Anti-aging plastic and application thereof

Abstract

The invention relates to the technical field of plastics, in particular to an anti-aging plastic and application thereof. The aging-resistant plastic disclosed by the invention is prepared from polypropylene, low-density polyethylene, DLTP-loaded organic montmorillonite, intercalated montmorillonite, a compatilizer and a lubricant. According to the invention, intercalated montmorillonite prepared by a solvent intercalation method and DLTP-loaded organic montmorillonite prepared by modifying montmorillonite through functionalized quaternary ammonium salt and further loading an antioxidant DLTP are added into raw materials, so that the aging resistance, mechanical properties and environmental stability of the material are remarkably improved, the material preparation process is simple and convenient, and the cost is low. The double-screw extruder is suitable for continuous production, is widely applied to the fields of automobiles, electronic appliances, buildings, outdoor packaging and the like, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastics, in particular to a kind of anti-aging plastics and application thereof. BACKGROUND

[0002] Plastics have the advantages of light weight, stable chemical properties, no rust, good impact resistance, good transparency, good insulation, good coloring and lower processing cost, polypropylene is a kind of excellent performance thermoplastic synthetic resin, which is colorless and translucent thermoplastic lightweight general-purpose plastic, it has chemical resistance, heat resistance, electrical insulation, high strength mechanical properties and good high wear resistance processing performance, etc., and is widely used in many fields such as machinery, automobile, electronic and electrical appliances, building, textile, packaging, agriculture, forestry, fishery and food industry.

[0003] Patent technology document CN111484673B discloses a modified polypropylene plastic, which is prepared by adding silicone powder to improve the mechanical properties of polypropylene plastic and improve the toughness of polypropylene plastic; the silicone powder and PE wax are compounded to synergistically improve the mechanical properties of polypropylene plastic; patent technology document CN116253951B discloses a flame-retardant polypropylene plastic, which is improved by composite flame retardant, and is non-toxic, harmless, efficient and safe, so that the composite flame retardant gives the polypropylene plastic uniform and durable, non-toxic, harmless, efficient and safe flame-retardant properties.

[0004] However, when plastics are used in outdoor environment, their service life is often affected by aging. SUMMARY

[0005] Therefore, the present application aims to provide an anti-aging plastic and its application to solve the problem of poor anti-aging performance and short service life of traditional plastics.

[0006] To achieve the above purpose, the present application provides an anti-aging plastic prepared from the following raw materials by weight: 100-110 parts of polypropylene, 10-15 parts of low-density polyethylene, 10-15 parts of DLTP-loaded organic montmorillonite, 5-7 parts of intercalated montmorillonite, 3-7 parts of crosslinking agent, 1-2 parts of sulfur, 1-2 parts of compatibilizer and 1-2 parts of lubricant. The intercalated montmorillonite is prepared by solvent intercalation method in acetone from antioxidant 1010 and nano-montmorillonite; The preparation steps of the DLTP-loaded organic montmorillonite are as follows: S1: under nitrogen atmosphere, 1-vinyl-1,2,4-triazole and p-methoxyphenol were added into anhydrous acetonitrile, cooled to 2-4℃ in ice bath, then 1,5-dibromopentane was added, stirred at room temperature for 12h, then 1,3,5-tris(bromomethyl)benzene and 1-bromododecane were added, heated to 60℃, stirred for 10-12h, rotary evaporation, purification, vacuum drying to obtain functionalized quaternary ammonium salt; S2: nano-montmorillonite was added into deionized water, ultrasonic treatment at 60℃ to obtain a suspension; octadecyltrimethylammonium chloride and functionalized quaternary ammonium salt were dissolved in ethanol (60℃), stirred uniformly and then added into the suspension, keeping the temperature at 60℃, continuing to stir for 5-6h, after the reaction was completed, the precipitate was collected by centrifugation, purified to obtain quaternary ammonium salt intercalated organic montmorillonite; S3: dilaurylthiopropionate DLTP was melt intercalated with quaternary ammonium salt intercalated organic montmorillonite to obtain DLTP loaded organic montmorillonite.

[0007] Preferably, the polypropylene is Zhejiang Petrochemical K8003.

[0008] Preferably, the low-density polyethylene is Zhenhai Refinery 7050H.

[0009] Preferably, the crosslinking agent is dicumyl peroxide.

[0010] Preferably, the compatibilizer is polypropylene grafted maleic anhydride.

[0011] Preferably, the lubricant is one of polyethylene wax and calcium stearate.

