Tear-resistant PVC (polyvinyl chloride) profile protective film and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and provides a tear-resistant PVC (polyvinyl chloride) profile protective film and a preparation method thereof. The invention discloses a tear-resistant PVC (polyvinyl chloride) profile protective film. The composite material is prepared from the following raw materials in parts by weight: 90 to 100 parts of polyvinyl chloride, 6 to 8 parts of hyperbranched polyurethane, 15 to 25 parts of ethylene-vinyl acetate copolymer, 8 to 12 parts of phenylene ether silicone rubber, 5 to 10 parts of light calcium carbonate, 3 to 5 parts of nano silicon dioxide, 1 to 2 parts of carbon nanotube grafted graphene, 8 to 15 parts of chlorinated polyethylene, 3 to 5 parts of composite stabilizer and 0.5 to 1 part of antioxidant. 1-2 parts of an ultraviolet light absorber and 0.3-0.5 part of a rare earth lanthanum complex. The tear strength and aging resistance of the protective film prepared by the invention are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically, to a tear-resistant PVC profile protective film and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC), as an important thermoplastic, has been widely used in many fields such as building materials, industrial products, daily necessities, wire and cable, and packaging materials due to its good physical and mechanical properties and processing performance. As a kind of PVC product, PVC profiles are especially favored by the market because of their light weight, high strength, easy processing and installation, etc.

[0003] However, there are many problems in the use of traditional PVC profiles. On the one hand, in outdoor or harsh environments, they are easily torn and stretched by external forces, resulting in damage to the surface of the profiles, affecting their aesthetics and service life; on the other hand, the chemical resistance of traditional PVC profiles is poor. In some industrial sites or environments where there is a risk of chemical substance erosion, PVC profiles are prone to react with surrounding chemical substances. For example, in chemical industrial areas, acidic or alkaline gases diffused in the air will gradually corrode the surface of PVC profiles, causing the profiles to change color, become soft, and even have damages such as holes, seriously affecting the structural strength and appearance quality of the profiles. Moreover, when PVC profiles come into contact with certain organic solvents, swelling may occur, destroying the dimensional stability of the profiles and thus unable to perform their functions normally. These problems of poor chemical resistance greatly limit the application of traditional PVC profiles in more complex environments.

[0004] In view of the above problems, the present invention proposes a novel tear-resistant PVC profile protective film and a preparation method thereof. Summary of the Invention

[0005] The present invention proposes a tear-resistant PVC profile protective film and a preparation method thereof, which improve the tear strength and aging resistance of the tear-resistant PVC profile protective film.

[0006] The technical solution of the present invention is as follows: In the first aspect, the present invention proposes a tear-resistant PVC profile protective film, which is composed of the following raw materials in parts by weight: 90 - 100 parts of polyvinyl chloride, 6 - 8 parts of hyperbranched polyurethane, 15 - 25 parts of ethylene-vinyl acetate copolymer, 8 - 12 parts of phenylene ether silicone rubber, 5 - 10 parts of light calcium carbonate, 3 - 5 parts of nano-silica, 1 - 2 parts of carbon nanotube grafted graphene, 8 - 15 parts of chlorinated polyethylene, 3 - 5 parts of composite stabilizer, 0.5 - 1 part of antioxidant, 1 - 2 parts of ultraviolet absorber, and 0.3 - 0.5 part of rare earth lanthanum complex.

[0007] As a further technical solution, the particle size of the light calcium carbonate is 1-3 μm; the particle size of the nano-silica is 20-50 nm.

[0008] As a further technical solution, the preparation method of the carbon nanotube grafted graphene includes: introducing 40-60 sccm of hydrogen and 180-220 sccm of argon into a reaction vessel containing iron-loaded few-layer graphene, introducing 18-22 sccm of acetylene at a temperature of 750-770 °C and reacting for 15-25 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G.

[0009] As a further technical solution, the preparation method of the iron-loaded few-layer graphene includes: adding ferrocene to ethanol and performing ultrasonic dispersion for 30-40 min to obtain a ferrocene solution, impregnating the few-layer graphene therein for 1-2 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG.

