PES net film for automobile door panel and preparation method of PES net film

Abstract

The invention discloses a PES net film for an automobile door panel and a preparation method of the PES net film, and relates to the technical field of automobile interior materials. The invention discloses a PES net film for an automobile door panel. The modified PES copolymerized polyether sulfone material is prepared from the following raw materials in parts by weight: 20 to 30 parts of modified PES copolymerized polyether sulfone, 10 to 15 parts of ethylene-vinyl acetate copolymer, 8 to 12 parts of linear low-density polyethylene, 5 to 8 parts of butadiene styrene rubber, 3 to 6 parts of modified nano silicon dioxide, 2 to 4 parts of mica powder, 3 to 5 parts of decabromodiphenyl ether, 0.5 to 1 part of antioxidant 1010, 0.3 to 0.6 part of phenyl salicylate, 0.2 to 0.4 part of zinc stearate and 0.3 to 0.5 part of silane coupling agent KH-550. 5 to 8 parts of epoxidized soybean oil, 0.5 to 1 part of sodium benzoate and 0.1 to 0.3 part of graphene. The PES net film for the automobile door panel has remarkable advantages. In the aspect of raw materials, PES copolymerized polyethersulfone and nano silicon dioxide are modified in multiple steps and are cooperated with multiple auxiliaries. And in the process, conditions of each step are accurate, and the reaction and mixing effects are guaranteed. In the product structure, all the components are tightly interwoven, the net film is endowed with excellent flexibility, adhesion, flame retardance and the like, the comprehensive performance is excellent, and the net film is suitable for manufacturing automobile door panels.

Description

Technical Field

[0001] The present invention relates to the technical field of automotive interior materials, and particularly to a PES web for automotive door panels and a preparation method thereof. Background Art

[0002] At present, with the booming development of the automotive industry, consumers' requirements for the quality of automotive interiors are becoming increasingly stringent. As an important interior component in the vehicle, the material properties of automotive door panels directly affect the overall comfort, safety, and environmental friendliness of the vehicle.

[0003] Traditional automotive door panel materials have many deficiencies. In terms of environmental protection, some materials contain harmful substances such as formaldehyde, which continuously volatilize in the limited space inside the vehicle, seriously threatening the health of passengers and drivers. At the same time, these materials have a strong odor, greatly affecting the riding experience inside the vehicle.

[0004] From the perspective of performance, traditional materials have poor aging resistance. When exposed to sunlight, temperature changes, humidity, and other environments for a long time, they are prone to problems such as fading, deformation, and cracking, which not only affect the aesthetics of the door panels but also reduce their structural stability and functionality. Moreover, the sound insulation, flame retardancy, wear resistance, and other properties of traditional materials are also difficult to meet the requirements of modern vehicles. For example, poor sound insulation results in a large amount of noise inside the vehicle, affecting the quietness of the ride; insufficient flame retardancy cannot effectively delay the spread of fire in case of fire hazards, increasing the safety risk; poor wear resistance makes the door panels easily scratched and damaged during daily use, shortening their service life.

[0005] Existing web materials for automotive door panels also have defects in the bonding performance with other components, resulting in insufficient connection strength between the components of the door panels. During vehicle driving, problems such as loosening and abnormal noise may occur. In addition, with the development of the automotive industry towards lightweight, the disadvantage of the heavy weight of traditional materials has become increasingly prominent, which is not conducive to reducing vehicle energy consumption and increasing the driving range. To solve the above problems, it is urgent to develop a high-performance and environmentally friendly material for automotive door panels. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the present invention provides a PES web for automotive door panels and a preparation method thereof, which solve the above problems.

[0007] To achieve the above object, the present invention is realized through the following technical solutions: A PES web for automotive door panels, comprising the following raw materials in parts by weight: 20 - 30 parts of modified PES copolyethersulfone, 10 - 15 parts of ethylene - vinyl acetate copolymer, 8 - 12 parts of linear low - density polyethylene, 5 - 8 parts of styrene - butadiene rubber, 3 - 6 parts of modified nano - silica, 2 - 4 parts of mica powder, 3 - 5 parts of decabromodiphenyl ether, 0.5 - 1 part of antioxidant 1010, 0.3 - 0.6 part of phenyl salicylate, 0.2 - 0.4 part of zinc stearate, 0.3 - 0.5 part of silane coupling agent KH - 550, 5 - 8 parts of epoxidized soybean oil, 0.5 - 1 part of sodium benzoate, 0.1 - 0.3 part of graphene.

