Environment-friendly plastic floor and manufacturing process thereof

Abstract

This invention relates to the field of plastic flooring technology, specifically to an environmentally friendly plastic flooring and its manufacturing process. The environmentally friendly plastic flooring comprises the following raw material components: by weight, 35-45 parts PP, 35-45 parts modified PP, 20-35 parts modified montmorillonite, 8-12 parts toughening agent, 4-6 parts compatibilizer, 0.2-1 parts antioxidant, and 1-3 parts lubricant. The modified PP is prepared by acyl chloride reaction of unsaturated carboxylic acids to obtain an unsaturated acyl chloride product; then, the unsaturated acyl chloride product undergoes an amidation reaction with a nitro-containing piperazine; after reduction treatment, it first undergoes a Michael addition reaction with DOPO, and then an amidation reaction with the unsaturated acyl chloride product; finally, it is prepared by irradiation-induced crosslinking grafting with PP and a crosslinking agent. The modified montmorillonite is obtained by intercalation modification of montmorillonite with a quaternary ammonium salt intercalation modifier, followed by modification with a silane coupling agent.

Description

Technical Field

[0001] This invention relates to the field of plastic flooring technology, specifically to an environmentally friendly plastic floor and its manufacturing process. Background Technology

[0002] Traditional polypropylene (PP) plastic flooring has a low flame retardancy rating and relies heavily on halogenated flame retardants to achieve its fire-resistant effect. This type of plastic flooring easily releases toxic and corrosive fumes when burning, resulting in extremely poor environmental performance. Furthermore, these flame retardants pose a risk of migration and release, which, in the long run, presents significant hidden hazards to human health and the environment.

[0003] In addition, pure PP flooring has insufficient mechanical properties, is easily worn, and has poor dimensional stability. Long-term use can easily lead to problems such as warping, deformation, and cracking. Existing technologies usually use inorganic fillers to improve it, but inorganic fillers have poor interfacial compatibility with the PP matrix. If the amount added increases, it will actually cause the performance of PP plastic flooring to decline.

[0004] Based on this, the present invention provides an environmentally friendly and safe plastic flooring with excellent comprehensive performance based on polypropylene. It achieves flame retardancy through a halogen-free nitrogen-phosphorus synergistic flame retardant system, and the raw material components are tightly bound together, which greatly reduces the risk of small molecule substances migrating and precipitating, and improves the overall dimensional stability of the plastic flooring, which is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide an environmentally friendly plastic flooring and its manufacturing process to solve the related technical problems existing in the prior art.

[0006] To achieve the above objectives, the first aspect of the present invention provides the following specific technical solution: An environmentally friendly plastic flooring comprises the following raw material components: by weight, 35-45 parts polypropylene (PP), 35-45 parts modified PP, 20-35 parts modified montmorillonite, 8-12 parts toughening agent, 4-6 parts compatibilizer, 0.2-1 parts antioxidant, and 1-3 parts lubricant.

