, drawn, and cut to obtain the polyvinyl chloride plastic floor with wear-resistant and anti-slip properties.

[0026] The polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties described in this invention can be used as a non-metallic additive manufacturing material.

[0027] The polyvinyl chloride plastic flooring with wear-resistant and anti-slip properties described in this invention may also have a certain amount of terpolymer or fluororubber added.

[0028] This invention utilizes an in-situ composite process to form a multi-layered core-shell structure wear-resistant modifier with an inorganic rigid core, a flame-retardant buffer layer, and a reactive fluorine-containing outer shell. This modifier forms a multi-synergistic mechanism with the matrix polyvinyl chloride resin and additives such as plasticizers, composite stabilizers, anti-slip aggregates, fillers, lubricants, processing aids, and antioxidants. Firstly, nano-cerium dioxide, acting as a rigid core, provides wear resistance. After its surface is activated by vinyltriethoxysilane coupling, it synergistically interacts with the outer grafted glycidyl methacrylate. The active epoxy groups in the glycidyl methacrylate... During processing and molding, it can entangle with polyvinyl chloride matrix, overcoming the defect of inorganic nanoparticles being prone to agglomeration and stress concentration, and achieving nanoscale uniform dispersion and high-strength interfacial bonding of wear-resistant modifier in matrix; secondly, the cross-linked polyphosphazene layer formed by the reaction of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone, together with the fluorinated epoxy polymer shell formed by the copolymerization of hexafluorobutyl methacrylate and glycidyl methacrylate, coat the inorganic core, forming an elastic buffer microstructure. When the material is subjected to external friction or impact, Under stress, this cushioning structure absorbs and dissipates destructive impact stress, significantly improving the wear-resistant and anti-slip lifespan while maintaining the original flexibility of PVC flooring, preventing the material from becoming brittle and breaking due to the direct introduction of rigid particles. Simultaneously, the fluorinated monomer hexafluorobutyl methacrylate introduced into the outermost shell gives the flooring surface extremely low surface energy, achieving excellent hydrophobic and oleophobic properties. This effectively blocks the spread and penetration of water on the flooring surface, solving the problems of traditional plastic flooring easily accumulating dirt and grime and experiencing a significant decrease in anti-slip performance when wet. Safety hazards; Finally, the cross-linked polyphosphazene network in the intermediate coating layer is rich in phosphorus and nitrogen flame retardant elements and has excellent halogen-free flame retardant properties. When the material is heated or burned, it can promote the formation of a dense carbon layer on the surface, effectively blocking the transfer of oxygen and heat to the interior, providing a strong synergistic flame retardant effect for polyvinyl chloride body. It simultaneously solves multiple technical problems such as high wear resistance, high interfacial compatibility, anti-fouling and anti-slip attenuation and high flame retardancy in one component, so that all raw materials can exert a synergistic effect far exceeding that of simple physical mixing under a specific weight ratio.

[0029] Compared with the prior art, the beneficial effects of the present invention are: 1. In the synthesis of the wear-resistant modifier, nano-cerium dioxide is first activated by coupling with vinyltriethoxysilane, and then a fluorinated epoxy polymer shell containing active epoxy groups is grafted onto the outermost layer. This overcomes the aggregation defects of inorganic nanoparticles. It can absorb and dissipate impact stress, improving wear-resistant and anti-slip service life while maintaining the original flexibility of PVC.

[0030] 2. Wear-resistant modifiers reduce the surface energy of the flooring surface during processing and molding, giving the material hydrophobic and oleophobic properties. This structure makes the flooring surface less prone to dirt accumulation and provides stain resistance and self-cleaning capabilities.