[0008] Furthermore, the preparation steps of the modified PES copolyethersulfone are as follows: A1. In a three - necked flask, dissolve PES copolyethersulfone in dimethylacetamide, add maleic anhydride to the solution, and simultaneously add benzoyl peroxide; place the three - necked flask in an oil bath, and under the protection of nitrogen, stir and react. A2. Pour the reaction product obtained in A1 into a methanol solution containing antioxidant 1010 for precipitation, collect the precipitate by suction filtration, and wash it with methanol; place the washed product in a vacuum drying oven and dry it at 60 °C to obtain graft - modified PES; mix the graft - modified PES with 3 - mercaptopropyltrimethoxysilane, and add dibutyltin dilaurate, and carry out a melt - graft reaction in a twin - screw extruder. A3. Dissolve the product obtained in A2 in tetrahydrofuran, disperse carboxylated single - walled carbon nanotubes in deionized water, and under stirring conditions, drop the carbon nanotube aqueous dispersion into the tetrahydrofuran solution of PES and stir to mix, then pour it into a rotary evaporator for rotary evaporation, and then hot - press the obtained product. A4. Mix the pellets obtained in A3 with nano - silicon carbide, put them into a planetary ball mill for grinding, and add stearic acid during the process to obtain the modified PES copolyethersulfone.

[0009] Furthermore, in A1, the three - necked flask is placed in an oil bath at 110 °C, and stirred continuously at 300 r / min for 8 hours. The dosage ratio of PES copolyethersulfone, dimethylacetamide, maleic anhydride, and benzoyl peroxide is 100 g: 185.7 g: 12 g: 1.12 g; in A2, the drying oven temperature is 60 °C, and dried for 48 hours. The temperature of the twin - screw extruder is 150 °C, and the reaction is carried out for 6 hours. The dosage ratio of antioxidant 1010, methanol, 3 - mercaptopropyltrimethoxysilane, and dibutyltin dilaurate is 0.34 g: 200 mL: 20 g: 1.32 g.

[0010] Furthermore, the stirring speed in A3 is 800r / min, and after the addition of the carbon nanotube aqueous dispersion is completed, stirring is continued for 2 hours; the temperature of rotary evaporation is 70°C, the product is hot-pressed at 300°C, and the dosage ratio of tetrahydrofuran to single-walled carbon nanotubes is 528g:20g; the grinding speed in A4 is 400r / min, grinding is for 12 hours, and the dosage ratio of nano-silicon carbide to stearic acid is 12g:1.6g.

[0011] At 110°C, nitrogen protection and benzoyl peroxide as a free radical initiator, the double bonds of maleic anhydride and the PES copolymer polyethersulfone molecular chain undergo free radical grafting reaction. Benzoyl peroxide decomposes under heat to produce free radicals, which attack the double bonds of maleic anhydride to form active free radical intermediates. The intermediate reacts with the active sites on the PES molecular chain, and after capturing hydrogen atoms, the maleic anhydride free radical combines with the PES molecular chain, thereby successfully introducing anhydride groups on the PES molecular chain, enhancing the reactivity and polarity of PES.

[0012] Dibutyltin dilaurate is used as a catalyst to reduce the activation energy of the reaction. The mercapto group in 3-mercaptopropyltrimethoxysilane reacts with the anhydride group on the grafted PES, and the hydrogen atom of the mercapto group combines with an oxygen atom in the anhydride group to form a thioester bond. At the same time, the anhydride ring opens and introduces silanol groups on the PES molecular chain. After hydrolysis, silanol groups can form silanol groups, which can undergo condensation reactions with hydroxyl groups on the surface of other materials, thereby improving the adhesion and water resistance of PES to other materials.

[0013] Since carbon nanotubes are carboxylated, their surfaces are rich in carboxyl groups, and polar groups such as anhydride groups introduced in the first step and silanol groups generated by hydrolysis of silanoxy groups introduced in the second step exist on the PES molecular chain. There are many interactions between these carboxyl groups and polar groups, such as hydrogen bonding, where the hydrogen atoms on the carboxyl groups form weaker chemical bonds with the electronegative atoms in the polar groups; and electrostatic effects, where the difference in charge carried by different groups makes them attract each other. It is these interactions that enable carbon nanotubes to be evenly dispersed in the PES solution and avoid agglomeration.

[0014] During the grinding process, the long-chain fatty acid molecules of stearic acid are adsorbed on the surface of nano-SiC particles, which reduces the surface energy between particles and reduces the agglomeration phenomenon. At the same time, under the mechanical force of grinding, the nano-SiC particles are evenly dispersed in the granules. Nano-SiC itself has high hardness and good wear resistance. After uniform dispersion, the hardness and wear resistance of the material are effectively improved.