[0007] More preferably, the modified PP is prepared by acyl chloride reaction of unsaturated carboxylic acid to obtain unsaturated acyl chloride product; then the unsaturated acyl chloride product undergoes amidation reaction with piperazine containing nitro group; after reduction treatment, it first undergoes Michael addition reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and then undergoes amidation reaction with unsaturated acyl chloride product; finally, it is prepared by irradiation-induced crosslinking grafting with PP and crosslinking agent; the specific preparation method is as follows: (1) Under nitrogen protection, unsaturated carboxylic acid is added to toluene and stirred at 40-60℃. Add thionyl chloride and react for 3-6 hours. Distill under reduced pressure to obtain unsaturated acyl chloride product; (2) Add the unsaturated acyl chloride product to dichloromethane and stir to obtain mixture A. Divide the mixture into equal amounts of mixture A1 and mixture A2. Under nitrogen protection, add piperazine containing nitro and potassium carbonate to dichloromethane and stir to mix. Heat to 30-38℃ and then add mixture A1 dropwise at a rate of 1-3 mL / min while stirring. After the addition is complete, continue stirring and react for 8-12 hours. Distill under reduced pressure to obtain unsaturated nitro product; (3) Under nitrogen protection, unsaturated nitro products and sodium dithionite were added to ethyl acetate and stirred at 40-50℃ for 1-3 hours. The mixture was then distilled under reduced pressure to obtain unsaturated amino products. (4) The unsaturated amino products were added to toluene and stirred until homogeneous to obtain mixture B. Under nitrogen protection, DOPO was added to toluene and stirred until homogeneous. The temperature was raised to 90-100℃, and mixture B was added dropwise at a rate of 1-3 mL / min while stirring. After the addition was complete, the mixture was stirred for 3-6 hours and then distilled under reduced pressure to obtain DOPO grafted products. Amino products; (5) Under nitrogen protection, DOPO grafted amino products and potassium carbonate are added to dichloromethane, stirred and mixed, heated to 30-38℃, and then mixed solution A2 is added dropwise at a rate of 1-3 mL / min while stirring. After the addition is complete, the reaction is continued for 8-12 hours, and the mixture is distilled under reduced pressure to obtain unsaturated DOPO grafted amino products; (6) Under nitrogen protection, PP is added to toluene and stirred to dissolve at 95-105℃. Then, unsaturated DOPO grafted amino products and crosslinking agents are added and stirred and mixed. 60 Co-γ rays were used to irradiate the product with a dose of 20-60 kGy and a dose rate of 2-4 kGy / h, followed by vacuum distillation to obtain modified PP.

[0008] More preferably, in the preparation of the unsaturated acyl chloride product, the ratio of unsaturated carboxylic acid, thionyl chloride, and toluene is 0.8-1.2g:1.8-2.2g:30-40mL.

[0009] More preferably, the unsaturated carboxylic acid is a carboxylic acid containing a double bond, including but not limited to at least one of acrylic acid, methacrylic acid, butenoic acid, 5-hexenoic acid, and 7-octenic acid.

[0010] More preferably, in the preparation of the mixture A, the ratio of unsaturated acyl chloride product to dichloromethane is 0.80-1.20g: 8-12mL.

[0011] More preferably, in the preparation of the unsaturated nitro product, the ratio of the amount of nitro-containing piperazine, potassium carbonate, dichloromethane, and mixed solution A1 is 0.80-1.20g:0.25-0.40g:40-50mL:40-50mL.

[0012] More preferably, the nitro-containing piperazine includes, but is not limited to, at least one of 1-(5-nitropyridin-2-yl)piperazine, 1-(4-nitrophenyl)piperazine, 1-(2-nitrophenyl)piperazine, and 1-[(4-nitrophenyl)methyl]piperazine.

[0013] More preferably, in the preparation of the unsaturated amino product, the ratio of unsaturated nitro product, sodium dithionite, and ethyl acetate is 0.80-1.20g:0.60-0.80g:30-40mL.

[0014] More preferably, in the preparation of the DOPO grafted amino product, the ratio of DOPO, toluene, and mixture B is 0.80-1.20g:20-30mL:20-30mL; wherein, in the preparation of mixture B, the ratio of unsaturated amino product and toluene is 0.80-1.20g:8-12mL.

[0015] More preferably, in the preparation of the unsaturated DOPO grafted amino product, the dosage relationship of DOPO grafted amino product, potassium carbonate, dichloromethane, and mixed solution A2 is 0.80-1.20g:0.25-0.40g:40-50mL:40-50mL.

[0016] More preferably, in the preparation of the modified PP, the ratio of PP, toluene, unsaturated DOPO grafted amino product, and crosslinking agent is 20.00-30.00g: 80-120mL: 1.00-2.00g: 0.30-0.40g.

[0017] More preferably, the crosslinking agent is triallyl isocyanurate.

[0018] Crosslinking agents can promote the crosslinking and entanglement of modified PP and PP base materials during melt processing, thereby forming a dense three-dimensional crosslinked network, which can ensure the thermal stability of plastic flooring.