[0010] As a further technical solution, the concentration of the ferrocene solution is 0.9-1.1 mg / mL.

[0011] As a further technical solution, the preparation method of the few-layer graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 180-220 sccm and a volume ratio of 1:4 into a reaction vessel containing graphene oxide, and reducing at a temperature of 750-850 °C for 30-40 min to obtain it.

[0012] As a further technical solution, the preparation method of the rare earth lanthanum complex includes: dissolving lanthanum nitrate hexahydrate in deionized water and stirring until transparent to obtain a lanthanum nitrate solution, dissolving ascorbic acid in ethanol and performing ultrasonic dispersion for 10-20 min to obtain an ascorbic acid solution, performing a water bath at a temperature of 60-70 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution and stirring at 100-200 rpm for 4-5 h to precipitate, centrifuging, collecting, and drying to obtain the rare earth lanthanum complex La-AA.

[0013] As a further technical solution, the dosage ratio of the lanthanum nitrate hexahydrate, deionized water, ascorbic acid, and ethanol is 2-3 g: 45-55 mL: 1.7-1.8 g: 25-35 mL.

[0014] As a further technical solution, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010.

[0015] Second, the present invention proposes a preparation method of an anti-tear PVC profile protective film, and the steps include: (1)Premix: Polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica are premixed in a high-speed mixer; the rotation speed during premixing is 800 - 1000 rpm, the temperature is 80 - 90 °C, and the time is 10 - 12 min; (2)Internal mixing: Phenyl ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber, and rare earth lanthanum complex are added and mixed in an internal mixer; (3)Calendering: Calendered into a film by a four-roll calender, the roll temperature is 160 - 170 °C, and the linear speed is 5 - 8 m / min; (4)Cooling and winding: Water-cooled to below 40 °C, and wound to obtain a protective film with a thickness of 0.2 - 0.5 mm.

[0016] As a further technical solution, the temperature during internal mixing is 160 - 180 °C, the rotation speed is 40 - 60 rpm, and the time is 8 - 12 min.

[0017] The working principle and beneficial effects of the present invention are as follows: The present invention constructs a multi-scale toughening system. Hyperbranched polyurethane forms a dynamic hydrogen bond network with polyvinyl chloride through terminal active groups, realizing energy dissipation at the molecular level; the three-dimensional continuous network formed by carbon nanotube grafted graphene is anchored to the matrix through π-π conjugation, and the fracture toughness is improved by means of nano-sheet layer slip and crack bridging mechanisms; the synergistic effect of ethylene-vinyl acetate copolymer and chlorinated polyethylene forms an interpenetrating network structure; the synergistic filling of nano-silica and light calcium carbonate significantly increases the tortuosity of the crack propagation path through network construction and micro-cavitation effects.

[0018] First of all, carbon nanotube grafted graphene vertically grows carbon nanotubes on the surface of graphene by chemical vapor deposition to form a unique "thorn-ball-like" three-dimensional network structure. After this structure is uniformly dispersed in the polyvinyl chloride matrix, the carbon nanotubes, as high-modulus and high-strength reinforcements, significantly consume tearing energy through crack bridging and pulling-out effects. When an external force acts on the protective film, the crack propagates to the vicinity of CNT-G, and the carbon nanotubes are connected to the graphene sheets through covalent bonds to form a physical barrier, forcing the crack to bypass or pull the carbon tubes. At the same time, La3+ in the rare earth lanthanum complex (La-AA) forms dynamic coordination bonds with the chlorine atoms of the polyvinyl chloride molecular chains and the carboxyl groups of the ethylene-vinyl acetate copolymer, dissipating energy through the breakage and recombination of the bonds during the stress process. The synergistic effect of the enhanced rigidity of CNT-G and the dynamic crosslinking of La-AA increases the tear strength of the protective film to 56.3 kN / m.