[0015] Furthermore, the modified nano-silicon dioxide is specifically prepared in the following steps: B1. In a round-bottom flask, add a toluene solution containing γ-methacryloxypropyltrimethoxysilane, and then add nano-silica and glacial acetic acid. Heat the round-bottom flask in a water bath and stir for reaction. B2. Centrifuge and separate the nano-silica modified in B1, collect the precipitate, and wash the precipitate with toluene. Place the washed nano-silica in a vacuum drying oven for drying, and add the dried nano-silica to a xylene solution containing butyl acrylate. Add azobisisobutyronitrile, keep it in a constant-temperature water bath, and stir to carry out graft polymerization reaction. B3. Mix the nano-silica modified in B2 with an acetic acid aqueous solution containing chitosan, and shake for reaction. Mix the modified nano-silica with nano-titanium dioxide particles, and disperse and process them using high-speed air flow pulverization technology.

[0016] Further, in B1, the water bath temperature is 90 °C, stir for 6 hours in a nitrogen atmosphere, and the dosage ratio of nano-silica, γ-methacryloxypropyltrimethoxysilane, toluene, and glacial acetic acid is 100 g: 20 g: 80 g: 0.6 g; in B2, the drying oven temperature is 80 °C, dry for 18 hours; the constant-temperature water bath temperature is 70 °C, the stirring speed is 300 r / min, stir for 8 hours, and the dosage ratio of butyl acrylate, xylene, and azobisisobutyronitrile is 10 g: 220 g: 0.1 g.

[0017] Further, in B3, the pH value of the acetic acid aqueous solution is 6, the shaking reaction temperature is 40 °C, shake for 8 hours; use high-speed air flow pulverization technology, under argon protection, disperse and process at an air flow speed of 300 m / s for 2 hours, and the dosage ratio of chitosan, 1% acetic acid aqueous solution, and nano-titanium dioxide is 0.26 g: 13 g: 6.6 g.

[0018] The siloxy group of γ-methacryloxypropyltrimethoxysilane undergoes a chemical reaction with the hydroxyl group on the surface of nano-silica. Glacial acetic acid acts as a catalyst to promote the hydrolysis of the siloxy group, converting it into a silanol group. The silanol group undergoes a condensation reaction with the hydroxyl group on the surface of nano-silica, eliminating one molecule of water, and forming a stable Si-O-Si bond on the surface of nano-silica, thereby introducing a methacryloxy functional group and improving the compatibility between nano-silica and organic polymers.

[0019] Azobisisobutyronitrile decomposes when heated to generate free radicals, and these free radicals initiate the polymerization reaction of the double bond of butyl acrylate. The generated polymer free radicals react with the methacryloxy group on the surface of nano-silica, so that butyl acrylate is grafted onto the surface of nano-silica. The grafted polymer chain increases the interaction between nano-silica and the organic polymer matrix, and further improves the dispersibility and interfacial bonding force of nano-silica in the polymer.

[0020] Chitosan molecular chains contain a large number of amino and hydroxyl groups. Under weakly acidic conditions with a pH value of 6, some of the amino groups will be protonated and carry a positive charge. The surface of nano-silica has a certain negative charge due to previous modification. Through electrostatic and hydrogen bond interactions, chitosan adsorbs on the surface of nano-silica, forming a biocompatible coating and improving the surface properties of nano-silica. Under the impact of high-speed airflow, nano-titanium dioxide particles are dispersed and come into full contact with nano-silica particles. By adjusting the airflow pressure and feed rate, nano-titanium dioxide particles are evenly attached to the surface of nano-silica, endowing the material with functions such as antibacterial and self-cleaning.

[0021] A preparation method of a PES web for automobile door panels specifically includes the following steps: S1. Add the modified PES copolyether sulfone into a high-speed mixer and stir, then add ethylene-vinyl acetate copolymer and raise the temperature for stirring. S2. Sequentially add linear low-density polyethylene and styrene-butadiene rubber, stir evenly, then add the modified nano-silica and mica powder, and continue to raise the temperature and speed for stirring. S3. Sequentially add decabromodiphenyl ether, antioxidant 1010, and phenyl salicylate, stir, then add zinc stearate and silane coupling agent KH-550, and raise the temperature for stirring; add epoxidized soybean oil, sodium benzoate, and graphene, and stir at high temperature until evenly mixed. S4. Transfer the pre-mixed raw materials to an internal mixer for internal mixing, add the internally mixed raw materials to a twin-screw extruder for melt extrusion, introduce the extruded web blank into a stretching machine for biaxial stretching, and cool and shape the stretched web. When the temperature drops to room temperature, the final PES web for automobile door panels is formed.

[0022] Further, in S1, the temperature of the high-speed mixer is 50°C, the stirring speed is 800 r / min, stir for 5 minutes, after adding ethylene-vinyl acetate copolymer, raise the temperature to 70°C, and stir at a speed of 600 r / min for 10 minutes; in S2, after adding linear low-density polyethylene, stir for 8 minutes, then add styrene-butadiene rubber and stir for 10 minutes, then add the modified nano-silica and mica powder, raise the temperature to 90°C, and stir at a speed of 800 r / min for 10 minutes.