[0012] Preferably, the amount ratio of the antioxidant 1010, acetone and nano-montmorillonite is 3.6-4.5g: 50-80mL: 3-3.6g.

[0013] Preferably, the length of the nano-montmorillonite is 400-500nm, and the interlayer spacing is 1.2-1.4nm.

[0014] Preferably, the amount ratio of 1-vinyl-1,2,4-triazole, p-methoxyphenol, anhydrous acetonitrile, 1,5-dibromopentane, 1,3,5-tris(bromomethyl)benzene and 1-bromododecane in step S1 is 1.5-2.5g: 0.01-0.02g: 90-100g: 1-2g: 0.4-0.5g: 0.4-0.5g.

[0015] Preferably, the amount ratio of nano-montmorillonite, deionized water, octadecyltrimethylammonium chloride, functionalized quaternary ammonium salt and ethanol in step S2 is 10-15g: 500mL: 2-3g: 1.5-3g: 100-200mL.

[0016] Preferably, the particle size of the nanometer montmorillonite in step S2 is 171214154750 from Clariant, Karamay, China.

[0017] Preferably, the purification in step S2 is washing with ethanol / water (1:1) for 3 times, and finally drying at 60°C under vacuum for 24h.

[0018] Preferably, the amount ratio of the dilaurylthiopropionate DLTP, quaternary ammonium salt intercalated organic montmorillonite in step S3 is 5-10g:10-15g.

[0019] Preferably, the temperature of the melt intercalation in step S3 is 120°C, and the time is 15-20min.

[0020] Preferably, the preparation steps of the anti-aging plastic are as follows: polypropylene, low density polyethylene, DLTP loaded organic montmorillonite, intercalated montmorillonite, crosslinking agent, compatibilizer and lubricant are mixed uniformly in a high-speed mixer, and then sent into a twin-screw extruder for extrusion and granulation to obtain the anti-aging plastic material.

[0021] Preferably, the length-diameter ratio of the screw of the twin-screw extruder is 45, and the temperature from feeding to discharging is: the first section is 130°C, the second section is 170°C, the third section is 190°C, the fourth section is 170°C, and the fifth section is 160°C.

[0022] Further, the application also provides an application of the anti-aging plastic, which is applied in the fields of automobiles, electronic appliances, buildings and outdoor packaging.

[0023] The beneficial effects of the application are as follows: The application innovatively adopts a double composite system of intercalated montmorillonite and DLTP loaded organic montmorillonite, constructs a multi-level synergistic anti-aging protection network, and makes the antioxidant present a double release mode of "fast response-sustained protection" through the difference in the layer spacing of the two kinds of montmorillonite (the layer spacing of the intercalated montmorillonite is smaller and the layer spacing of the organic montmorillonite is larger), which significantly improves the long-term weather resistance of the material.

[0024] The application realizes a multiple interface enhancement effect by the special molecular design of the functional quaternary ammonium salt, which simultaneously introduces rigid benzene ring structure and long chain alkyl structure on the surface of the montmorillonite, which not only expands the layer spacing of the montmorillonite, is conducive to the loading and release of the antioxidant, but more importantly, forms a strong interface combination in the polymer matrix, effectively promotes stress transfer and energy dissipation, so that the material has high hardness and good impact toughness at the same time.

[0025] The present application realizes the nanometer uniform dispersion of the montmorillonite in the polymer matrix through the process design of stepwise intercalation and functional modification, the intercalation treatment of the antioxidant 1010 makes the surface of the montmorillonite sheet layer have suitable polarity, and the organic treatment of the functionalized quaternary ammonium salt adjusts the compatibility of the montmorillonite and the matrix, so that the montmorillonite can form a stable nanometer dispersion system, the sheet layer structure of the montmorillonite constructs a tortuous barrier path in the matrix, and the penetration rate of oxygen, moisture and ultraviolet can be effectively delayed. Meanwhile, the uniformly dispersed montmorillonite sheet layer serves as a physical reinforcing phase, and the surface hardness and dimensional stability of the material are significantly improved. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below with specific examples.

[0027] The properties or sources of the raw materials used in the examples and comparative examples of the present application are as follows: Polypropylene: Zhejiang Petrochemical K8003; Low-density polyethylene: Zhenhai Refinery 7050H; Nanometer montmorillonite: length: 400-500 nm, interlayer spacing: 1.2-1.4 nm.

