Manufacturing method of PC (Polycarbonate) composition for automobile part packaging material

Abstract

The invention provides a manufacturing method of a PC composition for an automobile part packaging material. The manufacturing method comprises the following steps: S1, pretreatment: carrying out vacuum drying on bisphenol A polycarbonate, amino-terminated polyethersulfone grafted modified polycarbonate and a modified nano aluminum nitride-polyaryletherketone compound at 100-120 DEG C for 4-6 hours; mixing an antistatic agent with absolute ethyl alcohol according to a mass ratio of 1: 3; drying other raw materials at 70-80 DEG C for 2-3 hours; s2, mixing: adding the pretreated solid components into a high-speed mixer, mixing at 500-700r / min for 15-20min, adding an antistatic agent solution in two times, and continuously mixing for 6-8min after adding each time; s3, extruding and granulating, namely adding the mixed material into a co-rotating twin-screw extruder for extruding, cooling extruded material strips with water, and granulating; and S4, molding: molding the master batch obtained in S3 by using an injection molding machine to obtain the product. The automobile part packaging box prepared from the PC composition has excellent mechanical properties, processing stability, aging resistance, flame retardance, antistatic property, wear resistance and thermal conductivity, and meets the packaging requirements of various automobile parts.

Description

Technical Field

[0001] This invention relates to the field of packaging materials technology, and more specifically to a method for manufacturing a PC composition for automotive parts packaging materials. Background Technology

[0002] Polycarbonate (PC), as a high-performance engineering plastic, possesses excellent mechanical strength, weather resistance, and processing fluidity, and has been widely used in the field of automotive parts packaging, providing basic protection for the components. As the automotive industry moves towards lightweighting and high precision, non-metallic additive materials, with their advantages of flexible molding, high customization, and controllable cost, are increasingly used in the manufacturing of precision automotive parts. These parts place higher demands on the protective performance of packaging materials, requiring effective prevention of damage during transportation and storage.

[0003] However, traditional PC packaging materials or conventional modified PC materials have obvious shortcomings: on the one hand, the interfacial compatibility between components is poor, making it difficult to balance rigidity and toughness, and easily causing deformation or brittleness during transportation collisions, affecting the reliability of protection; on the other hand, for precision parts used in non-metallic additive manufacturing, existing materials lack sufficient wear resistance, thermal conductivity and antistatic synergistic properties, which can easily cause scratches on the surface of parts, electrostatic damage or heat accumulation affecting dimensional accuracy, making it difficult to meet their high-standard packaging protection requirements. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention provides a method for manufacturing a PC composition for automotive parts packaging materials, which enables automotive parts packaging boxes made from the PC composition to have excellent mechanical properties, processing stability, aging resistance, flame retardancy, antistatic properties, and wear resistance and thermal conductivity, thus meeting the packaging needs of various automotive parts.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This application discloses a method for manufacturing a PC composition for automotive parts packaging materials. The PC composition comprises, by weight, 65-80 parts of bisphenol A polycarbonate, 3-8 parts of amino-terminated polyethersulfone grafted modified polycarbonate, 2-6 parts of modified nano-aluminum nitride-polyaryletherketone composite, 4-9 parts of polyolefin elastomer grafted maleic anhydride, 0.5-1.5 parts of compatibilizer, 0.3-0.9 parts of antioxidant, 5-12 parts of flame retardant, 0.4-1.2 parts of lubricant, 0.6-1.4 parts of antistatic agent, and 0.2-0.7 parts of light stabilizer. The method for manufacturing the PC composition includes the following steps: S1. Preprocessing: Bisphenol A polycarbonate, amino-terminated polyethersulfone grafted modified polycarbonate, and modified nano-aluminum nitride-polyaryletherketone composite were vacuum dried at 100-120℃ for 4-6 hours, with the moisture content controlled to ≤0.03%. Mix the antistatic agent with anhydrous ethanol at a mass ratio of 1:3 to form an antistatic agent solution. Other raw materials are dried at 70-80℃ for 2-3 hours, with the moisture content controlled to be ≤0.1%; S2, Mixing: Add the pretreated solid components to a high-speed mixer and mix at 500-700 r / min for 15-20 min. Add the antistatic agent solution in two portions, and continue mixing for 6-8 min after each addition. Control the mixing temperature to ≤60℃. S3, Extrusion granulation: The mixture is fed into a co-rotating twin-screw extruder for extrusion. The temperature of the extruder is 220-240℃ in zone 1, 240-260℃ in zone 2, 250-270℃ in zone 3, 260-280℃ in zone 4, and 250-270℃ at the die head. The screw speed is 300-450 r / min, the feeding speed is 20-35 kg / h, and the vacuum degree is -0.07 MPa to -0.09 MPa. The extruded strip is water-cooled at 25-35℃ and then pelletized, with an average particle size of 2-3 mm. S4, Molding: After drying the masterbatch obtained from S3 at 100-110℃ for 3-5 hours, it is molded using an injection molding machine with a barrel temperature of 240-270℃, a mold temperature of 70-90℃, an injection pressure of 80-110MPa, a holding pressure of 50-70MPa, and a holding time of 10-18s to obtain the finished product.