[0023] Further, when decabromodiphenyl ether, antioxidant 1010 and phenyl salicylate are added in sequence in S3, after each raw material is added, it is stirred at a speed of 600 r / min at 90 °C for 5 minutes; after zinc stearate and silane coupling agent KH-550 are added, the temperature is raised to 110 °C and stirred at 600 r / min for 10 minutes; in S4, it is stirred at a speed of 600 r / min at 110 °C for 10 minutes; in S5, the mixed raw materials are kneaded and mixed in a kneader at 120 °C for 20 minutes, melted and extruded at 290 °C in a twin-screw extruder, and the screw speed of the extruder is 400 r / min; it is biaxially stretched in a stretching machine at 150 °C, and the stretching ratio is 5 times.

[0024] The present invention provides a PES web for automotive door panels and a preparation method thereof, having the following beneficial effects: 1. Through the cooperation and modification of various raw materials, the PES web of the present invention realizes a comprehensive improvement in performance. In terms of mechanical properties, PES copolyethersulfone is modified in multiple steps, combined with carbon nanotubes and nano-silicon carbide, the tensile strength is increased, and the flexural modulus is improved, effectively enhancing the structural stability of the door panel and making it not easily deformed when subjected to external force impact. In terms of thermal properties, the introduced modified components increase the thermal decomposition temperature, and in a high-temperature environment, the dimensional stability is better and thermal deformation is not likely to occur. In terms of chemical properties, the introduction of groups such as silane oxy groups enhances the chemical corrosion resistance and can effectively resist the erosion of chemical substances such as cleaning agents and rainwater.

[0025] 2. At the environmental protection level, the PES web of the present invention has prominent advantages. It completely abandons harmful substances such as formaldehyde, cutting off the source of air pollution in the car from the source. At the same time, through the action of the low-odor additive graphene, the odor is greatly reduced. After testing, the odor level reaches the industry's high-quality standard, creating a healthy and comfortable in-car environment. In addition, in terms of raw material selection, some raw materials can be recycled and reused, which conforms to the concept of circular economy and plays a demonstration role in the process of environmental protection of automotive interior materials, reducing the potential harm to the environment.

[0026] 3. From the perspective of cost-effectiveness, the PES web of the present invention has obvious advantages. On the one hand, by optimizing the raw material formula and reasonably using raw materials with relatively low prices but excellent performance, such as nano-silica and mica powder, the material cost is reduced while ensuring high performance. On the other hand, its good processing performance reduces the defective rate in the production process, improves the production efficiency, significantly reduces the comprehensive production cost, and improves the economic benefits and market competitiveness of the enterprise.

[0027] 4. The PES mesh of the present invention exhibits excellent adaptability and scalability. Its excellent adhesive properties enable it to firmly bond with various materials commonly used in automotive door panels, such as metals, plastics, fabrics, etc., ensuring the integrity and stability of the door panel structure. At the same time, based on its basic formulation and modification process, the raw material ratio and degree of modification can be flexibly adjusted according to the needs of different automotive brands, models, and usage scenarios, and a variety of derivative materials with specific properties can be developed. For example, for high-end models, its sound insulation and antibacterial properties can be further improved; for economy models, the balance between cost and performance can be optimized, so it can be widely used in the manufacturing field of various automotive door panels. Detailed implementation mode

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of 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 shall fall within the protection scope of the present invention.

[0029] Example 1, preparation of modified PES copolyethersulfone, the specific preparation method is as follows: A1. In a three-necked flask, dissolve 100 g of PES copolyethersulfone in 185.7 g of dimethylacetamide. Add 12 g of maleic anhydride to the solution, and at the same time add 1.12 g of benzoyl peroxide; place the three-necked flask in an oil bath at 110 °C, and under the protection of nitrogen, continuously stir and react at 300 r / min for 8 hours; A2. Pour the reaction product obtained in A1 into a 200 mL methanol solution containing 0.34 g of antioxidant 1010 for precipitation. Collect the precipitate by suction filtration and wash it repeatedly with methanol; place the washed product in a vacuum drying oven and dry it at 60 °C for 48 hours to obtain graft-modified PES; mix the graft-modified PES with 20 g of 3-mercaptopropyltrimethoxysilane, and add 1.32 g of dibutyltin dilaurate, and carry out melt grafting reaction at 150 °C in a twin-screw extruder for 6 hours; A3. Dissolve the product obtained in A2 in 528 g of tetrahydrofuran. Disperse 20 g of carboxylated single-walled carbon nanotubes in deionized water. Under the stirring condition of 800 r / min, drop the carbon nanotube aqueous dispersion into the tetrahydrofuran solution of PES. After dropping, continue to stir for 2 hours, and then rotary evaporate at 70 °C; then hot press the obtained product at 300 °C; A4. Mix the pellets obtained in A3 with 12 g of nano-silicon carbide, put them into a planetary ball mill, and grind at a speed of 400 r / min for 12 hours. During the grinding process, add 1.6 g of stearic acid to obtain modified PES copolyethersulfone.

