Anti-aging high-tensile PVC (polyvinyl chloride) film and processing technology thereof

Abstract

The invention relates to the technical field of PVC (polyvinyl chloride) films, in particular to an anti-aging high-tensile PVC film and a processing technology thereof. The preparation method comprises the following steps: mixing aminated hexagonal boron nitride, aminated halloysite nanotubes and carbon nanotubes, and carrying out a reflux reaction to obtain a mixed material; and adding tetraethyl silicate and 1H, 1H, 2H, 2H-perfluorodecyl trimethoxy silane to modify the mixed material, so as to obtain the composite filler. And mixing the polyvinyl chloride resin, the composite filler, the plasticizer, the flexibilizer, the stabilizer, the antioxidant and the pigment, and carrying out plasticizing extrusion and calendaring molding to obtain an anti-aging high-tensile PVC film finished product. The finished product prepared by the invention has good mechanical properties and corrosion resistance, so that the finished product has a wide application prospect in the technical field of PVC films.

Description

Technical Field

[0001] This invention relates to the field of PVC film technology, specifically to an aging-resistant, high-tensile-strength PVC film and its processing technology. Background Technology

[0002] In modern industry and daily life, PVC film possesses irreplaceable value due to its unique properties and wide range of applications. In the packaging industry, PVC film is widely used due to its excellent flexibility, transparency, and printability. Using PVC film in food packaging not only effectively blocks oxygen, moisture, and bacteria, extending the shelf life of food, but also attracts consumers' attention through attractive printing, enhancing the market competitiveness of products. Meanwhile, in the packaging of daily necessities and electronic products, PVC film has become the preferred material for businesses due to its reliable protective performance and aesthetically pleasing packaging effects. Furthermore, PVC film performs exceptionally well in the construction industry. It can be used as a waterproof, moisture-proof, and decorative material. In areas such as roofs and basements, PVC film effectively prevents rainwater penetration, protecting the structural safety of buildings.

[0003] However, when using PVC film to package heavier items, if the film's tensile strength is insufficient, it may be unable to withstand the weight of the items and the tensile forces during handling, easily leading to packaging breakage and product damage. Furthermore, some food and cosmetic products may contain corrosive ingredients such as acids and organic solvents. If the PVC film has poor corrosion resistance, it will be corroded by these substances, causing a decline in the film's physical properties and even affecting the quality and safety of the packaged goods.

[0004] To overcome the shortcomings of the prior art, the present invention provides an aging-resistant, high-tensile-strength PVC film and its processing technology. Summary of the Invention

[0005] The purpose of this invention is to provide an aging-resistant, high-tensile-strength PVC film and its processing technology to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A processing technology for an aging-resistant, high-tensile-strength PVC film includes the following steps: mixing polyvinyl chloride resin, composite filler, plasticizer, toughening agent, stabilizer, antioxidant, and pigment, followed by plasticizing extrusion and calendering to obtain the finished product.

[0007] In a more optimized manner, the content of each component in the finished product is as follows: by mass parts, 90-100 parts polyvinyl chloride resin, 20-25 parts composite filler, 30-40 parts plasticizer, 5-8 parts toughening agent, 2-5 parts stabilizer, 1-2 parts antioxidant, and 10-15 parts pigment.

[0008] More preferably, the plasticizer is phthalate; the toughening agent is polyamide; the stabilizer is methyl mercaptan heat stabilizer; and the antioxidant is specifically antioxidant 1010.

[0009] A more optimized preparation process for composite fillers is as follows: Step S1: Mix aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically disperse for 1.5-2.0 h, then add carbon nanotubes and continue ultrasonic dispersion for 2-3 h. After dispersion, stir and reflux at 60-65℃ for 20-25 h. After the reaction, filter, wash and dry to obtain the mixture. Step S2: Add the mixture to anhydrous ethanol, then add ammonia water to adjust the pH to 9-11, and ultrasonically disperse at 25-30℃ for 15-20 min. Then add tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane dropwise, and react at 70-75℃ for 12-15 h. After the reaction is completed, centrifuge, wash and dry to obtain the composite filler.

[0010] In a more optimized manner, in step S1, the mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes, and carbon nanotubes is (1.5-1.8):(0.7-0.9):(3-4).

[0011] In a more optimized manner, in step S2, the mass-to-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane is 0.5 g : (60-65) mL : (1.2-1.3) mL : 1 mL.