[0006] Using the above technical solution, bisphenol A polycarbonate forms the basic mechanical framework, amino-terminated polyethersulfone grafted modified polycarbonate and compatibilizer synergistically strengthen the interfacial bonding of each component, polyolefin elastomer grafted with maleic anhydride improves the material's impact resistance, and modified nano-aluminum nitride-polyaryletherketone composite imparts good thermal conductivity and wear resistance to the material; antioxidants and light stabilizers jointly delay material aging, flame retardants ensure the material's flame retardant safety, antistatic agents reduce the material's surface resistivity, and lubricants optimize processing fluidity. After pretreatment, uniform mixing, precise extrusion granulation, and injection molding processes, the finished product possesses excellent mechanical properties, processing stability, aging resistance, flame retardancy, antistatic properties, and wear resistance and thermal conductivity, making it suitable for automotive parts packaging applications related to non-metallic additive materials.

[0007] Preferably, the number average molecular weight of bisphenol A polycarbonate is 20,000-30,000 Da; the grafting rate of maleic anhydride onto the polyolefin elastomer is 1.0-1.5%, and the number average molecular weight is 15,000-25,000 Da.

[0008] Using the above technical solution, bisphenol A polycarbonate can construct a stable basic mechanical framework, ensuring the core load-bearing capacity and structural integrity of the material; maleic anhydride is grafted onto a polyolefin elastomer with a grafting rate of 1.0-1.5% and a number average molecular weight of 15000-25000 Da. The anhydride groups can effectively react with the amino groups of the amino-terminated polyether sulfone grafted and modified polycarbonate to improve interfacial compatibility. The elastic segments can efficiently absorb impact energy, synergistically giving the material good low-temperature impact resistance.

[0009] Preferably, the compatibilizer is at least one of KH-550, KH-560, and KH-570, and the antioxidant is at least one of antioxidant 1076, antioxidant 168, and antioxidant 626.

[0010] Using the above technical solution, at least one of KH-550, KH-560, and KH-570 is used as a compatibilizer. Its silane group can react with the amino groups of amino-terminated polyethersulfone grafted modified polycarbonate and the hydroxyl groups of modified nano-aluminum nitride-polyaryletherketone composite, reducing the separation between components and improving the interfacial bonding stability. Antioxidant 1076 (hindered phenol) can capture free radicals, and antioxidants 168 and 626 (phosphite) can decompose hydrogen peroxide. The antioxidant system composed of at least one of the three can synergistically delay the thermo-oxidative aging of the material and maintain the performance stability of the material for long-term use.

[0011] Preferably, the flame retardant is one of bisphenol A-bis(diphenyl phosphate) or ammonium polyphosphate; the lubricant is one of N,N'-ethylene bis-stearamide, pentaerythritol stearate or calcium stearate; the antistatic agent is one of quaternary ammonium salt type antistatic agent HT-300 or antistatic agent SN; and the light stabilizer is one of ultraviolet absorber UV-327, ultraviolet absorber UV-531 or hindered amine light stabilizer 770.