[0030] Example 2. Preparation of modified nano-silica. The specific preparation method is as follows: B1. In a round-bottom flask, add 80 g of toluene solution containing 20 g of γ-methacryloxypropyltrimethoxysilane, then add 100 g of nano-silica and 0.6 g of glacial acetic acid. Heat the round-bottom flask in a water bath at 90 °C and stir the reaction at 400 / min for 6 hours under nitrogen protection; B2. Centrifuge and separate the nano-silica modified in B1, collect the precipitate, and wash the precipitate with toluene. Place the washed nano-silica in a vacuum drying oven and dry it at 80 °C for 18 hours. Add the dried nano-silica to 220 g of xylene solution containing 10 g of butyl acrylate, add 0.1 g of azobisisobutyronitrile, keep the temperature in a water bath at 70 °C, and continuously stir the reaction at 300 r / min for 8 hours for graft polymerization; B3. Mix the nano-silica modified in B2 with 13 g of acetic acid aqueous solution containing 0.26 g of chitosan, adjust the pH value of the buffer solution to 6, and oscillate the reaction at 40 °C for 8 hours. Mix the modified nano-silica with 6.6 g of nano-titanium dioxide particles, and use the high-speed airflow pulverization technology to disperse and process at an airflow speed of 300 m / s for 2 hours under argon protection to obtain the modified nano-silica.

[0031] Example 3. Preparation of PES mesh for automobile door panels. The specific preparation method is as follows: S1. Add 20 parts of modified PES copolyether sulfone to a high-speed mixer, stir at 800 r / min at 50 °C for 5 minutes, then add 10 parts of ethylene-vinyl acetate copolymer, raise the temperature to 70 °C, and stir at 600 r / min for 10 minutes; S2. Add 8 parts of linear low-density polyethylene and 5 parts of styrene-butadiene rubber in sequence. Stir for 8 minutes after adding each raw material, then add 3 parts of modified nano-silica and 2 parts of mica powder, raise the temperature to 90 °C, and stir at 800 r / min for 10 minutes; S3. Add 3 parts of decabromodiphenyl ether, 0.5 part of antioxidant 1010, and 0.3 part of phenyl salicylate in sequence. Stir at 600 r / min at 90 °C for 5 minutes after adding each raw material, then add 0.2 part of zinc stearate and 0.3 part of silane coupling agent KH-550, raise the temperature to 110 °C, and stir at 600 r / min for 8 minutes. Add 5 parts of epoxy soybean oil, 0.5 part of sodium benzoate, and 0.1 part of graphene, and stir at 600 r / min at 110 °C for 10 minutes; S2. Transfer the pre-mixed raw materials to an internal mixer, mix them at 120 °C for 20 minutes, add the well-mixed raw materials into a twin-screw extruder, melt and extrude at 290 °C, the screw speed of the extruder is 400 r / min, introduce the extruded web blank into a stretching machine, perform biaxial stretching at 150 °C, the stretching ratio is 5 times, and cool and shape the stretched web until the temperature drops to room temperature to form the final PES web for automotive door panels.

[0032] Example 4. Prepare a PES web for automotive door panels. The specific preparation method is as follows: S1. Add 30 parts of modified PES copolyethersulfone into a high-speed mixer, stir at 50 °C at 800 r / min for 5 minutes, then add 15 parts of ethylene-vinyl acetate copolymer, raise the temperature to 70 °C, and stir at 600 r / min for 10 minutes; S2. Add 12 parts of linear low-density polyethylene and 8 parts of styrene-butadiene rubber in sequence, stir for 8 minutes after adding each raw material, then add 6 parts of modified nano-silica and 4 parts of mica powder, raise the temperature to 90 °C, and stir at 800 r / min for 10 minutes; S3. Add 5 parts of decabromodiphenyl ether, 1 part of antioxidant 1010, and 0.6 part of phenyl salicylate in sequence, stir at 90 °C at 600 r / min for 5 minutes after adding each raw material, then add 0.4 part of zinc stearate and 0.5 part of silane coupling agent KH-550, raise the temperature to 110 °C, and stir at 600 r / min for 8 minutes; add 8 parts of epoxidized soybean oil, 1 part of sodium benzoate, and 0.3 part of graphene, and stir at 110 °C at 600 r / min for 10 minutes; S2. Transfer the pre-mixed raw materials to an internal mixer, mix them at 120 °C for 20 minutes, add the well-mixed raw materials into a twin-screw extruder, melt and extrude at 290 °C, the screw speed of the extruder is 400 r / min, introduce the extruded web blank into a stretching machine, perform biaxial stretching at 150 °C, the stretching ratio is 5 times, and cool and shape the stretched web until the temperature drops to room temperature to form the final PES web for automotive door panels.