[0019] Secondly, La-AA can delay photo-oxidative aging. The d-orbital electrons of La³⁺ and the π electrons of ascorbic acid ligands act synergistically to form a broadband absorption layer in the 280-400 nm ultraviolet region, effectively shielding the UVA and UVB bands. In addition, the high thermal conductivity of CNT-G accelerates the diffusion of local heat, reducing the rate of thermal-oxidative aging. Its graphene sheets also block the penetration of oxygen and water vapor through the "labyrinth effect". After 1000 h of QUV accelerated aging, the tear strength retention rate of the protective film containing La-AA and CNT-G reaches 86%, significantly superior to the comparative example.

[0020] In addition, the three-dimensional network of CNT-G fills the pores of the PVC matrix through physical densification, significantly delaying the penetration of corrosive media. La-AA further enhances corrosion resistance through chemical passivation: La³⁺ reacts with SO4²⁻ or OH⁻ in the corrosive medium to form a dense layer of La2(SO4)3 or La(OH)3, blocking further erosion; the carboxyl groups of ascorbic acid can neutralize the alkaline medium, maintain local pH stability, and inhibit the dehydrochlorination reaction of PVC. Therefore, in this invention, the synergistic effect of CNT-G and La-AA realizes a breakthrough in the performance of the PVC protective film from multiple scales: the three-dimensional network enhancement and barrier effect of CNT-G dominate the improvement of mechanical properties and chemical resistance, while La-AA optimizes aging resistance and corrosion resistance through dynamic crosslinking, ultraviolet shielding, and chemical passivation mechanisms. Detailed implementation manners Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0021] It should be noted that in the present invention, the polyvinyl chloride is of SG-5 type (degree of polymerization 1000-1100); the ethylene-vinyl acetate copolymer is of model UL00628 (VA content 28%, melt index 6 g / 10min); the phenylene ether silicone rubber is of model PMV-9922 (phenyl content 10%); the chlorinated polyethylene is of 135A type (chlorine content 35%); the calcium-zinc stabilizer is of model CZ-168 (calcium / zinc = 3:1); graphene oxide (GO, purity >99%, sheet diameter 5-10μm, Nanjing Xianfeng Nano); ferrocene (purity 99.9%, Aladdin reagent); lanthanum nitrate hexahydrate (purity 99.99%, Sinopharm Group); ascorbic acid (AA, vitamin C, purity ≥99%, Sigma-Aldrich).

[0022] Example 1 In this embodiment, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of phenylene ether silicone rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 1.5 parts of carbon nanotube grafted graphene, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber, and 0.4 part of rare earth lanthanum complex; Among them, the particle size of light calcium carbonate is 1-3μm; the particle size of nano-silica is 20-50nm; The preparation method of carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 200 sccm and a volume ratio of 1:4 into a reaction vessel containing graphene oxide, and reducing it at 800°C for 35 minutes to obtain few-layer graphene; adding ferrocene to ethanol and performing ultrasonic dispersion for 35 minutes to obtain a ferrocene solution with a concentration of 1 mg / mL, impregnating the few-layer graphene therein for 1.5 minutes, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 50 sccm of hydrogen and 200 sccm of argon into a reaction vessel containing iron-loaded few-layer graphene, introducing 20 sccm of acetylene at 760°C and reacting for 20 minutes, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the preparation method of rare earth lanthanum complex includes: dissolving 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.75 g of ascorbic acid in 30 mL of ethanol, performing ultrasonic dispersion for 15 minutes to obtain an ascorbic acid solution, performing a water bath at 65°C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 150 rpm for 4.5 hours to precipitate, centrifuging to collect the precipitate, washing it 3 times with ethanol, and drying it in vacuo at 60°C for 12 hours to obtain rare earth lanthanum complex La-AA; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1) Premix: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85°C, and the time is 11 minutes; (2) Internal mixing: Add phenylene ether silicone rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber, and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 170°C, the rotation speed is 50 rpm, and the time is 10 minutes; (3)Calendering: Calendered into a film by a four-roll calender, with the roll temperature at 165 °C and the linear speed at 6 m / min; (4)Cooling and winding: Water-cooled to below 40 °C, and wound to obtain a protective film with a thickness of 0.3 mm.