[0012] A more optimized preparation process for aminated hexagonal boron nitride is as follows: Step S1: Mix hexagonal boron nitride and sodium perborate and ball mill. After ball milling, wash with 1.0-1.2 mol / L hydrochloric acid, wash with deionized water, and vacuum filter to obtain crude product. Then add the crude product to a solvent, disperse by ultrasonication, centrifuge, vacuum filter, and dry to obtain pretreated hexagonal boron nitride. Step S2: Mix deionized water and anhydrous ethanol, then add γ-aminopropyltriethoxysilane and hydrochloric acid in sequence. After stirring evenly, stir at 60-65℃ for 3.0-3.5h. Then add pretreated hexagonal boron nitride and continue stirring for 3.0-4.0h. After stirring, filter, wash and dry to obtain amino-modified hexagonal boron nitride.

[0013] In a more optimized manner, the mass ratio of hexagonal boron nitride to sodium perborate is (8-10):1; the solvent includes deionized water and anhydrous ethanol, with a volume ratio of 1:(1.0-1.5); the volume ratio of deionized water, anhydrous ethanol, and γ-aminopropyltriethoxysilane is 1:(8-10):1; and the mass-volume ratio of γ-aminopropyltriethoxysilane to pretreated hexagonal boron nitride is (0.8-1.0) mL:1 g.

[0014] The optimized preparation process of aminated halloysite nanotubes is as follows: Step S1: Mix halloysite nanotubes with 5-6 mol / L sodium hydroxide solution, stir evenly, and then ultrasonically disperse at 50-55℃ for 1-2 h. After centrifugation, washing, and drying, pretreated halloysite nanotubes are obtained. Add 2-mercaptobenzothiazole to ethanol and stir evenly to obtain a 2-mercaptobenzothiazole solution. Mix the pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution, stir for 15-20 h, and then vacuum extract for 1.0-1.5 h. After standing for 0.8-1.0 h, vacuum extract and stand for 2 times to obtain supported halloysite nanotubes. Step S2: Add supported halloysite nanotubes to deionized water, then add anhydrous sodium carbonate to adjust the pH to 10.0-10.5, stir at 80-85℃ for 1.0-1.5h, add acetic acid to adjust the pH to 7.8-8.0, then add γ-aminopropyltriethoxysilane, stir at 80-85℃ for 5-6h, wash and dry after reaction to obtain aminated halloysite nanotubes.

[0015] In a more optimized manner, the mass-to-volume ratio of halloysite nanotubes to sodium hydroxide solution is 2 g: (90-100) mL; the concentration of 2-mercaptobenzothiazole solution is 0.06-0.07 g / mL; the mass-to-volume ratio of pretreated halloysite nanotubes to 2-mercaptobenzothiazole solution is 1 g: (30-35) mL; and the volume-to-mass ratio of γ-aminopropyltriethoxysilane to supported halloysite nanotubes is (1.0-1.2) mL: 1 g.

[0016] The beneficial effects of this invention are: The key feature of this invention is that hexagonal boron nitride and sodium perborate are mixed and ball-milled, then treated with hydrochloric acid and other processes to obtain pretreated hexagonal boron nitride. This pretreated hexagonal boron nitride has a large number of active hydroxyl groups on its surface, so γ-aminopropyltriethoxysilane is added to modify the pretreated hexagonal boron nitride to obtain aminated hexagonal boron nitride. Then, the pretreated halloysite nanotubes are mixed with a 2-mercaptobenzothiazole solution, vacuum-extracted, and allowed to stand to obtain supported halloysite nanotubes. γ-aminopropyltriethoxysilane is then used to modify the supported halloysite nanotubes to obtain aminated halloysite nanotubes.

[0017] Hexagonal boron nitride (HNTs) possesses a graphite-like layered structure, with atoms within each layer linked by strong covalent bonds, resulting in high intrinsic strength and modulus. Halloysite nanotubes (HNTs) exhibit a natural nanotube structure, with walls composed of aluminum-oxygen octahedra and silicon-oxygen tetrahedra, inherently possessing a certain strength. However, HNTs have a relatively inert surface and poor compatibility with the matrix material. Alkaline treatment generates more active groups such as hydroxyl groups on their surface, while simultaneously removing surface impurities and improving the dispersibility of the nanotubes. Furthermore, loading 2-mercaptobenzothiazole into the pretreated halloysite nanotubes can enhance the material's corrosion resistance.