[0033] Example 5. Prepare a PES web for automotive door panels. The specific preparation method is as follows: S1. Add 25 parts of modified PES copolyethersulfone into a high-speed mixer, stir at 50 °C at 800 r / min for 5 minutes, then add 12 parts of ethylene-vinyl acetate copolymer, raise the temperature to 70 °C, and stir at 600 r / min for 10 minutes; S2. Add 10 parts of linear low-density polyethylene and 6 parts of styrene-butadiene rubber in sequence, stir for 8 minutes after adding each raw material, then add 4 parts of modified nano-silica and 3 parts of mica powder, raise the temperature to 90 °C, and stir at 800 r / min for 10 minutes; S3. Add 4 parts of decabromodiphenyl ether, 0.7 parts of antioxidant 1010, and 0.4 parts of phenyl salicylate in sequence. After adding each raw material, stir at 90 °C at 600 r / min for 5 minutes. Then add 0.3 parts of zinc stearate and 0.4 parts of silane coupling agent KH-550, heat up to 110 °C, and stir at 600 r / min for 8 minutes; add 6 parts of epoxidized soybean oil, 0.7 parts of sodium benzoate, and 0.2 parts of graphene, and stir at 110 °C at 600 r / min for 10 minutes; S2. Transfer the pre-mixed raw materials to an internal mixer, mix them internally at 120 °C for 20 minutes, add the internally mixed raw materials into a twin-screw extruder, melt and extrude at 290 °C, the screw speed of the extruder is 400 r / min, introduce the extruded web blank into a stretching machine, stretch it bidirectionally at 150 °C, the stretching ratio is 5 times, and cool and shape the stretched web until the temperature drops to room temperature to form the final PES web for automotive door panels.

[0034] Comparative Example 1. Prepare a PES web for automotive door panels. The specific preparation method is as follows: Keep the remaining steps unchanged, only replace the modified PES copolyethersulfone in Example 4 with unprocessed PES copolyethersulfone to prepare a PES web for automotive door panels.

[0035] Comparative Example 2. Prepare a PES web for automotive door panels. The specific preparation method is as follows: Keep the remaining steps unchanged, only replace the modified nano-silica in Example 4 with unprocessed nano-silica to prepare a PES web for automotive door panels.

[0036] Test Items Test Methods Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Tensile Strength (MPa) According to the GB / T1040.2 - 2006 standard, using a universal material testing machine, tensile speed 50mm / min 45 48 46 30 32 Tear Strength (N / mm) According to the GB / T529 - 2008 standard, using the trouser tear method, tensile speed 50mm / min 38 40 39 25 27 Peel Strength (N / cm) According to the GB / T2790 - 1995 standard, conduct a 180° peel test on the mesh and common automotive door panel materials (such as PP plastic sheets), tensile speed 100mm / min 32 35 33 18 20 Heat Distortion Temperature (°C) According to the GB / T1634.2 - 2004 standard, measure at a load of 0.45MPa with a heating rate of 120°C / h 120 125 123 100 105 Softening Point (°C) Adopt the ring and ball method (GB / T4507 - 1999 standard), make the sample into a specimen of specified size, put it into the softening point tester, heat at a heating rate of 5°C / min, and record the temperature when the steel ball drops to the specified distance 145 148 146 120 125 Flame Retardancy Performance (Grade) Conduct a vertical burning test according to the UL94 standard V-0 V-0 V-0 V-2 V-2 Aging Resistance Performance (Appearance Change) Place the sample in a xenon lamp aging test chamber, observe after 1000h of light exposure according to the GB / T16422.2 - 2014 standard Slight color change, no obvious deformation or cracking Slight color change, no obvious deformation or cracking Slight color change, no obvious deformation or cracking Obvious color change, with a small number of fine lines Obvious color change, with slight deformation Water Resistance Performance (Water Absorption Rate, %) Immerse the sample in water at 23°C for 48h, measure according to the GB / T1034 - 2008 standard 0.8 0.7 0.8 1.5 1.3 Antibacterial Performance (Bacteriostasis Rate, %) Refer to the GB / T21510 - 2008 standard to test Escherichia coli and Staphylococcus aureus 98 99 98 80 82 Odor Grade (Grade) According to the VDA270 standard, conduct odor discrimination scoring by professional odor discriminators (1 - 6 grades, grade 1 is the best) 2 2 2 4 4 Sound Insulation Performance (Noise Reduction Amount, dB) In the reverberation chamber - anechoic chamber method sound insulation test device, test the average noise reduction amount in the frequency range of 100 - 5000Hz according to the GB / T19889.3 - 2005 standard 25 26 25 18 20 Generally speaking, Examples 3 - 5 have high tensile strength, tear strength, and peel strength, indicating that the mechanical properties of the materials are excellent and can withstand large external forces without being easily damaged; the heat distortion temperature is high, and the flame retardancy reaches V-0 level, reflecting good thermal stability and fire safety; the aging resistance is good, and the appearance changes slightly after 1000 h of light exposure, proving that it can effectively resist the erosion of environmental factors during long-term use; the water resistance is good, the water absorption rate is low, which can reduce the performance degradation caused by water erosion; the antibacterial property is outstanding, the antibacterial rate is high, which helps to maintain the hygiene inside the vehicle; the odor level is low, and the sound insulation performance is good, which can create a comfortable interior environment for the driver and passengers.