[0031] 3. A cross-linked polyphosphazene flame-retardant layer, generated by the reaction of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone, is introduced in situ between the inorganic core and shell of the wear-resistant modifier. This provides synergistic flame-retardant protection for the polyvinyl chloride matrix, achieving high wear resistance, anti-fouling, anti-slip, and flame-retardant functions simultaneously through a single modifier component. Attached Figure Description

[0032] Figure 1 This is a comparison chart of some performance tests in the embodiments and comparative examples of the present invention. Detailed Implementation

[0033] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely 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. Example 1

[0034] Preparation of a polyvinyl chloride (PVC) plastic flooring with wear-resistant and slip-resistant properties: 1. The raw material composition by weight is as follows: 100 parts of suspension general-purpose polyvinyl chloride resin SG-5, 30 parts of dioctyl phthalate, 4 parts of calcium-zinc composite stabilizer, 20 parts of wear-resistant modifier, 10 parts of quartz sand with a particle size of 40-60 mesh, 25 parts of light calcium carbonate, 1.5 parts of calcium stearate, 3 parts of acrylate copolymer ACR-401, and 0.8 parts of antioxidant 1010. The suspension-type general-purpose polyvinyl chloride resin SG-5 was purchased from Hangzhou Electrochemical New Materials Co., Ltd. The acrylate copolymer ACR-401 mentioned above was purchased from Shandong Ruifeng Polymer Materials Co., Ltd.

[0035] 2. Preparation of wear-resistant modifier: 2.1 The raw material composition by weight is as follows: 35 parts of nano-cerium dioxide with a particle size of 30-40 nanometers, 200 parts of anhydrous acetonitrile, 2.5 parts of vinyltriethoxysilane, 300 parts of tetrahydrofuran, 12 parts of hexachlorocyclotriphosphazene, 15 parts of 4,4'-dihydroxydiphenyl sulfone, 9 parts of triethylamine, 400 parts of deionized water, 2 parts of sodium dodecyl sulfate, 18 parts of hexafluorobutyl methacrylate, 10 parts of glycidyl methacrylate, and 0.8 parts of potassium persulfate.

[0036] 2.2 Preparation method: Step 1: Preparation of vinylated cerium dioxide nanoparticles: 35 parts by weight of cerium dioxide nanoparticles with a particle size of 30-40 nm were dispersed in 200 parts by weight of anhydrous acetonitrile and ultrasonically treated in an ultrasonic cleaner for 30 minutes to ensure full dispersion of the nanoparticles; then 2.5 parts by weight of vinyltriethoxysilane were added to the above dispersion, and the mixture was heated to 65 degrees Celsius and stirred under reflux for 4 hours under nitrogen protection; after the reaction was completed, the product was centrifuged, washed three times with anhydrous ethanol and deionized water, and dried in a vacuum drying oven at 60 degrees Celsius for 12 hours to obtain vinylated cerium dioxide nanoparticles.

[0037] The second step is the preparation of the core-shell intermediate: the above-mentioned vinylized cerium dioxide nanoparticles are redispersed in 300 parts by weight of tetrahydrofuran and ultrasonically dispersed for 20 minutes; 12 parts by weight of hexachlorocyclotriphosphazene and 15 parts by weight of 4,4'-dihydroxydiphenyl sulfone are added sequentially, and 9 parts by weight of triethylamine is slowly added dropwise as an acid-binding agent under ice bath conditions, controlling the dropping rate so that the system temperature does not exceed 10 degrees Celsius; after the addition is completed, the temperature is raised to 55 degrees Celsius and the reaction is continuously stirred for 12 hours; after the reaction is completed, the mixture is centrifuged and washed three times with tetrahydrofuran to obtain a core-shell intermediate with residual vinyl groups on the surface.