[0028] Example 1: A kind of anti-aging plastic, the specific preparation steps are as follows: (1) 3 g of nanometer montmorillonite is pretreated at 80℃ for 30 min to obtain pretreated nanometer montmorillonite; then 3.6 g of antioxidant 1010 is dissolved in 50 mL of acetone, the pretreated nanometer montmorillonite is added, ultrasonic treatment is carried out for 30 min, continuous stirring is carried out at 50℃ for 2 h, and rotary evaporation is carried out to obtain intercalated montmorillonite; (2) Under the nitrogen atmosphere, 1.5 g of 1-vinyl-1, 2, 4-triazole and 0.01 g of p-methoxyphenol are added to 90 g of anhydrous acetonitrile, cooled to 2℃ in an ice bath, then 1 g of 1, 5-dibromopentane is added, stirred at room temperature for 12 h, then 0.4 g of 1, 3, 5-tris (bromomethyl) benzene and 0.4 g of 1-bromododecane are added, the temperature is increased to 60℃, and stirring is carried out for 10 h, rotary evaporation is carried out, methanol / dichloromethane (volume ratio 1:1) is used for reprecipitation twice, and vacuum drying is carried out to obtain a functionalized quaternary ammonium salt; (3) 10 g of nanometer montmorillonite is added to 500 mL of deionized water, ultrasonic treatment is carried out at 60℃ to obtain a suspension; 2 g of octadecyltrimethylammonium chloride and 1.5 g of the functionalized quaternary ammonium salt are dissolved in 100 mL of hot ethanol (60℃), and after stirring uniformly, the suspension is added, the temperature is kept at 60℃, and stirring is continued for 5 h; after the reaction is completed, the precipitate is collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60℃ under vacuum for 24 h to obtain organic montmorillonite intercalated with quaternary ammonium salt; (4) 5 g of dilaurylthiopropionate DLTP and 10 g of quaternary ammonium salt intercalated organic montmorillonite were melt intercalated at 120 °C for 15 min to obtain DLTP loaded organic montmorillonite; (5) 100 g of polypropylene, 10 g of low density polyethylene, 10 g of DLTP loaded organic montmorillonite, 5 g of intercalated montmorillonite, 3 g of dicumyl peroxide, 1 g of sulfur, 1 g of polypropylene grafted maleic anhydride and 1 g of polyethylene wax were uniformly mixed in a high-speed mixer, and then were sent into a twin-screw extruder for extrusion granulation to obtain an anti-aging plastic material, wherein the length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: 130 °C for the first section, 170 °C for the second section, 190 °C for the third section, 170 °C for the fourth section and 160 °C for the fifth section.

[0029] Example 2: An anti-aging plastic, the specific preparation steps are as follows: (1) 3.3 g of nano montmorillonite was pretreated at 80 °C for 30 min to obtain pretreated nano montmorillonite; then 4 g of antioxidant 1010 was dissolved in 70 mL of acetone, and the pretreated nano montmorillonite was added, ultrasonic treatment was performed for 30 min, and then continuous stirring was performed at 50 °C for 3 h, and rotary evaporation was performed to obtain intercalated montmorillonite; (2) Under a nitrogen atmosphere, 2 g of 1-ethenyl-1,2,4-triazole and 0.015 g of p-methoxyphenol were added to 95 g of anhydrous acetonitrile, cooled to 3 °C in an ice bath, and then 1.5 g of 1,5-dibromopentane was added, stirred at room temperature for 12 h, and then 0.45 g of 1,3,5-tris(bromomethyl)benzene and 0.45 g of 1-bromododecane were added, and the temperature was increased to 60 °C and stirred for 11 h, and rotary evaporation was performed, and reprecipitation was performed twice with methanol / dichloromethane (volume ratio 1:1), and vacuum drying was performed to obtain a functionalized quaternary ammonium salt; (3) 13 g of nano montmorillonite was added to 500 mL of deionized water, and ultrasonic treatment was performed to obtain a suspension at 60 °C; 2.5 g of octadecyltrimethylammonium chloride and 2.5 g of the functionalized quaternary ammonium salt were dissolved in 150 mL of hot ethanol (60 °C), and after uniform stirring, the suspension was added, and the temperature was maintained at 60 °C, and stirring was continued for 6 h, and after the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally vacuum dried at 60 °C for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (4) 8 g of dilaurylthiopropionate DLTP and 13 g of quaternary ammonium salt intercalated organic montmorillonite were melt intercalated at 120 °C for 18 min to obtain DLTP loaded organic montmorillonite; (5) 105 g of polypropylene, 13 g of low-density polyethylene, 13 g of DLTP-loaded organic montmorillonite, 6 g of intercalated montmorillonite, 5 g of dicumyl peroxide, 1.5 g of sulfur, 1.5 g of polypropylene grafted maleic anhydride, and 1.5 g of polyethylene wax were mixed uniformly in a high-speed mixer and then fed into a twin-screw extruder for extrusion granulation. The length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: 130°C for the first section, 170°C for the second section, 190°C for the third section, 170°C for the fourth section, and 160°C for the fifth section.