[0019] Preferably, the modified montmorillonite is obtained by intercalating montmorillonite with a quaternary ammonium salt intercalation modifier and then modifying it with a silane coupling agent. The specific preparation method is as follows: (1) Add montmorillonite to deionized water, stir and mix, adjust the pH to 8-12, stir and mix at 60-80℃ for 1-2 hours, add the quaternary ammonium salt intercalation modifier, continue stirring and mixing for 1-2 hours, filter, wash, and dry to obtain intercalated modified montmorillonite; (2) Add the intercalated modified montmorillonite and silane coupling agent to a 50-60wt% ethanol aqueous solution, stir and mix at 45-55℃ for 2-4 hours, filter, and dry to obtain modified montmorillonite.

[0020] More preferably, in the preparation of the intercalated modified montmorillonite, the dosage relationship of montmorillonite, deionized water, and quaternary ammonium salt intercalation modifier is 0.8-1.2g: 20-40mL: 0.2-0.3g.

[0021] More preferably, the quaternary ammonium salt intercalation modifier includes at least one of hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.

[0022] More preferably, in the preparation of the modified montmorillonite, the dosage relationship of the intercalated modified montmorillonite, the silane coupling agent, and the ethanol aqueous solution is 0.8-1.2g:0.15-0.25g:90-110mL.

[0023] More preferably, the silane coupling agent is obtained by compounding an aminosilane coupling agent and a vinylsilane coupling agent in a mass ratio of 0.3-0.6:1-2.

[0024] More preferably, the toughening agent is at least one selected from polyolefin elastomer (POE), acrylic elastomer (PBE), styrene-butadiene-styrene block copolymer (SBS), and hydrogenated styrene-butadiene block copolymer (SEBS).

[0025] More preferably, the compatibilizer is maleic anhydride-grafted polypropylene (MAH-g-PP).

[0026] The second aspect of the present invention provides a manufacturing process for the environmentally friendly plastic flooring described above, comprising the following steps: mixing PP, modified PP, modified montmorillonite, toughening agent, compatibilizer, antioxidant, and lubricant according to the formula ratio, adding them into a twin-screw extruder, melting and blending them, extruding them into a mold, extruding and molding them, and cooling them to obtain the environmentally friendly plastic flooring.

[0027] Preferably, the operating parameters of the twin-screw extruder are as follows: feeding section temperature 170-190℃, melting section temperature 190-210℃, homogenization section temperature 180-200℃, die head temperature 200-210℃; screw speed 100-200 r / min, and feeding speed 50-80 r / min.

[0028] More preferably, the parameters for the extrusion molding are: extrusion pressure of 3-10 MPa and extrusion time of 5-15 min.

[0029] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, modified PP containing piperazine nitrogen-containing groups and DOPO phosphorus-containing groups is used to modify PP base material. The modified PP and PP base material have good compatibility. At the same time, it can be further covalently cross-linked with other raw material components in subsequent melting, thereby constructing a permanent nitrogen-phosphorus synergistic halogen-free flame retardant system. This makes the prepared plastic flooring have both excellent structural density and excellent flame retardant properties.

[0030] 2. In this invention, montmorillonite is used as a filler, which can significantly enhance the wear resistance and flame retardant properties of PP base materials. To improve the dispersibility of montmorillonite in PP base materials, the method first uses a quaternary ammonium salt intercalation modifier to intercalate and modify montmorillonite. After intercalation modification, the interlayer spacing of montmorillonite is expanded, resulting in better dispersibility in subsequent melt blending. At the same time, the antistatic properties of montmorillonite are also enhanced after intercalation modification, which can effectively improve the defect of poor antistatic performance of polypropylene plastic flooring, reduce the adsorption of dust by plastic flooring, and enhance the cleanliness maintenance of plastic flooring to a certain extent. In order to further enhance the dispersibility of montmorillonite, the proposed method uses a combination of vinyl silane coupling agents and amino silane coupling agents to modify the intercalated montmorillonite. Vinyl and amino groups are further introduced into the montmorillonite. Vinyl groups can react with free radicals in melt blending to improve the structural density of the plastic flooring and thus improve its dimensional stability. Amino groups can form covalent interactions with the anhydrides of the compatibilizer to further enhance interfacial bonding and assist in enhancing structural density.