[0023] Example 2 In this example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 90 parts of polyvinyl chloride, 6 parts of hyperbranched polyurethane, 15 parts of ethylene-vinyl acetate copolymer, 8 parts of phenylene ether siloxane rubber, 5 parts of light calcium carbonate, 3 parts of nano-silica, 1 part of carbon nanotube grafted graphene, 8 parts of chlorinated polyethylene, 3 parts of composite stabilizer, 0.5 part of antioxidant, 1 part of ultraviolet absorber, and 0.3 part of rare earth lanthanum complex; Among them, the particle size of the light calcium carbonate is 1 - 3 μm; the particle size of the nano-silica is 20 - 50 nm; The preparation method of carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 180 sccm and a volume ratio of 1:4 into the reaction vessel containing graphene oxide, and reducing it at 750 °C for 30 min to obtain few-layer graphene; adding ferrocene to ethanol and ultrasonically dispersing it for 30 min to obtain a ferrocene solution with a concentration of 0.9 mg / mL, impregnating the few-layer graphene in it for 1 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 40 sccm of hydrogen and 180 sccm of argon into the reaction vessel containing iron-loaded few-layer graphene, introducing 18 sccm of acetylene at 750 °C and reacting for 15 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the preparation method of the rare earth lanthanum complex includes: dissolving 2 g of lanthanum nitrate hexahydrate in 45 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.7 g of ascorbic acid in 30 mL of ethanol, ultrasonically dispersing it for 10 min to obtain an ascorbic acid solution, performing a water bath at 60 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 100 rpm for 4 h to precipitate, centrifuging to collect the precipitate, washing it with ethanol 3 times, and vacuum drying at 60 °C for 12 h to obtain the rare earth lanthanum complex La-AA; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1)Premix: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 800 rpm, the temperature is 80 °C, and the time is 10 min; (2) Internal Mixing: Add polyphenyl ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 160 °C, the rotation speed is 40 rpm, and the time is 8 min; (3) Calendering: Calender into a film with a four-roll calender, the roll temperature is 160 °C, and the linear speed is 5 m / min; (4) Cooling and Rewinding: Cool with water to below 40 °C, and rewind to obtain a protective film with a thickness of 0.3 mm.

[0024] Example 3 In this example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 8 parts of hyperbranched polyurethane, 25 parts of ethylene-vinyl acetate copolymer, 12 parts of polyphenyl ether siloxane rubber, 10 parts of light calcium carbonate, 5 parts of nano-silica, 2 parts of carbon nanotube grafted graphene, 15 parts of chlorinated polyethylene, 5 parts of composite stabilizer, 1 part of antioxidant, 2 parts of ultraviolet absorber and 0.5 part of rare earth lanthanum complex; Among them, the particle size of light calcium carbonate is 1 - 3 μm; the particle size of nano-silica is 20 - 50 nm; The preparation method of carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 220 sccm and a volume ratio of 1:4 into a reaction vessel containing graphene oxide, and reducing it at 850 °C for 40 min to obtain few-layer graphene; adding ferrocene to ethanol and ultrasonically dispersing it for 40 min to obtain a ferrocene solution with a concentration of 1.1 mg / mL, impregnating the few-layer graphene in it for 2 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 60 sccm of hydrogen and 220 sccm of argon into a reaction vessel containing iron-loaded few-layer graphene, introducing 22 sccm of acetylene at 770 °C and reacting for 25 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the preparation method of rare earth lanthanum complex includes: dissolving 3 g of lanthanum nitrate hexahydrate in 55 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.8 g of ascorbic acid in 35 mL of ethanol, ultrasonically dispersing it for 20 min to obtain an ascorbic acid solution, performing a water bath at 70 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 200 rpm for 5 h to precipitate, centrifuging to collect the precipitate, washing it 3 times with ethanol, and vacuum drying at 60 °C for 12 h to obtain rare earth lanthanum complex La-AA; Among them, the composite stabilizer is calcium-zinc stabilizer, the ultraviolet absorber is UV531 ultraviolet absorber, and the antioxidant is antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film comprises the following steps: (1) Premixing: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 1000 rpm, the temperature is 90 °C, and the time is 12 min; (2) Kneading: Add phenyl ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber, and rare earth lanthanum complex, and knead in a kneader; the temperature during kneading is 180 °C, the rotation speed is 60 rpm, and the time is 12 min; (3) Calendering: Calender into a film with a four-roll calender, the roll temperature is 170 °C, and the linear speed is 8 m / min; (4) Cooling and winding: Cool with water to below 40 °C, and wind to obtain a protective film with a thickness of 0.3 mm.