[0030] Example 3: A kind of anti-aging plastic, the specific preparation steps are as follows: (1) 3.6 g of nano-montmorillonite was pretreated at 80°C for 30 min to obtain pretreated nano-montmorillonite; then 4.5 g of antioxidant 1010 was dissolved in 80 mL of acetone, and the pretreated nano-montmorillonite was added, ultrasonic treatment for 30 min, and then continuous stirring at 50°C for 3 h, rotary evaporation to obtain intercalated montmorillonite; (2) Under a nitrogen atmosphere, 2.5 g of 1-ethenyl-1,2,4-triazole and 0.02 g of p-methoxyphenol were added to 100 g of anhydrous acetonitrile, cooled to 4°C in an ice bath, then 2 g of 1,5-dibromopentane was added, stirred at room temperature for 12 h, then 0.5 g of 1,3,5-tris(bromomethyl)benzene and 0.5 g of 1-bromododecane were added, and the temperature was raised to 60°C, stirred for 12 h, rotary evaporation, and then reprecipitated twice with methanol / dichloromethane (1:1 by volume), and vacuum dried to obtain a functionalized quaternary ammonium salt; (3) 15 g of nano-montmorillonite was added to 500 mL of deionized water and ultrasonically treated at 60°C to obtain a suspension; 3 g of octadecyltrimethylammonium chloride and 3 g of functionalized quaternary ammonium salt were dissolved in 200 mL of hot ethanol (60°C), stirred uniformly, and then added to the suspension, keeping the temperature at 60°C, and continuing to stir for 6 h; after the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60°C under vacuum for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (4) 10 g of dilaurylthiopropionate DLTP was melt intercalated with 15 g of quaternary ammonium salt intercalated organic montmorillonite at 120°C for 20 min to obtain DLTP-loaded organic montmorillonite; (5) 110 g of polypropylene, 15 g of low density polyethylene, 15 g of DLTP loaded organic montmorillonite, 7 g of intercalated montmorillonite, 7 g of dicumyl peroxide, 2 g of sulfur, 2 g of polypropylene grafted maleic anhydride and 2 g of polyethylene wax were mixed uniformly in a high-speed mixer, and then were sent into a twin-screw extruder for extrusion granulation to obtain the anti-aging plastic material, wherein the length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: 130°C for the first section, 170°C for the second section, 190°C for the third section, 170°C for the fourth section and 160°C for the fifth section.

[0031] Comparative Example 1: The difference from Example 2 is that no intercalated montmorillonite is added, and the specific steps are as follows: (1) 2 g of 1-vinyl-1, 2, 4-triazole and 0.015 g of p-methoxyphenol were added to 95 g of anhydrous acetonitrile under a nitrogen atmosphere, cooled to 3°C in an ice bath, and then 1.5 g of 1, 5-dibromopentane was added, stirred at room temperature for 12 h, and then 0.45 g of 1, 3, 5-tris (bromomethyl) benzene and 0.45 g of 1-bromododecane were added, and the temperature was increased to 60°C, and stirred for 11 h, and then rotary evaporation was performed, and reprecipitation was performed twice with methanol / dichloromethane (volume ratio 1:1), and vacuum drying was performed to obtain a functionalized quaternary ammonium salt; (2) 13 g of nano montmorillonite was added to 500 mL of deionized water, and a suspension was obtained by ultrasonic treatment at 60°C; 2.5 g of octadecyltrimethylammonium chloride and 2.5 g of the functionalized quaternary ammonium salt were dissolved in 150 mL of hot ethanol (60°C), and after being stirred uniformly, they were added to the suspension, and the temperature was maintained at 60°C, and stirring was continued for 6 h, and after the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60°C under vacuum for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (3) 8 g of dilaurylthiopropionate DLTP was melt intercalated with 13 g of quaternary ammonium salt intercalated organic montmorillonite at 120°C for 18 min to obtain DLTP loaded organic montmorillonite; (4) 105 g of polypropylene, 13 g of low density polyethylene, 19 g of DLTP loaded organic montmorillonite, 5 g of dicumyl peroxide, 1.5 g of sulfur, 1.5 g of polypropylene grafted maleic anhydride and 1.5 g of polyethylene wax were mixed uniformly in a high-speed mixer, and then were sent into a twin-screw extruder for extrusion granulation to obtain the anti-aging plastic material, wherein the length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: 130°C for the first section, 170°C for the second section, 190°C for the third section, 170°C for the fourth section and 160°C for the fifth section.