[0018] The present invention is characterized by mixing aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically dispersing the mixture, adding carbon nanotubes, continuing ultrasonic dispersion, and then refluxing the reaction to obtain a mixture. Tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane are then added to modify the mixture, resulting in a composite filler.

[0019] This step first involves ultrasonically mixing aminated hexagonal boron nitride and aminated halloysite nanotubes. Hydrogen bonds form between the amino groups on their surfaces, promoting their interaction and uniform dispersion. This uniform dispersion allows stress to be more evenly distributed throughout the system under load, preventing stress concentration and premature material failure. Then, carbon nanotubes are added to undergo an amidation reaction, forming stronger chemical bonds between the three materials. These bonds enhance the interfacial bonding strength between the different components, allowing for more effective stress transfer at the interface when the material is subjected to external forces, thereby improving the material's tensile strength. Furthermore, this invention sets the mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes, and carbon nanotubes to (1.5-1.8):(0.7-0.9):(3-4). At this ratio, the two-dimensional sheet structure of hexagonal boron nitride can effectively interweave with the one-dimensional tubular structures of halloysite and carbon nanotubes, forming a three-dimensional network structure. This structure increases the specific surface area and interfacial area of ​​the material, enabling more effective stress transfer between materials of different dimensions. These components work synergistically to resist external forces, improving the overall performance of the material. Furthermore, the hydrolysis of tetraethyl silicate forms a silica network structure that covers the surface of the composite filler. Silica possesses excellent chemical stability and density, effectively preventing contact with corrosive media. The fluorine atoms in 1H,1H,2H,2H-perfluorodecyltrimethoxysilane have extremely low surface energy and strong electronegativity, forming a fluoride layer on the surface of the composite filler. This fluoride layer not only exhibits good hydrophobicity but also prevents the adhesion of moisture and corrosive liquids, and resists the erosion of various chemicals, further enhancing the corrosion resistance of the composite filler.

[0020] The present invention is characterized by mixing polyvinyl chloride resin, composite filler, plasticizer, toughening agent, stabilizer, antioxidant, and pigment, followed by plasticizing extrusion and calendering to obtain a finished PVC film. The raw materials in this finished product work synergistically to provide protection. The stabilizer and antioxidant protect the PVC matrix, while the composite filler provides a physical barrier; together, they form a multi-layered protective system, effectively improving the overall performance of the PVC film. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Raw material source: Hexagonal boron nitride, supplied by Shijiazhuang Dongming New Material Technology Co., Ltd., grade D50; halloysite nanotubes, supplied by Lingshou Judian Mining Co., Ltd., specification 300 mesh; polyvinyl chloride resin, supplied by Jinan Huiteng Chemical Co., Ltd., model 14441; pigment, supplied by Shenyang Jintianyuan Chemical Co., Ltd., effective ingredient content 99%; polyamide, supplied by Dongguan Changping Chuangshi New Material, grade 80G33L; methyl mercaptan tin heat stabilizer, supplied by Shandong Suihua Biotechnology Co., Ltd., effective ingredient content 19%; carbon nanotubes, specifically carboxylated carbon nanotubes, supplied by Angxing New Carbon Materials Changzhou Co., Ltd., carboxyl content 0.25-1.28wt%; by mass, one part is 1g.