[0038] Step 3, grafting of fluorinated epoxy polymer shell: The above core-shell intermediate is dispersed in 400 parts by weight of deionized water, and 2 parts by weight of sodium dodecyl sulfate is added as an emulsifier. The mixture is ultrasonically emulsified for 30 minutes. Nitrogen gas is introduced to replace the air in the system, and the temperature is raised to 75 degrees Celsius. 18 parts by weight of hexafluorobutyl methacrylate, 10 parts by weight of glycidyl methacrylate, and 0.8 parts by weight of a pre-prepared potassium persulfate aqueous solution (the potassium persulfate aqueous solution is prepared by dissolving 0.8 parts by weight of potassium persulfate in 10 parts by weight of deionized water) are mixed and added dropwise to the reaction system at a uniform rate, controlling the dropwise addition time to 2 hours. After the dropwise addition is completed, the reaction is continued at a constant temperature of 75 degrees Celsius for 6 hours. After the reaction is completed, excess sodium chloride solution is added to break the emulsion, filtered, and washed with deionized water until the filtrate is neutral. The filtrate is then freeze-dried under vacuum (-50 degrees Celsius, 10 Pascals, 24 hours) to obtain the wear-resistant modifier with the multilayer core-shell structure.

[0039] 3. The preparation method of polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties is as follows: Hot and cold mixing processes: Weighed polyvinyl chloride resin, dioctyl phthalate, calcium-zinc composite stabilizer, light calcium carbonate, calcium stearate, acrylate copolymer ACR-401, antioxidant 1010, and the above-prepared wear-resistant modifier are added to a high-speed mixer. The speed is set to 800 rpm, and the temperature is raised to 115 degrees Celsius for high-speed hot mixing for 12 minutes to fully melt and mix the components and pre-plasticize them. Then, the hot-mixed material is discharged into a cold mixer, and cooling water is introduced to cool it down to 45 degrees Celsius to reduce the material temperature to near room temperature and prevent overheating and degradation, thus obtaining a premixed material.

[0040] Extrusion and molding process: The premixed material after cold mixing is mixed with quartz sand anti-slip aggregate in a low-speed mixer for 5 minutes to ensure that the anti-slip aggregate is evenly coated on the surface of the premixed material; then the mixture is fed into a twin-screw extruder, and the barrel temperature is set from the feeding section to the die head as follows: 160 degrees Celsius, 165 degrees Celsius, 170 degrees Celsius, 175 degrees Celsius, 170 degrees Celsius, and the screw speed is 30 rpm for melt extrusion and plasticization; the extruded molten material is pressed into a sheet with a thickness of 2.0 mm by a four-roll calendering molding machine, and the roller temperature is controlled at 165 degrees Celsius, 170 degrees Celsius, 175 degrees Celsius, 170 degrees Celsius; the calendered sheet is cooled to room temperature by a cooling roller group, drawn to a cutting device, and cut into standard sizes (600 mm in length × 600 mm in width), thus obtaining the PVC plastic floor with wear-resistant and anti-slip properties. Example 2

[0041] The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, except that dioctyl phthalate is replaced with dioctyl terephthalate, and the rest is the same as in Example 1. Example 3

[0042] The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, except that the quartz sand is replaced with corundum, and the rest is the same as in Example 1. Example 4

[0043] The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, except that the light calcium carbonate is replaced with ultrafine talc powder, and the rest is the same as in Example 1.

[0044] Comparative Example 1 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is the same as in Example 1, except that the wear-resistant modifier is not added.

[0045] Comparative Example 2 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is the same as in Example 1, except that glycidyl methacrylate is not added.

[0046] Comparative Example 3 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, except that glycidyl methacrylate is replaced with methyl methacrylate, and the rest is the same as in Example 1.

[0047] Comparative Example 4 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is the same as in Example 1, except that hexafluorobutyl methacrylate is not added.

[0048] Comparative Example 5 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, except that hexafluorobutyl methacrylate is replaced with methyl methacrylate, and the rest is the same as in Example 1.

[0049] Comparative Example 6 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is carried out by referring to the preparation method of Example 1, without the preparation of wear-resistant modifiers, by directly blending the same weight parts of nano-cerium dioxide and hexachlorocyclotriphosphazene with the resin matrix, and the rest is the same as in Example 1.

[0050] Comparative Example 7 The preparation of a polyvinyl chloride plastic floor with wear-resistant and anti-slip properties is the same as in Example 1, except that hexachlorocyclotriphosphazene is not added.