[0032] Comparative Example 2: The difference from Example 2 is that no DLTP loaded organic montmorillonite is added, and the specific steps are as follows: (1) 3.3 g nano-montmorillonite was pretreated at 80 °C for 30 min to obtain pretreated nano-montmorillonite; then 4 g antioxidant 1010 was dissolved in 70 mL acetone, and the pretreated nano-montmorillonite was added, and after ultrasonic treatment for 30 min, continuous stirring was carried out at 50 °C for 3 h, and rotary evaporation was carried out to obtain intercalated montmorillonite; (2) 105 g polypropylene, 13 g low-density polyethylene, 19 g intercalated montmorillonite, 5 g dicumyl peroxide, 1.5 g sulfur, 1.5 g polypropylene grafted maleic anhydride and 1.5 g polyethylene wax were uniformly mixed in a high-speed mixer, and then were sent into a twin-screw extruder for extrusion and granulation to obtain an anti-aging plastic material, wherein the length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: the first section 130 °C, the second section 170 °C, the third section 190 °C, the fourth section 170 °C, and the fifth section 160 °C.

[0033] Comparative Example 3: The difference from Example 2 is that no functionalized quaternary ammonium salt is added in step (3), and the specific steps are as follows: (1) 3.3 g nano-montmorillonite was pretreated at 80 °C for 30 min to obtain pretreated nano-montmorillonite; then 4 g antioxidant 1010 was dissolved in 70 mL acetone, and the pretreated nano-montmorillonite was added, and after ultrasonic treatment for 30 min, continuous stirring was carried out at 50 °C for 3 h, and rotary evaporation was carried out to obtain intercalated montmorillonite; (2) 13 g nano-montmorillonite was added to 500 mL deionized water, and ultrasonic treatment was carried out at 60 °C to obtain a suspension; 2.5 g octadecyl trimethyl ammonium chloride was dissolved in 150 mL hot ethanol (60 °C), and after uniform stirring, it was added to the suspension, and the temperature was maintained at 60 °C, and the stirring was continued for 6 h; after the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60 °C under vacuum for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (3) 8 g dilaurylthiopropionate DLTP and 13 g quaternary ammonium salt intercalated organic montmorillonite were melt intercalated at 120 °C for 18 min to obtain DLTP loaded organic montmorillonite; (4) 105 g polypropylene, 13 g low-density polyethylene, 13 g DLTP loaded organic montmorillonite, 6 g intercalated montmorillonite, 5 g dicumyl peroxide, 1.5 g sulfur, 1.5 g polypropylene grafted maleic anhydride and 1.5 g polyethylene wax were uniformly mixed in a high-speed mixer, and then were sent into a twin-screw extruder for extrusion and granulation to obtain an anti-aging plastic material, wherein the length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: the first section 130 °C, the second section 170 °C, the third section 190 °C, the fourth section 170 °C, and the fifth section 160 °C Comparative Example 4: The difference from Example 2 is that no 1,3,5-tris(bromomethyl)benzene is added in step (2), and the specific steps are as follows: (1) 3.3 g of nano-montmorillonite was pretreated at 80 °C for 30 min to obtain pretreated nano-montmorillonite; then 4 g of antioxidant 1010 was dissolved in 70 mL of acetone, and the pretreated nano-montmorillonite was added, ultrasonic treatment was performed for 30 min, and then continuous stirring was performed at 50 °C for 3 h, and rotary evaporation was performed to obtain intercalated montmorillonite; (2) 2 g of 1-ethenyl-1,2,4-triazole and 0.015 g of p-methoxyphenol were added to 95 g of anhydrous acetonitrile under a nitrogen atmosphere, cooled to 3 °C in an ice bath, and then 1.5 g of 1,5-dibromopentane was added, stirred at room temperature for 12 h, and then 0.45 g of 1-bromododecane was added, heated to 60 °C, and stirred for 11 h. Rotary evaporation was performed, and reprecipitation was performed twice with methanol / dichloromethane (1:1 by volume), and vacuum drying was performed to obtain a functionalized quaternary ammonium salt; (3) 13 g of nano-montmorillonite was added to 500 mL of deionized water, and ultrasonic treatment was performed at 60 °C to obtain a suspension; 2.5 g of octadecyltrimethylammonium chloride and 2.5 g of the functionalized quaternary ammonium salt were dissolved in 150 mL of hot ethanol (60 °C), and then added to the suspension after uniform stirring, and the temperature was maintained at 60 °C, and stirring was continued for 6 h. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60 °C under vacuum for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (4) 8 g of dilaurylthiopropionate DLTP was melt intercalated with 13 g of quaternary ammonium salt intercalated organic montmorillonite at 120 °C for 18 min to obtain DLTP loaded organic montmorillonite; (5) 105 g of polypropylene, 13 g of low-density polyethylene, 13 g of DLTP loaded organic montmorillonite, 6 g of intercalated montmorillonite, 5 g of dicumyl peroxide, 1.5 g of sulfur, 1.5 g of polypropylene grafted maleic anhydride, and 1.5 g of polyethylene wax were uniformly mixed in a high-speed mixer, and then sent to a twin-screw extruder for extrusion and granulation to obtain an anti-aging plastic material. The length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: the first section was 130 °C, the second section was 170 °C, the third section was 190 °C, the fourth section was 170 °C, and the fifth section was 160 °C.