[0023] Example 1: Step S1: Hexagonal boron nitride and sodium perborate were mixed and ball-milled. After ball milling, the mixture was washed with 1.1 mol / L hydrochloric acid, washed with deionized water, and vacuum filtered to obtain a crude product. The crude product was then added to a solvent, ultrasonically dispersed, centrifuged, vacuum filtered, and dried to obtain pretreated hexagonal boron nitride. The mass ratio of hexagonal boron nitride to sodium perborate was 9:1. The solvent included deionized water and anhydrous ethanol, with a volume ratio of 1:1.3. Step S2: Deionized water and anhydrous ethanol were mixed, and then γ-aminopropyltriethoxysilane and hydrochloric acid were added sequentially. After stirring evenly, the mixture was stirred at 65°C for 3.5 h. Then, pretreated hexagonal boron nitride was added, and stirring was continued for 4.0 h. After stirring, the mixture was filtered, washed, and dried to obtain amino-modified hexagonal boron nitride. The volume ratio of deionized water, anhydrous ethanol, and γ-aminopropyltriethoxysilane was 1:9:1; the mass-volume ratio of γ-aminopropyltriethoxysilane and pretreated hexagonal boron nitride was 0.9 mL:1 g. Step S3: Halloysite nanotubes were mixed with 5.5 mol / L sodium hydroxide solution, stirred evenly, and ultrasonically dispersed at 55℃ for 2 h. After centrifugation, washing, and drying, pretreated halloysite nanotubes were obtained. 2-Mercaptobenzothiazole was added to ethanol and stirred evenly to obtain a 2-mercaptobenzothiazole solution. The pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution were then mixed and stirred for 20 h. After vacuum extraction for 1.5 h, the mixture was allowed to stand for 1.0 h, and then vacuum extraction and standing were repeated twice to obtain supported halloysite nanotubes. The mass-to-volume ratio of halloysite nanotubes to sodium hydroxide solution was 2 g:95 mL; the concentration of the 2-mercaptobenzothiazole solution was 0.065 g / mL; and the mass-to-volume ratio of pretreated halloysite nanotubes to the 2-mercaptobenzothiazole solution was 1 g:32 mL. Step S4: Add the supported halloysite nanotubes to deionized water, then add anhydrous sodium carbonate to adjust the pH to 10.5, stir at 85℃ for 1.5 h, add acetic acid to adjust the pH to 8.0, then add γ-aminopropyltriethoxysilane, stir at 85℃ for 6 h, and after the reaction is complete, wash and dry to obtain aminated halloysite nanotubes; the volume-to-mass ratio of γ-aminopropyltriethoxysilane to supported halloysite nanotubes is 1.1 mL: 1 g; Step S5: Mix aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically disperse for 2.0 h, then add carbon nanotubes and continue ultrasonic dispersion for 3 h. After dispersion, stir and reflux at 65℃ for 25 h. After the reaction, filter, wash and dry to obtain the mixture. The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes and carbon nanotubes is 1.6:0.8:3.5. Step S6: Add the mixture to anhydrous ethanol, then add ammonia water to adjust the pH to 11, and ultrasonically disperse at 30℃ for 20 min. Then add tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane dropwise, and react at 75℃ for 15 h. After the reaction is completed, centrifuge, wash, and dry to obtain the composite filler. The mass-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane is 0.5 g: 63 mL: 1.25 mL: 1 mL. Step S7: Mix 90g of polyvinyl chloride resin, 20g of composite filler, 30g of phthalate, 5g of polyamide, 2g of methyl mercaptan heat stabilizer, 1g of antioxidant 1010, and 10g of pigment, and then plasticize, extrude, and calender to obtain the finished product.

[0024] Example 2: Step S1: Hexagonal boron nitride and sodium perborate were mixed and ball-milled. After ball milling, the mixture was washed with 1.1 mol / L hydrochloric acid, washed with deionized water, and vacuum filtered to obtain a crude product. The crude product was then added to a solvent, ultrasonically dispersed, centrifuged, vacuum filtered, and dried to obtain pretreated hexagonal boron nitride. The mass ratio of hexagonal boron nitride to sodium perborate was 9:1. The solvent included deionized water and anhydrous ethanol, with a volume ratio of 1:1.3. Step S2: Deionized water and anhydrous ethanol were mixed, and then γ-aminopropyltriethoxysilane and hydrochloric acid were added sequentially. After stirring evenly, the mixture was stirred at 62°C for 3.2 h. Then, pretreated hexagonal boron nitride was added, and stirring was continued for 3.5 h. After stirring, the mixture was filtered, washed, and dried to obtain amino-modified hexagonal boron nitride. The volume ratio of deionized water, anhydrous ethanol, and γ-aminopropyltriethoxysilane was 1:9:1; the mass-volume ratio of γ-aminopropyltriethoxysilane and pretreated hexagonal boron nitride was 0.9 mL:1 g. Step S3: Halloysite nanotubes were mixed with 5.5 mol / L sodium hydroxide solution, stirred until homogeneous, and then ultrasonically dispersed at 53℃ for 1.5 h. After centrifugation, washing, and drying, pretreated halloysite nanotubes were obtained. 2-Mercaptobenzothiazole was added to ethanol and stirred until homogeneous to obtain a 2-mercaptobenzothiazole solution. The pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution were then mixed and stirred for 17 h. After vacuum extraction for 1.3 h, the mixture was allowed to stand for 0.9 h, and then vacuum extraction and standing were repeated twice to obtain supported halloysite nanotubes. The mass-to-volume ratio of halloysite nanotubes to sodium hydroxide solution was 2 g:95 mL; the concentration of the 2-mercaptobenzothiazole solution was 0.065 g / mL; and the mass-to-volume ratio of pretreated halloysite nanotubes to the 2-mercaptobenzothiazole solution was 1 g:32 mL. Step S4: Add the supported halloysite nanotubes to deionized water, then add anhydrous sodium carbonate to adjust the pH to 10.3, stir at 82℃ for 1.3 h, add acetic acid to adjust the pH to 7.9, then add γ-aminopropyltriethoxysilane, stir at 83℃ for 5.5 h, and after the reaction is complete, wash and dry to obtain aminated halloysite nanotubes; the volume-to-mass ratio of γ-aminopropyltriethoxysilane to supported halloysite nanotubes is 1.1 mL: 1 g; Step S5: Mix aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically disperse for 1.7 h, then add carbon nanotubes and continue ultrasonic dispersion for 2.5 h. After dispersion, stir and reflux at 62 °C for 23 h. After the reaction, filter, wash and dry to obtain the mixture. The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes and carbon nanotubes is 1.6:0.8:3.5. Step S6: Add the mixture to anhydrous ethanol, then add ammonia to adjust the pH to 10, and ultrasonically disperse at 27℃ for 17 min. Then add tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane dropwise, and react at 73℃ for 14 h. After the reaction is complete, centrifuge, wash, and dry to obtain the composite filler. The mass-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane is 0.5 g: 63 mL: 1.25 mL: 1 mL. Step S7: Mix 90g of polyvinyl chloride resin, 20g of composite filler, 30g of phthalate, 5g of polyamide, 2g of methyl mercaptan heat stabilizer, 1g of antioxidant 1010, and 10g of pigment, and then plasticize, extrude, and calender to obtain the finished product.