[0031] 3. Since the modified montmorillonite content in this invention is relatively high, in order to reduce the risk of brittle fracture of the plastic flooring, a toughening agent is also added to modify it. Through the action of the toughening agent, the plastic flooring has both rigidity and toughness, thereby ensuring the wear resistance and dimensional stability of the plastic flooring.

[0032] 4. In this invention, MAH-g-PP is added as a compatibilizer, which can effectively enhance the interfacial compatibility of modified PP, modified montmorillonite and PP base materials, and is the basic guarantee for the flame retardant performance, wear resistance and dimensional stability of plastic flooring.

[0033] In summary, this invention, through the synergistic effect of modified PP, modified montmorillonite, compatibilizer, and toughening agent, comprehensively prepares a plastic flooring with excellent flame retardancy, wear resistance, and dimensional stability. This plastic flooring utilizes a halogen-free nitrogen-phosphorus flame retardant system, has a dense and stable material structure that effectively prevents the migration and precipitation of small molecules, and contains no formaldehyde, heavy metals, or other harmful substances, exhibiting overall environmentally friendly and safe characteristics, thus possessing significant practical application value. Detailed Implementation

[0034] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. It should be understood that the embodiments described herein are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort should fall within the protection scope of the present invention; unless otherwise specified, the related raw materials are all conventional settings.

[0035] In the following examples, PP (model 1024T); acrylic acid; sulfoxide; toluene; dichloromethane; 1-(4-nitrophenyl)piperazine (CAS No. 6269-89-2); sodium dithionite (CAS No. 7775-14-6); ethyl acetate; DOPO (CAS No. 35948-25-5); potassium carbonate; triallyl isocyanurate (CAS No. 1025-15-6); montmorillonite (ion exchange capacity 145 meq / 100g, aspect ratio 200-400, average particle size 16-22μm); hexadecyltrimethylammonium bromide; POE (model Dow 8999); MAH-g-PP (model CMG9801); antioxidant 1010; calcium stearate; vinyltriethoxysilane; 3-aminopropyltriethoxysilane; all were commercially available; each part by weight was 100g. Preliminary preparations: Preparation of silane coupling agent: 3-aminopropyltriethoxysilane and vinyltriethoxysilane are mixed and compounded in a mass ratio of 0.5:1.5 to obtain silane coupling agent; The dimensions of the environmentally friendly plastic flooring are 45.72cm long × 45.72cm wide × 2.00mm thick.