[0034] Comparative Example 5: The difference from Example 2 is that no 1-bromododecane is added in step (2), and the specific steps are as follows: (1) 3.3 g of nano-montmorillonite was pretreated at 80 °C for 30 min to obtain pretreated nano-montmorillonite; then 4 g of antioxidant 1010 was dissolved in 70 mL of acetone, and the pretreated nano-montmorillonite was added, ultrasonic treatment was performed for 30 min, and then continuous stirring was performed at 50 °C for 3 h, and rotary evaporation was performed to obtain intercalated montmorillonite; (2) Under nitrogen atmosphere, 2 g of 1-vinyl-1,2,4-triazole and 0.015 g of p-methoxyphenol were added into 95 g of anhydrous acetonitrile, cooled to 3°C in an ice bath, and then 1.5 g of 1,5-dibromopentane was added. After stirring at room temperature for 12 h, 0.45 g of 1,3,5-tris(bromomethyl)benzene was added, and the temperature was increased to 60°C. After stirring for 11 h, rotary evaporation was performed, and re-precipitation was performed twice with methanol / dichloromethane (1:1 by volume). After vacuum drying, a functionalized quaternary ammonium salt was obtained; (3) 13 g of nanometer-sized montmorillonite was added into 500 mL of deionized water, and a suspension was obtained by ultrasonic treatment at 60°C. Separately, 2.5 g of octadecyltrimethylammonium chloride and 2.5 g of the functionalized quaternary ammonium salt were dissolved in 150 mL of hot ethanol (60°C), and the solution was added to the suspension after being stirred uniformly. The temperature was maintained at 60°C, and stirring was continued for 6 h. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol / water (1:1) for 3 times, and finally dried at 60°C under vacuum for 24 h to obtain quaternary ammonium salt intercalated organic montmorillonite; (4) 8 g of dilaurylthiopropionate (DLTP) and 13 g of the quaternary ammonium salt intercalated organic montmorillonite were melt intercalated at 120°C for 18 min to obtain DLTP-loaded organic montmorillonite; (5) 105 g of polypropylene, 13 g of low-density polyethylene, 13 g of the DLTP-loaded organic montmorillonite, 6 g of the intercalated montmorillonite, 5 g of dicumyl peroxide, 1.5 g of sulfur, 1.5 g of polypropylene grafted maleic anhydride, and 1.5 g of polyethylene wax were uniformly mixed in a high-speed mixer, and then fed into a twin-screw extruder for extrusion and granulation to obtain an anti-aging plastic material. The length-diameter ratio of the screw of the twin-screw extruder was 45, and the temperature from the feeding to the discharging was: 130°C for the first section, 170°C for the second section, 190°C for the third section, 170°C for the fourth section, and 160°C for the fifth section.