[0025] Example 3: Step S1: Hexagonal boron nitride and sodium perborate were mixed and ball-milled. After ball milling, the mixture was washed with 1.1 mol / L hydrochloric acid, washed with deionized water, and vacuum filtered to obtain a crude product. The crude product was then added to a solvent, ultrasonically dispersed, centrifuged, vacuum filtered, and dried to obtain pretreated hexagonal boron nitride. The mass ratio of hexagonal boron nitride to sodium perborate was 9:1. The solvent included deionized water and anhydrous ethanol, with a volume ratio of 1:1.3. Step S2: Deionized water and anhydrous ethanol were mixed, and then γ-aminopropyltriethoxysilane and hydrochloric acid were added sequentially. After stirring evenly, the mixture was stirred at 6°C for 3 hours. Then, pretreated hexagonal boron nitride was added, and stirring was continued for 3 hours. After stirring, the mixture was filtered, washed, and dried to obtain amino-modified hexagonal boron nitride. The volume ratio of deionized water, anhydrous ethanol, and γ-aminopropyltriethoxysilane was 1:9:1; the mass-volume ratio of γ-aminopropyltriethoxysilane and pretreated hexagonal boron nitride was 0.9 mL:1 g. Step S3: Halloysite nanotubes were mixed with 5.5 mol / L sodium hydroxide solution, stirred until homogeneous, and then ultrasonically dispersed at 50°C for 1 h. After centrifugation, washing, and drying, pretreated halloysite nanotubes were obtained. 2-Mercaptobenzothiazole was added to ethanol and stirred until homogeneous to obtain a 2-mercaptobenzothiazole solution. The pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution were then mixed and stirred for 15 h. After vacuum extraction for 1 h, the mixture was allowed to stand for 0.8 h, and then vacuum extraction and standing were repeated twice to obtain supported halloysite nanotubes. The mass-to-volume ratio of halloysite nanotubes to sodium hydroxide solution was 2 g:95 mL; the concentration of the 2-mercaptobenzothiazole solution was 0.065 g / mL; and the mass-to-volume ratio of pretreated halloysite nanotubes to the 2-mercaptobenzothiazole solution was 1 g:32 mL. Step S4: Add the supported halloysite nanotubes to deionized water, then add anhydrous sodium carbonate to adjust the pH to 10, stir at 80℃ for 1 h, add acetic acid to adjust the pH to 7.8, then add γ-aminopropyltriethoxysilane, stir at 80℃ for 5 h, and after the reaction is complete, wash and dry to obtain aminated halloysite nanotubes; the volume-to-mass ratio of γ-aminopropyltriethoxysilane to supported halloysite nanotubes is 1.1 mL: 1 g; Step S5: Mix aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically disperse for 1.5 h, then add carbon nanotubes and continue ultrasonic dispersion for 2 h. After dispersion, stir and reflux at 60 °C for 20 h. After the reaction, filter, wash and dry to obtain the mixture. The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes and carbon nanotubes is 1.6:0.8:3.5. Step S6: Add the mixture to anhydrous ethanol, then add ammonia to adjust the pH to 9, and ultrasonically disperse at 25℃ for 15 min. Then add tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane dropwise, and react at 70℃ for 12 h. After the reaction is complete, centrifuge, wash, and dry to obtain the composite filler. The mass-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane is 0.5 g: 63 mL: 1.25 mL: 1 mL. Step S7: Mix 90g of polyvinyl chloride resin, 20g of composite filler, 30g of phthalate, 5g of polyamide, 2g of methyl mercaptan heat stabilizer, 1g of antioxidant 1010, and 10g of pigment, and then plasticize, extrude, and calender to obtain the finished product.