[0051] Performance testing: 1. Combined Dry and Wet Anti-slip Performance Test: The dry anti-slip performance was tested according to the method specified in GB / T22374-2018, using a pendulum friction coefficient tester (BPN) to measure the anti-slip level in the dry state; the wet anti-slip performance was tested according to ASTM E303-93 standard, by uniformly spraying a 3mm thick deionized water film on the floor surface, allowing it to stand for 30 seconds, and then measuring the wet pendulum friction coefficient. The data are shown in Table 1.

[0052] 2. Anti-fouling and self-cleaning performance test: GB / T9780-2013 was adopted. Standard oil-based markers were used as the pollution source to test the wiping removal rate after contamination. The data are shown in Table 1.

[0053] 3. Synergistic flame retardant performance test: The vertical burning performance was tested according to GB / T2408-2008 to determine the flame retardant rating. The data are shown in Table 1.

[0054] 4. Mechanical properties: Tensile strength was tested according to GB / T1040.2-2006, and the data are shown in Table 1.

[0055] Table 1 Comparative Example 1 lacks the core multi-layered core-shell structure wear-resistant modifier of this patent. The PVC matrix lacks the physical support of the rigid nano-cerium dioxide core, making the floor surface difficult to resist external friction. Simultaneously, there is no fluorinated shell to reduce surface energy, nor a polyphosphazene network to provide a synergistic phosphorus-nitrogen flame-retardant effect. Therefore, this group of materials only possesses the basic properties of ordinary PVC flooring; its wear resistance, anti-slip performance in wet conditions, stain resistance and self-cleaning rate, and flame retardant rating are all at the lowest baseline levels.

[0056] In Comparative Example 2 (without glycidyl methacrylate), the absence of GMA resulted in the loss of the ability of the outer fluorinated shell of the wear-resistant modifier to entangle with the polyvinyl chloride matrix. This led to a deterioration in the interfacial compatibility between the inorganic wear-resistant phase and the organic resin matrix. The modifier particles were prone to agglomeration in the matrix, causing internal stress concentration. Macroscopically, this manifested as a significant decrease in the tensile strength and other mechanical properties of the material, as well as a shortened wear life.

[0057] Comparative Example 3 (where glycidyl methacrylate was replaced with methyl methacrylate), although methyl methacrylate (MMA) can participate in polymerization to form a shell, it lacks the active epoxy groups unique to GMA. It can only undergo weak physical blending with the PVC matrix and cannot form high-strength entanglement. Therefore, under continuous external friction or impact shear force, the modifier particles are easily peeled or detached from the matrix, and its mechanical toughness and long-term wear resistance and anti-slip performance will be significantly inferior to those of Example 1.

[0058] Comparative Example 4 (without hexafluorobutyl methacrylate): Hexafluorobutyl methacrylate is a key fluorinated monomer that imparts ultra-low surface energy to the material. Without this component, the outermost layer of the modifier loses its hydrophobic and oleophobic properties. When moisture comes into contact with the floor surface, the water film spreads rapidly and wets the surface, causing a decrease in the wet anti-slip friction coefficient. Simultaneously, the high surface energy allows contaminants such as oil-based markers to easily penetrate and adhere firmly, completely eliminating the material's stain-resistant and self-cleaning capabilities.

[0059] In Comparative Example 5 (where hexafluorobutyl methacrylate was replaced with methyl methacrylate), although the replaced MMA maintained the structural integrity of the shell, the MMA molecule lacked fluorine atoms, thus failing to achieve the extremely low surface energy effect provided by the fluorine-containing groups. Its degradation mechanism was similar to Comparative Example 4, with the shell unable to effectively block the penetration of moisture and oil. Therefore, this flooring performed far worse than Example 1, which had a fluorine-containing shell, in terms of stain resistance, self-cleaning removal rate, and wet slip resistance.