[0035] The plastic particles obtained in the examples and comparative examples were subjected to injection molding to prepare flat test panels. The injection molding process was as follows: barrel temperature 200°C, nozzle 190°C, screw rotation speed 120 rpm, and the injection-molded panels had a thickness of 4 mm. The panels were then cut into test panels with a width of 10 mm and a length of 80 mm for performance testing. Abrasion resistance: According to GB / T6739-2006 (Determination of film hardness by pencil method for paints and varnishes), the surface of the test panel was scraped with pencils of different hardnesses starting from 3B, and the hardness of the pencil was gradually increased until a scratch was made. The test results are shown in Table 1. Impact strength: The obtained test panels were subjected to impact performance testing according to GB / T1043.1-2008, “Plastics-Determination of Charpy Impact Strength-Part 1”. The test results are shown in Table 1. Anti-aging ability: according to GB / T16422.2-2014 "Plastics-Laboratory light source exposure test method", the xenon arc lamp was filtered by filter, exposed according to method A cycle sequence 1, with 102min drying and 18min spraying as a cycle period, irradiated for 500h, broadband irradiance was 60W / m 2 , narrowband irradiance was 0.51W / m 2 , black tag temperature was 65℃, test box temperature was 38℃, impact strength was tested, and the test results are shown in Table 1.

[0036] Table 1 Performance test results

[0037] Data analysis: from the data of the examples in Table 1, it can be seen that the anti-aging plastic has excellent comprehensive performance, the rigid sheet layer of the montmorillonite as a physical reinforcing phase improves the surface hardness of the material, the nanoscale dispersion in the matrix forms a tortuous path, effectively blocks the penetration of oxygen, ultraviolet and moisture, and inhibits the diffusion rate of photo-oxidation reaction, and the montmorillonite sheet itself has ultraviolet shielding properties, can construct a multi-level defense system with the loaded antioxidant 1010 and auxiliary antioxidant DLTP, block the oxidation chain reaction through synergistic effect, maintain the mechanical integrity of the material under long-term irradiation; at the same time, the intercalation modification of antioxidant 1010 and the functionalization of quaternary ammonium salt strengthen the interface bonding between montmorillonite and polymer chain, can form physical crosslinking or ionic interaction with polymer chain, reduce the microcrack expansion caused by stress concentration, improve the interfacial adhesion, promote the dissipation of impact energy in the matrix, prevent rapid crack propagation, so as to ensure that the material has good wear resistance, excellent impact resistance and anti-aging ability.

[0038] From the performance comparison of examples 2 and comparative examples 1 and 2, it can be seen that the modified montmorillonite containing the two components has better wear resistance, initial impact strength and anti-aging performance than comparative examples 1 (without intercalated montmorillonite) and comparative examples 2 (without organic montmorillonite), and the synergistic effect may be due to the following mechanism: the antioxidant 1010 loaded in the intercalated montmorillonite and the DLTP in the organic montmorillonite form a composite antioxidant system, the former inhibits the oxidation chain reaction by capturing free radicals, and the latter delays the aging of the material by decomposing peroxide, and the layered structure of the two modified montmorillonites in the matrix forms a multi-level barrier network, the antioxidant 1010 loaded montmorillonite with small interlayer spacing can provide rapid release protection, and the DLTP loaded organic montmorillonite with large interlayer spacing can provide long-acting slow-release protection, the difference in interlayer spacing and polarity matching makes the antioxidant show a dual release mode of "rapid response-sustained protection", forming a synergistic antioxidant protection mechanism.

[0039] The performance comparison of Example 2 and Comparative Example 3 shows that Example 2 is superior to Comparative Example 3 without adding functionalized quaternary ammonium salt in terms of wear resistance, initial impact strength and impact strength retention rate after aging, which is mainly because the interlayer spacing of the single intercalation of octadecyl trimethyl ammonium chloride is smaller than the synergistic intercalation of octadecyl trimethyl ammonium chloride and functionalized quaternary ammonium salt, and cannot form a mutual synergistic effect with the antioxidant 1010 loaded montmorillonite, thereby affecting its antioxidant capacity. Without the modification of functionalized quaternary ammonium salt, the interfacial bonding force between the loaded DLTP organic montmorillonite and the matrix is affected, thereby causing the mechanical strength to decrease.

[0040] The performance comparison of Example 2 and Comparative Examples 4 and 5 shows that the addition of 1,3,5-tris(bromomethyl)benzene and 1-bromododecane introduces branched structures with benzene rings and branched structures with long alkyl chains into the structure of functionalized quaternary ammonium salt. The rigid benzene ring structure of 1,3,5-tris(bromomethyl)benzene can enhance the interlayer bonding force of montmorillonite through π-π stacking effect, and its branched characteristics can expand the interlayer spacing. The long-chain alkyl of 1-bromododecane further improves the interlayer expansion degree through steric hindrance effect and enhances the compatibility with the polymer matrix, so that the loaded DLTP organic montmorillonite forms a more stable dispersion system in the matrix, and forms a synergistic antioxidant network with the antioxidant 1010 in the intercalated montmorillonite. In addition, the complete structure of the functionalized quaternary ammonium salt can optimize the loading efficiency of DLTP between the layers of montmorillonite, not only improve the initial mechanical properties of the material, but more importantly, build a more durable anti-aging protection system, so that the material maintains more excellent performance stability under long-term use conditions.