[0026] Comparative Example 1: The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes, and carbon nanotubes was adjusted to 1:0.5:5, and the rest was the same as in Example 1. The specific steps are as follows: Step S1: Hexagonal boron nitride and sodium perborate were mixed and ball-milled. After ball milling, the mixture was washed with 1.1 mol / L hydrochloric acid, washed with deionized water, and vacuum filtered to obtain a crude product. The crude product was then added to a solvent, ultrasonically dispersed, centrifuged, vacuum filtered, and dried to obtain pretreated hexagonal boron nitride. The mixing mass ratio of hexagonal boron nitride and sodium perborate was 9:1. The solvent included deionized water and anhydrous ethanol, with a volume ratio of 1:1.3. Step S2: Deionized water and anhydrous ethanol were mixed, and then γ-aminopropyltriethoxysilane and hydrochloric acid were added sequentially. After stirring evenly, the mixture was stirred at 65°C for 3.5 h. Then, pretreated hexagonal boron nitride was added, and stirring was continued for 4.0 h. After stirring, the mixture was filtered, washed, and dried to obtain amino-modified hexagonal boron nitride. The volume ratio of deionized water, anhydrous ethanol, and γ-aminopropyltriethoxysilane was 1:9:1; the mass-volume ratio of γ-aminopropyltriethoxysilane and pretreated hexagonal boron nitride was 0.9 mL:1 g. Step S3: Halloysite nanotubes were mixed with 5.5 mol / L sodium hydroxide solution, stirred evenly, and ultrasonically dispersed at 55℃ for 2 h. After centrifugation, washing, and drying, pretreated halloysite nanotubes were obtained. 2-Mercaptobenzothiazole was added to ethanol and stirred evenly to obtain a 2-mercaptobenzothiazole solution. The pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution were then mixed and stirred for 20 h. After vacuum extraction for 1.5 h, the mixture was allowed to stand for 1.0 h, and then vacuum extraction and standing were repeated twice to obtain supported halloysite nanotubes. The mass-to-volume ratio of halloysite nanotubes to sodium hydroxide solution was 2 g:95 mL; the concentration of the 2-mercaptobenzothiazole solution was 0.065 g / mL; and the mass-to-volume ratio of pretreated halloysite nanotubes to the 2-mercaptobenzothiazole solution was 1 g:32 mL. Step S4: Add the supported halloysite nanotubes to deionized water, then add anhydrous sodium carbonate to adjust the pH to 10.5, stir at 85℃ for 1.5 h, add acetic acid to adjust the pH to 8.0, then add γ-aminopropyltriethoxysilane, stir at 85℃ for 6 h, and after the reaction is complete, wash and dry to obtain aminated halloysite nanotubes; the volume-to-mass ratio of γ-aminopropyltriethoxysilane to supported halloysite nanotubes is 1.1 mL: 1 g; Step S5: Mix aminated hexagonal boron nitride and aminated halloysite nanotubes, ultrasonically disperse for 2.0 h, then add carbon nanotubes and continue ultrasonic dispersion for 3 h. After dispersion, stir and reflux at 65℃ for 25 h. After the reaction, filter, wash and dry to obtain the mixture. The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes and carbon nanotubes is 1:0.5:5. Step S6: Add the mixture to anhydrous ethanol, then add ammonia water to adjust the pH to 11, and ultrasonically disperse at 30℃ for 20 min. Then add tetraethyl silicate and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane dropwise, and react at 75℃ for 15 h. After the reaction is completed, centrifuge, wash, and dry to obtain the composite filler. The mass-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane is 0.5 g: 63 mL: 1.25 mL: 1 mL. Step S7: Mix 90g of polyvinyl chloride resin, 20g of composite filler, 30g of phthalate, 5g of polyamide, 2g of methyl mercaptan heat stabilizer, 1g of antioxidant 1010, and 10g of pigment, and then plasticize, extrude, and calender to obtain the finished product.