[0025] Comparative Example 1 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of phenyl ether siloxane rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 1.5 parts of carbon nanotubes, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber, and 0.4 part of rare earth lanthanum complex; Among them, the carbon nanotubes are multi-walled carbon nanotubes with a diameter of 20-30 nm and a length of 1-2 μm; the particle size of the light calcium carbonate is 1-3 μm; the particle size of the nano-silica is 20-50 nm; Among them, the preparation method of the rare earth lanthanum complex includes: Dissolve 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stir until transparent to obtain a lanthanum nitrate solution, dissolve 1.75 g of ascorbic acid in 30 mL of ethanol, and obtain an ascorbic acid solution after ultrasonic dispersion for 15 min. Perform a water bath at 65 °C, slowly drop the ascorbic acid solution into the lanthanum nitrate solution, stir at 150 rpm for 4.5 h to precipitate, centrifuge to collect the precipitate, wash it with ethanol 3 times, and vacuum dry it at 60 °C for 12 h. After drying, the rare earth lanthanum complex La-AA is obtained; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film comprises the following steps: (1) Premixing: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85 °C, and the time is 11 min; (2)Internal Mixing: Add polyphenylene ether siloxane rubber, carbon nanotubes, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 170 °C, the rotation speed is 50 rpm, and the time is 10 min; (3)Calendering: Calender into a film with a four-roll calender, the roll temperature is 165 °C, and the linear speed is 6 m / min; (4)Cooling and Rewinding: Cool with water to below 40 °C, and wind up to obtain a protective film with a thickness of 0.3 mm.

[0026] Comparative Example 2 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of polyphenylene ether siloxane rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 1.5 parts of few-layer graphene, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber and 0.4 part of rare earth lanthanum complex; Among them, the particle size of light calcium carbonate is 1-3 μm; the particle size of nano-silica is 20-50 nm; The preparation method of few-layer graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 200 sccm and a volume ratio of 1:4 into a reaction vessel containing graphene oxide, and reducing it at 800 °C for 35 min to obtain few-layer graphene; Among them, the preparation method of rare earth lanthanum complex includes: dissolving 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.75 g of ascorbic acid in 30 mL of ethanol, ultrasonically dispersing for 15 min to obtain an ascorbic acid solution, performing a water bath at 65 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 150 rpm for 4.5 h to precipitate, centrifuging to collect the precipitate, washing it with ethanol 3 times, and drying it in vacuum at 60 °C for 12 h to obtain the rare earth lanthanum complex La-AA; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1)Premixing: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85 °C, and the time is 11 min; (2) Internal Mixing: Add polyphenylene ether siloxane rubber, few-layer graphene, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 170 °C, the rotation speed is 50 rpm, and the time is 10 min; (3) Calendering: Calender into a film using a four-roll calender, the roll temperature is 165 °C, and the linear speed is 6 m / min; (4) Cooling and Rewinding: Cool with water to below 40 °C, and rewind to obtain a protective film with a thickness of 0.3 mm.

[0027] Comparative Example 3 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of polyphenylene ether siloxane rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber and 0.4 part of rare earth lanthanum complex; Among them, the particle size of light calcium carbonate is 1 - 3 μm; the particle size of nano-silica is 20 - 50 nm; Among them, the preparation method of the rare earth lanthanum complex includes: Dissolve 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stir until transparent to obtain a lanthanum nitrate solution, dissolve 1.75 g of ascorbic acid in 30 mL of ethanol, and obtain an ascorbic acid solution after ultrasonic dispersion for 15 min. Perform a water bath at 65 °C, slowly drop the ascorbic acid solution into the lanthanum nitrate solution, stir at 150 rpm for 4.5 h to precipitate, centrifuge to collect the precipitate, wash it with ethanol 3 times, and dry it in vacuum at 60 °C for 12 h. After drying, the rare earth lanthanum complex La-AA is obtained; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1) Premixing: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85 °C, and the time is 11 min; (2) Internal Mixing: Add polyphenylene ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 170 °C, the rotation speed is 50 rpm, and the time is 10 min; (3) Calendering: Calender into a film using a four-roll calender, the roll temperature is 165 °C, and the linear speed is 6 m / min; (4) Cooling and winding: Cool with water to below 40°C and wind to obtain a protective film with a thickness of 0.3 mm.