[0037] In contrast, Comparative Example 1 and Comparative Example 2 are significantly inferior to Examples 3-5 in terms of various properties. In Comparative Example 1, since the raw materials were not modified, the softening point was lower when facing high temperatures, and it was more likely to soften and deform. At the same time, the mechanical properties, aging resistance, water resistance, etc. were poor, which might affect the service life and safety of automotive door panels. Similarly, in Comparative Example 2, due to the unmodified part of the raw materials, various properties also decreased significantly, failing to meet the high-performance requirements of automotive door panels for materials.

[0038] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the invention or exceed the scope defined by this claim book, they should fall within the protection scope of the present invention.

Claims

1. A PES mesh for automobile door panels, characterized in that: It contains the following raw materials in parts by weight: 20 - 30 parts of modified PES copolyethersulfone, 10 - 15 parts of ethylene - vinyl acetate copolymer, 8 - 12 parts of linear low - density polyethylene, 5 - 8 parts of styrene - butadiene rubber, 3 - 6 parts of modified nano - silica, 2 - 4 parts of mica powder, 3 - 5 parts of decabromodiphenyl ether, 0.5 - 1 part of antioxidant 1010, 0.3 - 0.6 part of phenyl salicylate, 0.2 - 0.4 part of zinc stearate, 0.3 - 0.5 part of silane coupling agent KH - 550, 5 - 8 parts of epoxidized soybean oil, 0.5 - 1 part of sodium benzoate, 0.1 - 0.3 part of graphene.

2. The PES web for automotive door panels according to claim 1, characterized in that: The specific preparation steps of the modified PES copolyethersulfone are as follows: A1. In a three - necked flask, dissolve PES copolyethersulfone in dimethylacetamide, add maleic anhydride to the solution, and simultaneously add benzoyl peroxide; place the three - necked flask in an oil bath, and under the protection of nitrogen, stir and react. A2. Pour the reaction product obtained in A1 into a methanol solution containing antioxidant 1010 for precipitation, collect the precipitate by suction filtration, and wash it with methanol; place the washed product in a vacuum drying oven and dry it at 60 °C to obtain graft - modified PES; mix the graft - modified PES with 3 - mercaptopropyltrimethoxysilane, and add dibutyltin dilaurate, and carry out a melt - graft reaction in a twin - screw extruder. A3. Dissolve the product obtained in A2 in tetrahydrofuran, disperse carboxylated single - walled carbon nanotubes in deionized water, and under stirring conditions, drop the carbon nanotube aqueous dispersion into the tetrahydrofuran solution of PES and stir and mix. Then pour it into a rotary evaporator for rotary evaporation, and then hot - press the obtained product. A4. Mix the pellets obtained in A3 with nano - silicon carbide, put them into a planetary ball mill for grinding, and add stearic acid during the process to obtain modified PES copolyethersulfone.

3. The PES web for automotive door panels according to claim 2, wherein: In A1, the three - necked flask is placed in an oil bath at 110 °C, and stirred continuously at 300 r / min for 8 hours. The dosage ratio of PES copolyethersulfone, dimethylacetamide, maleic anhydride, and benzoyl peroxide is 100 g: 185.7 g: 12 g: 1.12 g; in A2, the drying oven temperature is 60 °C, dried for 48 hours, the twin - screw extruder temperature is 150 °C, and the reaction is 6 hours. The dosage ratio of antioxidant 1010, methanol, 3 - mercaptopropyltrimethoxysilane, and dibutyltin dilaurate is 0.34 g: 200 mL: 20 g: 1.32 g.

4. The PES web for automotive door panels according to claim 2, characterized in that: In A3, the stirring speed is 800 r / min. After the addition of the carbon nanotube aqueous dispersion is completed, continue to stir for 2 hours; the rotary evaporation temperature is 70 °C, and the product is hot - pressed at 300 °C. The dosage ratio of tetrahydrofuran and single - walled carbon nanotubes is 528 g: 20 g; in A4, the grinding speed is 400 r / min, grinding for 12 hours, and the dosage ratio of nano - silicon carbide and stearic acid is 12 g: 1.6 g.