[0027] Comparative Example 2: The composite filler was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step S1: 90g of polyvinyl chloride resin, 30g of phthalate, 5g of polyamide, 2g of methyl mercaptan heat stabilizer, 1g of antioxidant 1010 and 10g of pigment were mixed, and then plasticized, extruded and calendered to obtain the finished product.

[0028] Mechanical property testing: Referring to GB / T 1040.3-2006 "Determination of tensile properties of plastics", the finished film prepared by this invention was used as a sample. The sample size was a dumbbell-shaped strip of 115×6×0.1mm. The tensile rate was 500mm / min, and the tensile strength was recorded.

[0029] Alkali corrosion resistance test: Referring to GB / T 11547-2008 "Determination of resistance to liquid chemical reagents of plastics", the finished film prepared by this invention was used as a sample and placed in an oven. After the weight stabilized, the sample was weighed and recorded as M1. The sample was then placed in a 40wt% NaOH solution and left to stand at 80℃ for 30 days. After removal, the sample was cleaned, dried, and weighed again, recorded as M2. The weight loss rate was then calculated using the formula: (M1-M2) / M1 × 100%. The results are shown in the table below:

[0030] Conclusion: In Examples 1-3, the dosage remained unchanged, with only some reaction parameters modified. Experimental data show that the various properties of the samples did not exhibit significant fluctuations.

[0031] Comparative Example 1: The mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes, and carbon nanotubes was adjusted to 1:0.5:5, while the rest remained the same as in Example 1. Experimental data showed that compared to Example 1, the tensile strength decreased to 22.6 MPa, and the weight loss rate increased to 4.66%. The reason for this is that the mixing ratio of aminated hexagonal boron nitride, aminated halloysite nanotubes, and carbon nanotubes was set to (1.5-1.8):(0.7-0.9):(3-4). Under this ratio, the two-dimensional sheet structure of hexagonal boron nitride and the one-dimensional tubular structure of halloysite nanotubes and carbon nanotubes can effectively interweave and synergize to form a network structure. This structure effectively improves the overall performance of the material. Therefore, after adjusting the ratio, the tensile strength decreased and the weight loss rate increased.

[0032] Comparative Example 2: The composite filler was removed, and the rest was the same as in Example 1. The experimental data showed that compared with Example 1, the tensile strength decreased to 19.0 MPa, and the weight loss rate increased to 8.73%. The reason for this is that the composite filler contains reinforcing materials and a stable cross-linked structure, thus possessing excellent mechanical properties. Therefore, removing the composite filler reduced the tensile strength. In addition, the composite filler contains the corrosion inhibitor 2-mercaptobenzothiazole, as well as silica and fluorine structures, thus possessing excellent corrosion resistance. Therefore, removing the composite filler increased the weight loss rate.

[0033] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.

[0034] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for the manufacture of an age resistant high tensile PVC film, characterized in that: Comprise the following steps: The polyvinyl chloride resin, composite filler, plasticizer, toughening agent, stabilizer, antioxidant, pigment are mixed, and the plasticizing extrusion, calendering molding are carried out to obtain the finished product.

2. The process for processing of an age resistant high tensile PVC film as claimed in claim 1, wherein: The content of each component of the finished product is: 90-100 parts of polyvinyl chloride resin, 20-25 parts of composite filler, 30-40 parts of plasticizer, 5-8 parts of toughening agent, 2-5 parts of stabilizer, 1-2 parts of antioxidant, 10-15 parts of pigment.

3. The process for processing of an age resistant high tensile PVC film as claimed in claim 1, wherein: The preparation process of the composite filler is: Step S1: The amino hexagonal boron nitride and amino halloysite nanotube are mixed, ultrasonic dispersion is carried out for 1.5-2.0h, then carbon nanotube is added, ultrasonic dispersion is continued for 2-3h, after dispersion, reflux reaction is carried out at 60-65℃ for 20-25h, after reaction, the mixture is obtained by filtration, washing and drying; Step S2: The mixture is added to anhydrous ethanol, then ammonia water is added, the pH is adjusted to 9-11, ultrasonic dispersion is carried out at 25-30℃ for 15-20min, then tetraethyl silicate and 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane are added dropwise, reaction is carried out at 70-75℃ for 12-15h, after reaction, the composite filler is obtained by centrifugation, washing and drying.