[0028] Comparative Example 4 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of phenylene ether siloxane rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 1.5 parts of carbon nanotube grafted graphene, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, and 1.5 parts of ultraviolet absorber; Among them, the particle size of light calcium carbonate is 1 - 3 μm; the particle size of nano-silica is 20 - 50 nm; The preparation method of carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 200 sccm and a volume ratio of 1:4 into the reaction vessel containing graphene oxide, and reducing it at 800°C for 35 min to obtain few-layer graphene; adding ferrocene to ethanol and performing ultrasonic dispersion for 35 min to obtain a ferrocene solution with a concentration of 1 mg / mL, impregnating the few-layer graphene in it for 1.5 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 50 sccm of hydrogen and 200 sccm of argon into the reaction vessel containing iron-loaded few-layer graphene, introducing 20 sccm of acetylene at 760°C for 20 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1) Premixing: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85°C, and the time is 11 min; (2) Kneading: Add phenylene ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, and ultraviolet absorber, and knead in a kneader; the temperature during kneading is 170°C, the rotation speed is 50 rpm, and the time is 10 min; (3) Calendering: Calender into a film with a four-roll calender, the roll temperature is 165°C, and the linear speed is 6 m / min; (4) Cooling and winding: Cool with water to below 40°C and wind to obtain a protective film with a thickness of 0.3 mm.

[0029] Comparative Example 5 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of phenylene ether silicone rubber, 7 parts of light calcium carbonate, 4 parts of nano-silica, 1.5 parts of carbon nanotube grafted graphene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber, and 0.4 part of rare earth lanthanum complex; Among them, the particle size of the light calcium carbonate is 1-3 μm; the particle size of the nano-silica is 20-50 nm; The preparation method of the carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 200 sccm and a volume ratio of 1:4 into a reaction vessel containing graphene oxide, and reducing it at a temperature of 800 °C for 35 min to obtain few-layer graphene; adding ferrocene to ethanol and ultrasonically dispersing it for 35 min to obtain a ferrocene solution with a concentration of 1 mg / mL, impregnating the few-layer graphene in it for 1.5 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 50 sccm of hydrogen and 200 sccm of argon into a reaction vessel containing iron-loaded few-layer graphene, introducing 20 sccm of acetylene at a temperature of 760 °C and reacting for 20 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the preparation method of the rare earth lanthanum complex includes: dissolving 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.75 g of ascorbic acid in 30 mL of ethanol, ultrasonically dispersing it for 15 min to obtain an ascorbic acid solution, performing a water bath at a temperature of 65 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 150 rpm for 4.5 h to precipitate, centrifuging to collect the precipitate, washing it with ethanol 3 times, and drying it in a vacuum at 60 °C for 12 h to obtain the rare earth lanthanum complex La-AA; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1) Premix: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, light calcium carbonate, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85 °C, and the time is 11 min; (2) Kneading: Add phenylene ether silicone rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber, and rare earth lanthanum complex, and knead in a kneader; the temperature during kneading is 170 °C, the rotation speed is 50 rpm, and the time is 10 min; (3) Calendering: Calendered into a film by a four-roll calender, the roll temperature is 165 °C, and the linear speed is 6 m / min; (4) Cooling and winding: Water-cooled to below 40 °C, and wound to obtain a protective film with a thickness of 0.3 mm.