5. A PES web for automotive door panels according to claim 1, characterized in that: The specific preparation steps of the modified nano - silica are as follows: B1. In a round-bottom flask, add a toluene solution containing γ-methacryloxypropyltrimethoxysilane, and then add nano-silica and glacial acetic acid. Heat the round-bottom flask in a water bath and stir to react. B2. Centrifuge and separate the nano-silica modified in B1, collect the precipitate, and wash the precipitate with toluene. Place the washed nano-silica in a vacuum drying oven for drying. Add the dried nano-silica to a xylene solution containing butyl acrylate, add azobisisobutyronitrile, keep it in a constant-temperature water bath, and stir to carry out graft polymerization reaction. B3. Mix the nano-silica modified in B2 with an acetic acid aqueous solution containing chitosan, and shake to react. Mix the modified nano-silica with nano-titanium dioxide particles, and disperse them by high-speed air flow pulverization technology.

6. The PES web for automotive door panels according to claim 5, characterized in that: In B1, the water bath temperature is 90 °C, stir for 6 hours in a nitrogen atmosphere, and the dosage ratio of nano-silica, γ-methacryloxypropyltrimethoxysilane, toluene, and glacial acetic acid is 100 g: 20 g: 80 g: 0.6 g. In B2, the drying oven temperature is 80 °C and dry for 18 hours. The constant-temperature water bath temperature is 70 °C, the stirring speed is 300 r / min, stir for 8 hours, and the dosage ratio of butyl acrylate, xylene, and azobisisobutyronitrile is 10 g: 220 g: 0.1 g.

7. A PES web for automotive door panels according to claim 5, characterized in that: In B3, the pH value of the acetic acid aqueous solution is 6, the shaking reaction temperature is 40 °C, shake for 8 hours. Adopt high-speed air flow pulverization technology, under argon protection, disperse at an air flow speed of 300 m / s for 2 hours, and the dosage ratio of chitosan, 1% acetic acid aqueous solution, and nano-titanium dioxide is 0.26 g: 13 g: 6.6 g.

8. A preparation method of a PES web for an automobile door panel, characterized in that: Specifically, it includes the following steps: S1. Add the modified PES copolyethersulfone to a high-speed mixer and stir, then add ethylene-vinyl acetate copolymer, and raise the temperature and stir. S2. Add linear low-density polyethylene and styrene-butadiene rubber in sequence, stir evenly, then add the modified nano-silica and mica powder, and continue to raise the temperature and speed to stir. S3. Add decabromodiphenyl ether, antioxidant 1010, and phenyl salicylate in sequence, stir, then add zinc stearate and silane coupling agent KH-550, and raise the temperature to stir. Add epoxidized soybean oil, sodium benzoate, and graphene, and stir at high temperature to mix evenly. S4. Transfer the pre-mixed raw materials to an internal mixer for internal mixing. Add the internally mixed raw materials to a twin-screw extruder for melt extrusion. Introduce the extruded web blank into a stretching machine for biaxial stretching. Cool and shape the stretched web, and lower the temperature to room temperature to form the final PES web for automobile door panels.

9. The preparation method of a PES web for automotive door panels according to claim 8, characterized in that: In S1, the temperature of the high-speed mixer is 50 °C, the stirring speed is 800 r / min, stir for 5 minutes, after adding ethylene-vinyl acetate copolymer, raise the temperature to 70 °C, and stir at a speed of 600 r / min for 10 minutes. In S2, after adding linear low-density polyethylene, stir for 8 minutes, then add styrene-butadiene rubber and stir for 8 minutes, then add the modified nano-silica and mica powder, raise the temperature to 90 °C, and stir at a speed of 800 r / min for 10 minutes.

10. The preparation method of a PES web for an automobile door panel according to claim 8, characterized in that: When adding decabromodiphenyl ether, antioxidant 1010, and phenyl salicylate in sequence in S3, after each raw material is added, stir at a speed of 600 r / min at 90°C for 5 minutes; after adding zinc stearate and silane coupling agent KH-550, raise the temperature to 110°C and stir at 600 r / min for 10 minutes. After adding epoxidized soybean oil, sodium benzoate, and graphene, stir at a speed of 600 r / min at 110°C for 10 minutes; in S4, the mixed raw materials are kneaded and mixed in a kneader at 120°C for 20 minutes, and melt-extruded at 290°C in a twin-screw extruder, and the screw speed of the extruder is 400 r / min; perform biaxial stretching in a stretching machine at 150°C, and the stretching ratio is 5 times.