[0060] Comparative Example 6 (direct physical blending, without core-shell structure preparation) This is a traditional physical addition method. The surface energy of unactivated and uncoated cerium dioxide nanoparticles is extremely high, leading to severe agglomeration in organic PVC and plasticizer systems. This agglomeration fails to leverage the wear resistance advantages of nanoparticles; instead, it creates significant microscopic defects within the material, resulting in severe embrittlement. Furthermore, the lack of an in-situ generated elastic polyphosphazene buffer layer prevents the material from dissipating impact stress, and the synergistic effect mechanism of various properties completely fails in this group.

[0061] Comparative Example 7 (without hexachlorocyclotriphosphazene): Hexachlorocyclotriphosphazene is the core precursor for constructing the cross-linked polyphosphazene flame-retardant layer. Without this component, a phosphorus- and nitrogen-rich elastic buffer network is lost between the inorganic rigid core and the outer polymer shell. This not only prevents the material from effectively catalyzing the formation of a dense char layer on the surface during heating and combustion, resulting in a significant decrease in vertical burning rating and flame-retardant performance; it also weakens the modifier's ability to absorb and dissipate external impact stress, compromising the flooring's performance in balancing high wear resistance and flexibility.

[0062] 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 alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A type of polyvinyl chloride (PVC) plastic flooring with wear-resistant and slip-resistant properties, characterized in that, Its raw materials include the following components in parts by weight: 100 parts polyvinyl chloride resin, 25 to 35 parts plasticizer, 3 to 5 parts composite stabilizer, 15 to 25 parts wear-resistant modifier, 8 to 12 parts anti-slip aggregate, 20 to 30 parts filler, 1 to 2 parts lubricant, 2 to 4 parts processing aid, and 0.5 to 1 part antioxidant; The wear-resistant modifier has a multi-layer core-shell structure, including an inorganic rigid core, a cross-linked polyphosphazene flame retardant layer coated on the surface of the inorganic rigid core, and a fluorinated epoxy polymer shell grafted on the outside of the cross-linked polyphosphazene flame retardant layer. The inorganic rigid core is nano-cerium dioxide that has been surface-activated with vinyltriethoxysilane; The cross-linked polyphosphazene flame retardant layer is formed by the polycondensation reaction of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone. The fluorinated epoxy polymer shell is formed by the polymerization of hexafluorobutyl methacrylate and glycidyl methacrylate.

2. The polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 1, characterized in that, The polyvinyl chloride resin is selected from one or more of the following: suspension general-purpose polyvinyl chloride resin SG-3 and suspension general-purpose polyvinyl chloride resin SG-5. The plasticizer is selected from one or more of dioctyl phthalate, dibutyl phthalate, dioctyl terephthalate, and epoxidized soybean oil; The composite stabilizer is selected from one or more of calcium-zinc composite stabilizers, barium-zinc composite stabilizers, rare earth composite stabilizers, and organotin stabilizers.

3. The polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 1, characterized in that, The anti-slip aggregate is selected from one or more of the following: quartz sand, corundum, silicon carbide particles, and glass microspheres. The filler is selected from one or more of calcium carbonate powder, ultrafine talc powder, calcined kaolin, and wollastonite powder; The lubricant is selected from one or more of stearic acid, calcium stearate, polyethylene wax, and oxidized polyethylene wax.

4. The polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 1, characterized in that, The processing aid is selected from one or more of the following: acrylate copolymer ACR-201, acrylate copolymer ACR-401, and acrylate copolymer ACR-503. The antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and triphenyl phosphite.