[0036] Example 1: A manufacturing process for an environmentally friendly plastic flooring: S1: Preparation of modified PP: (1) Under nitrogen protection, acrylic acid was added to toluene, and thionyl chloride was added while stirring at 50°C. After reacting for 5 hours, the mixture was distilled under reduced pressure to obtain unsaturated acyl chloride product. The ratio of acrylic acid, thionyl chloride, and toluene was 1 g: 2 g: 35 mL. (2) The unsaturated acyl chloride product was added to dichloromethane and stirred to obtain mixture A. Mixture A was divided into equal amounts of mixture A1 and mixture A2. The ratio of unsaturated acyl chloride product to dichloromethane was 1 g: 10 mL. Under nitrogen protection, 1-(4-nitrophenyl)piperazine and potassium carbonate were added to dichloromethane and stirred to obtain mixture A. The mixture was heated to 30°C. At 5℃, add the mixture A1 dropwise at a rate of 2 mL / min while stirring. After the addition is complete, continue stirring and react for 10 h. Distill under reduced pressure to obtain the unsaturated nitro product. The ratio of 1-(4-nitrophenyl)piperazine, potassium carbonate, dichloromethane, and mixture A1 is 1 g: 0.32 g: 45 mL: 45 mL. (3) Under nitrogen protection, add the unsaturated nitro product and sodium dithionite to ethyl acetate. Stir and react at 45℃ for 2 h. Distill under reduced pressure to obtain the unsaturated amino product. The ratio of 1 g: 0.32 g: 45 mL: 45 mL is 1 g: 0.32 g: 45 mL: 45 mL. 7g:35mL; (4) Add the unsaturated amino product to toluene, stir and mix well to obtain mixture B, wherein the ratio of unsaturated amino product to toluene is 1g:10mL; Under nitrogen protection, add DOPO to toluene, stir and mix well, heat to 95℃, and then add mixture B dropwise at a rate of 2mL / min while stirring. After the addition is complete, continue stirring and reacting for 5h, and distill under reduced pressure to obtain DOPO grafted amino product, wherein the ratio of DOPO, toluene, and mixture B is 1g:25mL:25mL; (5) Under nitrogen protection, add DOPO grafted amino product to toluene. Add potassium carbonate to dichloromethane, stir and mix, heat to 35°C, and then add mixed solution A2 dropwise at a rate of 2 mL / min while stirring. After the addition is complete, continue stirring and reacting for 10 h. Distill under reduced pressure to obtain unsaturated DOPO grafted amino product. The ratio of the amounts of DOPO grafted amino product, potassium carbonate, dichloromethane, and mixed solution A2 is 1 g: 0.32 g: 45 mL: 45 mL. (6) Under nitrogen protection, add PP to toluene and stir to dissolve at 100°C. Then add unsaturated DOPO grafted amino product and triallyl isocyanurate, stir and mix, and then use... 60 Co-γ rays were used to irradiate the product at a dose of 40 kGy and a dose rate of 3 kGy / h. The product was then distilled under reduced pressure to obtain modified PP. The ratio of PP, toluene, unsaturated DOPO grafted amino product, and triallyl isocyanurate was 25 g: 100 mL: 1.5 g: 0.35 g. S2: Preparation of modified montmorillonite: (1) Add montmorillonite to deionized water, stir and mix, adjust pH to 10, stir and mix at 70℃ for 1.5h, then add hexadecyltrimethylammonium bromide, continue stirring and mixing for 1.5h, filter, wash, and dry to obtain intercalated modified montmorillonite, wherein the ratio of montmorillonite, deionized water, and hexadecyltrimethylammonium bromide is 1g:30mL:0.25g; (2) Add intercalated modified montmorillonite and silane coupling agent to 55wt% ethanol aqueous solution, stir and mix at 50℃ for 3h, filter, and dry to obtain modified montmorillonite, wherein the ratio of intercalated modified montmorillonite, silane coupling agent, and ethanol aqueous solution is 1g:0.2g:100mL; S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 40 parts modified PP, 30 parts modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a die, extrude to form the flooring, and cool to obtain environmentally friendly plastic flooring. The operating parameters of the twin-screw extruder are: feeding section temperature 180±1℃, melting section temperature 200±1℃, homogenization section temperature 190±1℃, and die head temperature 205±1℃; screw speed 150r / min, and feed speed 65r / min. The extrusion molding parameters are: extrusion pressure 6MPa and extrusion time 10min.

[0037] The following examples are based on Example 1, with Examples 2-3 and Comparative Examples 1-9, as detailed below: Example 2: Example 2 is based on Example 1, but with adjustments made to the amount of raw material components used in the environmentally friendly plastic flooring, while other processes remain unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 35 parts PP, 35 parts modified PP, 20 parts modified montmorillonite, 8 parts POE, 4 parts MAH-g-PP, 0.2 parts antioxidant 1010, and 1 part calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0038] Example 3: Example 3 is based on Example 1, but with adjustments made to the amount of raw material components used in the environmentally friendly plastic flooring, while other processes remain unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 45 parts PP, 45 parts modified PP, 35 parts modified montmorillonite, 12 parts POE, 6 parts MAH-g-PP, 1 part antioxidant 1010, and 3 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0039] Comparative Example 1: Comparative Example 1 is based on Example 1, with the following adjustment: the amount of modified PP was reduced, while other processes remained unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 10 parts modified PP, 30 parts modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0040] Comparative Example 2: Comparative Example 2 is based on Example 1, with the following adjustment: the amount of modified montmorillonite was reduced, while other processes remained unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 40 parts modified PP, 10 parts modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0041] Comparative Example 3: Comparative Example 3 is based on Example 1, with the following adjustments: the amount of modified PP and modified montmorillonite was reduced, while other processes remained unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 10 parts modified PP, 10 parts modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0042] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustments: no modified PP is added, all PP is used, and other processes remain unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 80 parts PP, 30 parts modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate, add them to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, cool, and obtain environmentally friendly plastic flooring.