[0041] It should be understood by those skilled in the art that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the present application is limited to these examples; under the idea of the present application, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other changes of different aspects of the present application as described above. In order to be brief, they are not provided in detail.

Claims

1. An age-resistant plastic, characterized in that, It is prepared from the following raw materials in parts by weight: 100-110 parts of polypropylene, 10-15 parts of low-density polyethylene, 10-15 parts of DLTP-loaded organic montmorillonite, 5-7 parts of intercalated montmorillonite, 3-7 parts of crosslinking agent, 1-2 parts of sulfur, 1-2 parts of compatibilizer and 1-2 parts of lubricant; The intercalated montmorillonite is prepared by a solvent intercalation method in acetone from antioxidant 1010 and nano montmorillonite; The preparation steps of the DLTP-loaded organic montmorillonite are as follows: S1: Under a nitrogen atmosphere, 1-vinyl-1, 2, 4-triazole and p-methoxyphenol are added to anhydrous acetonitrile, cooled to 2-4℃ in an ice bath, then 1, 5-dibromopentane is added, stirred at room temperature for 12h, then 1, 3, 5-tris(bromomethyl)benzene and 1-bromododecane are added, heated to 60℃, stirred for 10-12h, rotary evaporated, purified, vacuum dried to obtain a functionalized quaternary ammonium salt; S2: Nano montmorillonite is added to deionized water to obtain a suspension; octadecyltrimethylammonium chloride and the functionalized quaternary ammonium salt are dissolved in ethanol, stirred uniformly and then added to the suspension, stirred for 5-6h, centrifuged, purified to obtain quaternary ammonium salt intercalated organic montmorillonite; S3: Di-lauryl thio propionate DLTP is melt intercalated with the quaternary ammonium salt intercalated organic montmorillonite to obtain DLTP-loaded organic montmorillonite.

2. The weatherable plastic of claim 1, wherein, The polypropylene is K8003 from Zhejiang Petrochemical; the low-density polyethylene is 7050H from Zhenhai Refinery and Chemical.

3. The weatherable plastic of claim 1, wherein, The crosslinking agent is dicumyl peroxide.

4. The weatherable plastic of claim 1, wherein, The compatibilizer is polypropylene grafted maleic anhydride; the lubricant is one of polyethylene wax and calcium stearate.

5. The weatherable plastic of claim 1, wherein, The dosage ratio of the antioxidant 1010, acetone and nano montmorillonite is 3.6-4.5g: 50-80mL: 3-3.6g.

6. The weatherable plastic of claim 1, wherein, The dosage ratio of 1-vinyl-1, 2, 4-triazole, p-methoxyphenol, anhydrous acetonitrile, 1, 5-dibromopentane, 1, 3, 5-tris(bromomethyl)benzene and 1-bromododecane in step S1 is 1.5-2.5g: 0.01-0.02g: 90-100g: 1-2g: 0.4-0.5g: 0.4-0.5g.

7. The weatherable plastic of claim 1, wherein, The dosage ratio of nano montmorillonite, deionized water, octadecyltrimethylammonium chloride, functionalized quaternary ammonium salt and ethanol in step S2 is 10-15g: 500mL: 2-3g: 1.5-3g: 100-200mL.

8. The weatherable plastic of claim 1, wherein, The dosage ratio of di-lauryl thio propionate DLTP and quaternary ammonium salt intercalated organic montmorillonite in step S3 is 5-10g: 10-15g.

9. The weatherable plastic of claim 1, wherein, The preparation steps are as follows: the polypropylene, low-density polyethylene, DLTP-loaded organic montmorillonite, intercalated montmorillonite, crosslinking agent, sulfur, compatibilizer and lubricant are uniformly mixed in a high-speed mixer, then sent into a twin-screw extruder for extrusion granulation to obtain an anti-aging plastic material.

10. Use of the weatherable plastic according to any one of claims 1 to 9, characterized in that It is applied in the fields of automobiles, electronic appliances, buildings and outdoor packaging.

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