[0030] Comparative Example 6 In this comparative example, a tear-resistant PVC profile protective film is provided, which is composed of the following raw materials in parts by weight: 95 parts of polyvinyl chloride, 7 parts of hyperbranched polyurethane, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of phenylene ether siloxane rubber, 4 parts of nano-silica, 1.5 parts of carbon nanotube grafted graphene, 11 parts of chlorinated polyethylene, 4 parts of composite stabilizer, 0.7 part of antioxidant, 1.5 parts of ultraviolet absorber, and 0.4 part of rare earth lanthanum complex; Among them, the particle size of the nano-silica is 20 - 50 nm; The preparation method of carbon nanotube grafted graphene includes: introducing a mixed gas of hydrogen and argon with a flow rate of 200 sccm and a volume ratio of 1:4 into the reaction vessel containing graphene oxide, and reducing it at 800 °C for 35 min to obtain few-layer graphene; adding ferrocene to ethanol and ultrasonically dispersing it for 35 min to obtain a ferrocene solution with a concentration of 1 mg / mL, impregnating the few-layer graphene in it for 1.5 min, and drying to obtain iron-loaded few-layer graphene Fe@FLG; introducing 50 sccm of hydrogen and 200 sccm of argon into the reaction vessel containing iron-loaded few-layer graphene, introducing 20 sccm of acetylene at 760 °C for 20 min, closing the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G; Among them, the preparation method of the rare earth lanthanum complex includes: dissolving 2.5 g of lanthanum nitrate hexahydrate in 50 mL of deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving 1.75 g of ascorbic acid in 30 mL of ethanol, ultrasonically dispersing it for 15 min to obtain an ascorbic acid solution, performing a water bath at 65 °C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 150 rpm for 4.5 h to precipitate, centrifuging to collect the precipitate, washing it with ethanol 3 times, and vacuum drying at 60 °C for 12 h to obtain the rare earth lanthanum complex La-AA; Among them, the composite stabilizer is a calcium-zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010; The preparation method of this tear-resistant PVC profile protective film includes the following steps: (1) Premix: Premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, and nano-silica in a high-speed mixer; the rotation speed during premixing is 900 rpm, the temperature is 85 °C, and the time is 11 min; (2)Internal Mixing: Add polyphenylene ether siloxane rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mix them in an internal mixer; the temperature during mixing is 170 °C, the rotation speed is 50 rpm, and the time is 10 min; (3)Calendering: Calender into a film with a four-roll calender, the roll temperature is 165 °C, and the linear speed is 6 m / min; (4)Cooling and Rewinding: Cool with water to below 40 °C, and rewind to obtain a protective film with a thickness of 0.3 mm.

[0031] Test Example 1: The protective films prepared in the aforementioned Examples 1-3 and Comparative Examples 1-6 were tested as follows: 1. Tear Strength: Test according to ASTM D1004 (right-angle tear method); specimen size: 150 mm × 50 mm, thickness 0.3 mm; test speed: 200 mm / min; number of specimens in each group: 6, take the average value; 2. Aging Resistance: QUV accelerated aging, UVB-313 lamp, 60 °C / 4 h light irradiation (irradiation intensity 0.7 W / m2) + 50 °C / 4 h condensation, cycle for 1000 h; Tear strength retention rate after aging = (Tear strength after aging / Initial tear strength) × 100%; 3. Chemical Resistance: Test according to GB / T 11547-2008, specimen size: 150 mm × 50 mm, thickness 0.3 mm; Immerse in 5wt% NaOH and 5wt% H2SO4 solutions at room temperature (25 ± 2 °C) for 48 h respectively; Loss rate = (Initial mass - Mass after soaking) / Initial mass × 100%.

[0032] The test results are shown in Table 1 below: Table 1

[0033] According to the data, the synergistic effect of carbon nanotube grafted graphene and rare earth lanthanum complex significantly improves the mechanical properties and aging resistance of the protective film. The absence of chlorinated polyethylene and light calcium carbonate will lead to a decline in the toughening effect and filling performance of the material.