[0043] Comparative Example 5: Comparative Example 5 is based on Example 1, with the following adjustment: montmorillonite was modified only by intercalation with hexadecyltrimethylammonium bromide, while other processes remained unchanged. Specifically: S2: Preparation of modified montmorillonite: Add montmorillonite to deionized water, stir and mix well, adjust the pH to 10, stir and mix at 70℃ for 1.5h, then add hexadecyltrimethylammonium bromide, continue stirring and mixing for 1.5h, filter, wash, and dry to obtain intercalated modified montmorillonite. The ratio of montmorillonite, deionized water, and hexadecyltrimethylammonium bromide is 1g:30mL:0.25g. S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 40 parts modified PP, 30 parts intercalated modified montmorillonite, 10 parts POE, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0044] Comparative Example 6: Comparative Example 6 is based on Example 1, with the following adjustments: the silane coupling agent used is only vinyltriethoxysilane, while other processes remain unchanged. Specifically: S2: Preparation of modified montmorillonite: (1) Add montmorillonite to deionized water, stir and mix, adjust pH to 10, stir and mix at 70℃ for 1.5h, then add hexadecyltrimethylammonium bromide, continue stirring and mixing for 1.5h, filter, wash, and dry to obtain intercalated modified montmorillonite, wherein the ratio of montmorillonite, deionized water, and hexadecyltrimethylammonium bromide is 1g:30mL:0.25g; (2) Add intercalated modified montmorillonite and vinyltriethoxysilane to 55wt% ethanol aqueous solution, stir and mix at 50℃ for 3h, filter, and dry to obtain modified montmorillonite, wherein the ratio of intercalated modified montmorillonite, vinyltriethoxysilane, and ethanol aqueous solution is 1g:0.2g:100mL.

[0045] Comparative Example 7: Comparative Example 7 is based on Example 1, with the following adjustment: POE is not added, while other processes remain unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 40 parts modified PP, 30 parts modified montmorillonite, 5 parts MAH-g-PP, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0046] Comparative Example 8: Comparative Example 8 is based on Example 1, with the following adjustment: MAH-g-PP is not added, while other processes remain unchanged. Specifically: S3: Manufacturing environmentally friendly plastic flooring: Mix 40 parts PP, 40 parts modified PP, 30 parts modified montmorillonite, 10 parts POE, 0.6 parts antioxidant 1010, and 2 parts calcium stearate. Add the mixture to a twin-screw extruder, melt-blend, extrude into a mold, extrude to form, and cool to obtain environmentally friendly plastic flooring.

[0047] Comparative Example 9: Plastic flooring was obtained using only PP processing, with the same processing parameters as in Example 1.

[0048] Performance testing: The environmentally friendly plastic flooring prepared in Examples 1-3 and Comparative Examples 1-9 were subjected to flame retardancy, abrasion resistance, and stability tests. The specific test methods are as follows: 1. Flame retardancy performance test: Flame retardancy performance is tested according to the UL-94 standard; 2. Abrasion resistance test: Abrasion resistance was tested using a Taber abrasion tester with ASTM D4060 as the reference standard, and the wear rate was calculated; the load was 500g, the grinding wheel was CS-17, and the number of wear cycles was 500. 3. Stability test: Place the environmentally friendly plastic flooring in a constant temperature oven for 24 hours, remove it, and remeasure its dimensions after it has cooled down. Calculate the rate of change of its length and width dimensions.