5. A method for preparing a polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties as described in any one of claims 1-4, characterized in that, Includes the following steps: In the first stage, the in-situ synthesis of the wear-resistant modifier: Nano-cerium dioxide was dispersed in anhydrous acetonitrile, ultrasonically treated, and then vinyltriethoxysilane was added for stirring and reflux reaction. After separation and drying, vinylized nano-cerium dioxide was obtained. The vinylized nano-cerium dioxide was redispersed in tetrahydrofuran, and hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenyl sulfone were added. After slowly adding an acid-binding agent, the temperature was raised to carry out the reaction, and a core-shell intermediate with residual vinyl groups on the surface was obtained. The core-shell intermediate was dispersed in deionized water, and sodium dodecyl sulfate was added for emulsification. After introducing a protective gas and raising the temperature, hexafluorobutyl methacrylate, glycidyl methacrylate, and potassium persulfate aqueous solution were added dropwise for isothermal reaction. After demulsification, washing with water, and drying, the wear-resistant modifier with the multi-layered core-shell structure was obtained. The second stage involves the blending and molding of PVC plastic flooring: Weighed PVC resin, plasticizer, composite stabilizer, filler, lubricant, processing aid, antioxidant, and the aforementioned wear-resistant modifier are added to a mixer for hot mixing; subsequently, the mixture is discharged into a cold mixer for cooling; the cold-mixed material is then mixed evenly with anti-slip aggregate, fed into a twin-screw extruder for melt extrusion plasticization, pressed into sheets by calendering equipment, cooled, drawn, and cut to obtain the PVC plastic flooring with wear-resistant and anti-slip properties.

6. The method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 5, characterized in that, The specific process for obtaining vinylated nano-cerium dioxide is as follows: 30 to 40 parts by weight of cerium dioxide with a particle size of 20 to 100 mesh are dispersed in 200 parts by weight of anhydrous acetonitrile, ultrasonically treated for 30 minutes, 2 to 3 parts by weight of vinyltriethoxysilane are added, and the mixture is stirred and refluxed at 65 degrees Celsius for 4 hours, centrifuged, washed and dried.

7. The method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 5, characterized in that, The specific process for obtaining the core-shell intermediate with residual vinyl groups on the surface is as follows: the vinylized cerium dioxide nanoparticles are redispersed in 300 parts by weight of tetrahydrofuran, and 10 to 15 parts by weight of hexachlorocyclotriphosphazene and 12 to 18 parts by weight of 4,4'-dihydroxydiphenyl sulfone are added sequentially, and 8 to 10 parts by weight of triethylamine are slowly added dropwise under an ice bath; after the addition is completed, the temperature is raised to 55 degrees Celsius and the reaction is carried out for 12 hours.

8. The method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 5, characterized in that, The specific process for obtaining the wear-resistant modifier with the multi-layer core-shell structure is as follows: the core-shell intermediate is dispersed in 400 parts by weight of deionized water, and 1.5 to 2.5 parts by weight of sodium dodecyl sulfate is added and emulsified for 30 minutes. Under nitrogen protection, the temperature was raised to 75 degrees Celsius. 15 to 20 parts by weight of hexafluorobutyl methacrylate, 8 to 12 parts by weight of glycidyl methacrylate, and 0.5 to 1 part by weight of potassium persulfate aqueous solution were added dropwise to the reaction system at a uniform rate over a period of 2 hours. The reaction was continued at a constant temperature for 6 hours. After the reaction was completed, the mixture was demulsified, washed with water, and freeze-dried under vacuum.

9. The method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 5, characterized in that, The specific process of hot mixing and cold mixing in the second stage is as follows: polyvinyl chloride resin, plasticizer, composite stabilizer, filler, lubricant, processing aid, antioxidant and wear-resistant modifier are put into a high-speed mixer and hot mixed at high speed for 10 to 15 minutes at 110 to 120 degrees Celsius; then discharged into a cold mixer and cooled to 40 to 50 degrees Celsius.

10. The method for preparing polyvinyl chloride (PVC) plastic flooring with wear-resistant and anti-slip properties according to claim 5, characterized in that, The specific process of extrusion and molding in the second stage is as follows: the cold-mixed material is mixed evenly with the anti-slip aggregate, fed into a twin-screw extruder, and melt-extruded and plasticized in a temperature range of 160 to 180 degrees Celsius. The material is then pressed into sheets by calendering equipment, and after cooling, traction, and cutting, the wear-resistant and anti-slip PVC plastic flooring is obtained.

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