[0034] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A tear-resistant PVC profile protective film, characterized in that: The invention is composed of the following raw materials in parts by weight: 90-100 parts of polyvinyl chloride, 6-8 parts of hyperbranched polyurethane, 15-25 parts of ethylene-vinyl acetate copolymer, 8-12 parts of phenylene ether silicone rubber, 5-10 parts of light calcium carbonate, 3-5 parts of nano silicon dioxide, 1-2 parts of carbon nanotube grafted graphene, 8-15 parts of chlorinated polyethylene, 3-5 parts of composite stabilizer, 0.5-1 parts of antioxidant, 1-2 parts of ultraviolet absorber and 0.3-0.5 parts of rare earth lanthanum complex.

2. The tear-resistant PVC profile protective film according to claim 1, characterized in that: The preparation method of carbon nanotube grafted graphene comprises: introducing 40-60 sccm hydrogen and 180-220 sccm argon into a reaction container containing iron-loaded few-layer graphene, introducing 18-22 sccm acetylene at a temperature of 750-770°C for reaction for 15-25 minutes, turning off the acetylene, and cooling to room temperature in a hydrogen and argon atmosphere to obtain carbon nanotube grafted graphene CNT-G.

3. The tear-resistant PVC profile protective film according to claim 2, characterized in that: The preparation method of the iron-loaded few-layer graphene comprises: adding ferrocene to ethanol and performing ultrasonic dispersion for 30-40 minutes to obtain a ferrocene solution, immersing the few-layer graphene in the ferrocene solution for 1-2 minutes, and drying to obtain the iron-loaded few-layer graphene Fe@FLG.

4. The tear-resistant PVC profile protective film according to claim 3, characterized in that: The concentration of the ferrocene solution is 0.9-1.1 mg / mL.

5. The tear-resistant PVC profile protective film according to claim 3, characterized in that: The preparation method of the few-layer graphene comprises: introducing a mixed gas of hydrogen and argon with a flow rate of 180-220 sccm and a volume ratio of 1:4 into a reaction container containing graphene oxide, and reducing the mixture at a temperature of 750-850° C. for 30-40 minutes to obtain the graphene.

6. The tear-resistant PVC profile protective film according to claim 1, characterized in that: The preparation method of the rare earth lanthanum complex comprises: dissolving lanthanum nitrate hexahydrate in deionized water, stirring until transparent to obtain a lanthanum nitrate solution, dissolving ascorbic acid in ethanol, ultrasonically dispersing for 10-20 minutes to obtain an ascorbic acid solution, water bathing at a temperature of 60-70°C, slowly dropping the ascorbic acid solution into the lanthanum nitrate solution, stirring at 100-200 rpm for 4-5 hours to precipitate, and collecting by centrifugation and drying to obtain the rare earth lanthanum complex La-AA.

7. The tear-resistant PVC profile protective film according to claim 6, characterized in that: The usage ratio of the lanthanum nitrate hexahydrate, deionized water, ascorbic acid and ethanol is (2-3) g: (45-55) mL: (1.7-1.8) g: (25-35) mL.

8. The tear-resistant PVC profile protective film according to claim 1, characterized in that: The composite stabilizer is a calcium zinc stabilizer, the ultraviolet absorber is a UV531 ultraviolet absorber, and the antioxidant is an antioxidant 1010.

9. The method for preparing a tear-resistant PVC profile protective film according to any one of claims 1 to 8, characterized in that the steps include: (1) Premix: premix polyvinyl chloride, hyperbranched polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene, light calcium carbonate and nano-silicon dioxide in a high-speed mixer; the speed of premixing is 800-1000 rpm, the temperature is 80-90°C, and the time is 10-12 minutes; (2) Internal mixing: adding phenyl ether silicone rubber, carbon nanotube grafted graphene, composite stabilizer, antioxidant, ultraviolet absorber and rare earth lanthanum complex, and mixing in an internal mixer; (3) Calendering: calendering film with a four-roll calender, the roller temperature is 160-170°C, and the line speed is 5-8m / min; (4) Cooling and rolling: Cool with water to below 40°C and roll up to obtain a protective film with a thickness of 0.2-0.5 mm.

10. The method for preparing a tear-resistant PVC profile protective film according to claim 9, characterized in that: The mixing temperature is 160-180° C., the rotation speed is 40-60 rpm, and the mixing time is 8-12 min.

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