[0049] The specific test results for the above test items are shown in Table 1 below: Table 1 Results Analysis: As shown in Table 1 above, this invention comprehensively prepares a halogen-free, environmentally friendly, and flame-retardant polypropylene plastic flooring with excellent performance through the synergistic effect of modified polypropylene, modified montmorillonite, toughening agent, and compatibilizer. At the same time, this polypropylene plastic flooring also has excellent wear resistance and dimensional stability, which has important practical application significance.

[0050] For those skilled in the art, it is obvious that the present invention is not limited to the details disclosed in the exemplary embodiments described above. The present invention can be implemented in other specific ways without departing from its spirit and essential characteristics. Therefore, the foregoing embodiments should be considered exemplary rather than restrictive from any perspective. The scope of protection of the present invention is defined by the appended claims. Therefore, all variations falling within the meaning and scope of the equivalent elements of the claims should be attributed to the scope of the present invention.

Claims

1. An environmentally friendly plastic flooring, characterized in that: It includes the following raw material components: by weight, 35-45 parts PP, 35-45 parts modified PP, 20-35 parts modified montmorillonite, 8-12 parts toughening agent, 4-6 parts compatibilizer, 0.2-1 parts antioxidant, and 1-3 parts lubricant; The modified PP is prepared by acyl chloride reaction of unsaturated carboxylic acid to obtain unsaturated acyl chloride product; then the unsaturated acyl chloride product undergoes amidation reaction with piperazine containing nitro group; after reduction treatment, it first undergoes Michael addition reaction with DOPO, and then undergoes amidation reaction with unsaturated acyl chloride product; finally, it is prepared by irradiation-induced crosslinking grafting with PP and crosslinking agent. The modified montmorillonite is obtained by intercalating montmorillonite with a quaternary ammonium salt intercalation modifier and then modifying it with a silane coupling agent.

2. The environmentally friendly plastic flooring according to claim 1, characterized in that: The specific preparation method of the modified PP is as follows: (1) Under nitrogen protection, unsaturated carboxylic acid and thionyl chloride are added to toluene, stirred and reacted at 40-60℃, and distilled under reduced pressure to obtain unsaturated acyl chloride product; (2) The unsaturated acyl chloride product is added to dichloromethane to obtain mixture A, which is divided into equal amounts of mixture A1 and mixture A2; Under nitrogen protection, piperazine containing nitro group and potassium carbonate are added to dichloromethane, and mixture A1 is added dropwise at 30-38℃ while stirring. After the addition is completed, the reaction is stirred and distilled under reduced pressure to obtain unsaturated nitro product; (3) Under nitrogen protection, unsaturated nitro product and sodium dithionite are added to ethyl acetate, stirred and reacted at 40-50℃, and distilled under reduced pressure to obtain unsaturated amino product. (4) Add the unsaturated amino product to toluene to obtain mixture B; under nitrogen protection, add DOPO to toluene, and then add mixture B dropwise at 90-100℃ while stirring. After the addition is complete, continue stirring and react, and then distill under reduced pressure to obtain the DOPO grafted amino product; (5) Under nitrogen protection, add the DOPO grafted amino product and potassium carbonate to dichloromethane, and then add mixture A2 dropwise at 30-38℃ while stirring. After the addition is complete, continue stirring and react, and then distill under reduced pressure to obtain the unsaturated DOPO grafted amino product; (6) Under nitrogen protection, add PP to toluene, stir and dissolve at 95-105℃, and then add the unsaturated DOPO grafted amino product and crosslinking agent. 60 The modified PP was obtained by irradiation treatment with Coγ rays at a dose of 20-60 kGy and a dose rate of 2-4 kGy / h, followed by vacuum distillation.