4. The process for processing the age resistant high tensile PVC film as claimed in claim 3, wherein: In step S1, the mixing ratio of amino hexagonal boron nitride, amino halloysite nanotube and carbon nanotube is (1.5-1.8):(0.7-0.9):(3-4).

5. The process for processing the age resistant high tensile PVC film as claimed in claim 3, wherein the said process is characterized by: In step S2, the mass-volume ratio of the mixture, anhydrous ethanol, tetraethyl silicate and 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane is 0.5g:(60-65)mL:(1.2-1.3)mL:1mL.

6. The process for processing of an age resistant high tensile PVC film as claimed in claim 4, wherein the said process is characterized by: The preparation process of the amino hexagonal boron nitride is: Step S1: Hexagonal boron nitride and sodium perborate are mixed and ball milled, after ball milling, the crude product is obtained by washing with 1.0-1.2mol / L hydrochloric acid, deionized water, vacuum filtration; then the crude product is added to a solvent, ultrasonic dispersion, centrifugation, vacuum filtration and drying are carried out to obtain pretreated hexagonal boron nitride; Step S2: Deionized water and anhydrous ethanol are mixed, then γ-aminopropyl triethoxysilane and hydrochloric acid are added in sequence, after stirring uniformly, stirring reaction is carried out at 60-65℃ for 3.0-3.5h, then pretreated hexagonal boron nitride is added, stirring is continued for 3.0-4.0h, after stirring, the amino hexagonal boron nitride is obtained by filtration, washing and drying.

7. The process for processing of an age resistant high tensile PVC film as claimed in claim 6, wherein the said process is characterized by: The mixing mass ratio of hexagonal boron nitride and sodium perborate is (8-10):1; the solvent includes deionized water and anhydrous ethanol, and the volume ratio of the two is 1:(1.0-1.5); the volume ratio of deionized water, anhydrous ethanol and γ-aminopropyl triethoxysilane is 1:(8-10):1; the mass-volume ratio of γ-aminopropyl triethoxysilane and pretreated hexagonal boron nitride is (0.8-1.0)mL:1g.

8. The process for processing of an age resistant high tensile PVC film as claimed in claim 4, wherein: The preparation process of the amino halloysite nanotube is: Step S1: Halloysite nanotube and 5-6mol / L sodium hydroxide solution are mixed, after stirring uniformly, ultrasonic dispersion is carried out at 50-55℃ for 1-2h, then centrifugation, washing and drying are carried out to obtain pretreated halloysite nanotube; adding 2-mercaptobenzothiazole into ethanol, stirring to obtain a 2-mercaptobenzothiazole solution; adding the pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution, stirring for 15-20 h, vacuum extraction for 1.0-1.5 h, standing for 0.8-1.0 h, vacuum extraction and standing for 2 times to obtain the supported halloysite nanotubes; step S2: adding the supported halloysite nanotubes into deionized water, adding anhydrous sodium carbonate, adjusting the pH to 10.0-10.5, stirring at 80-85℃ for 1.0-1.5 h, adding acetic acid after stirring to adjust the pH to 7.8-8.0, adding γ-aminopropyl triethoxysilane, stirring and reacting at 80-85℃ for 5-6 h, washing and drying after the reaction to obtain the aminated halloysite nanotubes.

9. The process for processing of an age resistant high tensile PVC film as claimed in claim 8, wherein: The mass-volume ratio of the halloysite nanotubes and the sodium hydroxide solution is 2g:(90-100)mL; the concentration of the 2-mercaptobenzothiazole solution is 0.06-0.07g / mL; the mass-volume ratio of the pretreated halloysite nanotubes and the 2-mercaptobenzothiazole solution is 1g:(30-35)mL; the volume-mass ratio of the γ-aminopropyl triethoxysilane and the supported halloysite nanotubes is (1.0-1.2)mL:1g.

10. An age resistant high tensile PVC film, characterized in that, The processing process is processed according to any one of claims 1-9. The processing process is processed according to any one of claims 1-9.

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