3. The environmentally friendly plastic flooring according to claim 2, characterized in that: In the preparation of the unsaturated acyl chloride product, the ratio of unsaturated carboxylic acid, thionyl chloride, and toluene is 0.8-1.2g:1.8-2.2g:30-40mL. In the preparation of the mixture A, the ratio of unsaturated acyl chloride product to dichloromethane is 0.80-1.20 g: 8-12 mL. In the preparation of the unsaturated nitro product, the ratio of the amount of nitro-containing piperazine, potassium carbonate, dichloromethane, and mixed solution A1 is 0.80-1.20g:0.25-0.40g:40-50mL:40-50mL; In the preparation of the unsaturated amino product, the ratio of unsaturated nitro product, sodium dithionite, and ethyl acetate is 0.80-1.20g:0.60-0.80g:30-40mL. In the preparation of the DOPO-grafted amino product, the ratio of DOPO, toluene, and mixture B is 0.80-1.20g:20-30mL:20-30mL; wherein, in the preparation of mixture B, the ratio of unsaturated amino product and toluene is 0.80-1.20g:8-12mL. In the preparation of the unsaturated DOPO grafted amino product, the ratio of DOPO grafted amino product, potassium carbonate, dichloromethane, and mixed solution A2 is 0.80-1.20g:0.25-0.40g:40-50mL:40-50mL. In the preparation of the modified PP, the ratio of PP, toluene, unsaturated DOPO grafted amino product, and crosslinking agent is 20.00-30.00g: 80-120mL: 1.00-2.00g: 0.30-0.40g.

4. The environmentally friendly plastic flooring according to claim 2, characterized in that: The unsaturated carboxylic acid is a carboxylic acid containing a double bond, including at least one of acrylic acid, methacrylic acid, butenoic acid, 5-hexenoic acid, and 7-octenic acid; The nitro-containing piperazine includes at least one of 1-(5-nitropyridin-2-yl)piperazine, 1-(4-nitrophenyl)piperazine, 1-(2-nitrophenyl)piperazine, and 1-[(4-nitrophenyl)methyl]piperazine; The crosslinking agent is triallyl isocyanurate.

5. The environmentally friendly plastic flooring according to claim 1, characterized in that: The specific preparation method of the modified montmorillonite is as follows: (1) Add montmorillonite to deionized water, stir and mix, adjust the pH to 8-12, stir and mix at 60-80℃, add quaternary ammonium salt intercalation modifier, continue stirring and mixing, filter, wash, and dry to obtain intercalated modified montmorillonite; (2) Add intercalated modified montmorillonite and silane coupling agent to ethanol aqueous solution, stir and mix at 45-55℃, filter, and dry to obtain modified montmorillonite.

6. The environmentally friendly plastic flooring according to claim 5, characterized in that: In the preparation of the intercalated modified montmorillonite, the dosage relationship of montmorillonite, deionized water, and quaternary ammonium salt intercalation modifier is 0.8-1.2g: 20-40mL: 0.2-0.3g; In the preparation of the modified montmorillonite, the dosage relationship of the intercalated modified montmorillonite, silane coupling agent, and ethanol aqueous solution is 0.8-1.2g:0.15-0.25g:90-110mL.

7. The environmentally friendly plastic flooring according to claim 5, characterized in that: The quaternary ammonium salt intercalation modifier includes at least one of hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide; The silane coupling agent is obtained by compounding aminosilane coupling agent and vinylsilane coupling agent in a mass ratio of 0.3-0.6:1-2.

8. The environmentally friendly plastic flooring according to claim 1, characterized in that: The toughening agent is at least one of POE, PBE, SBS, and SEBS; The compatibilizer is MAH-g-PP.

9. The manufacturing process of an environmentally friendly plastic flooring according to any one of claims 1-8, characterized in that: Includes the following steps: According to the formula ratio, PP, modified PP, modified montmorillonite, toughening agent, compatibilizer, antioxidant, and lubricant are mixed and added into a twin-screw extruder. After melt blending, the mixture is extruded into a mold, extruded into shape, and cooled to obtain environmentally friendly plastic flooring.

10. The manufacturing process of an environmentally friendly plastic flooring according to claim 9, characterized in that: The operating parameters of the twin-screw extruder are as follows: feeding section temperature 170-190℃, melting section temperature 190-210℃, homogenization section temperature 180-200℃, die head temperature 200-210℃; screw speed 100-200 r / min, feeding speed 50-80 r / min. The parameters for the extrusion molding are: extrusion pressure of 3-10 MPa and extrusion time of 5-15 min.

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