[0012] Using the above technical solution, bisphenol A-bis(diphenyl phosphate) or ammonium polyphosphate is used as a flame retardant, which can achieve the flame retardant function of the material through the corresponding flame retardant mechanism; N,N'-ethylene bis-stearamide, pentaerythritol stearate or calcium stearate is used as a lubricant, which can reduce melt viscosity, increase melt flow rate and improve the surface finish of the material; quaternary ammonium salt antistatic agent HT-300 or antistatic agent SN is used as an antistatic agent, which can migrate to the material surface to form a conductive film, reduce surface resistivity and avoid electrostatic damage to precision parts; UV absorber UV-327, UV absorber UV-531 or hindered amine light stabilizer 770 is used as a light stabilizer, which can absorb ultraviolet rays of a specific wavelength, prevent polycarbonate molecular chain breakage and improve the outdoor weather resistance of the material.

[0013] Preferably, the raw materials of the amino-terminated polyethersulfone grafted modified polycarbonate, by weight, include: 75-85 parts of bisphenol A polycarbonate oligomer, 10-18 parts of amino-terminated polyethersulfone, 2-4 parts of toluene diisocyanate, 0.1-0.3 parts of dibutyltin dilaurate, and 50-70 parts of anhydrous toluene.

[0014] Using the above technical solution, bisphenol A polycarbonate oligomers provide the basic framework for graft modification, amino-terminated polyethersulfone provides aromatic ring structure, flexible ether bonds and amino active sites, toluene diisocyanate achieves grafting by reacting its -NCO group with the -OH of bisphenol A polycarbonate oligomers and the -NH2 of amino-terminated polyethersulfone, dibutyltin dilaurate acts as a catalyst to promote efficient reaction, and anhydrous toluene acts as a solvent to promote uniform dispersion and dissolution of each raw material. The amino-terminated polyethersulfone graft-modified polycarbonate obtained by the joint preparation of each component can improve the rigidity, high temperature resistance and impact resistance of polycarbonate, and at the same time provide active sites for subsequent chemical bonding with other components.

[0015] Preferably, the number average molecular weight of the bisphenol A polycarbonate oligomer is 2500-3500 Da, and the number average molecular weight of the amino-terminated polyether sulfone is 3000-4000 Da.

[0016] Using the above technical solution, bisphenol A polycarbonate oligomers with a number average molecular weight of 2500-3500 Da have suitable reactivity and solubility, and can be used as the basic framework for grafting reactions. The -OH groups contained therein can react efficiently with the -NCO groups of toluene diisocyanate. The amino-terminated polyethersulfone with a number average molecular weight of 3000-4000 Da can ensure the reasonable distribution of aromatic rings, flexible ether bonds and amino active sites.

[0017] Preferably, the preparation method of amino-terminated polyethersulfone grafted modified polycarbonate includes the following steps: 1) Add bisphenol A polycarbonate oligomer to anhydrous toluene and stir at 200-300 r / min at 80-90℃ to dissolve it, controlling the water content of the system to ≤0.02%; then purge with nitrogen for protection, add amino-terminated polyethersulfone and dibutyltin dilaurate and stir evenly, raise the temperature to 100-110℃ and keep the reaction at this temperature for 1.5-2.5h; 2) Slowly add toluene diisocyanate dropwise to the reaction system obtained in 1), and continue to keep the reaction at the temperature for 2.5-3.5 h after the addition is complete; 3) The reactants obtained in 2) are heated to 120-130℃ and toluene is removed under a vacuum of -0.08MPa to -0.095MPa. Then, the molten strip is extruded through a twin-screw extruder (barrel temperature 200-220℃, screw speed 250-300r / min). After the extruded strip is cooled to 50-60℃, it is granulated to obtain amino-terminated polyethersulfone grafted modified polycarbonate with an average particle size of 1-2mm.

[0018] By adopting the above technical solution, hydrolysis can be avoided by controlling the water content of the system to ≤0.02%, and oxidation can be prevented by nitrogen protection. Under suitable temperature and stirring conditions, the grafting of bisphenol A polycarbonate oligomers (-OH), amino-terminated polyethersulfone (-NH2), and toluene diisocyanate (-NCO) is promoted to achieve efficient reaction. Toluene is removed by vacuum to ensure product purity. Then, amino-terminated polyethersulfone grafted modified polycarbonate with uniform particle size is obtained by twin-screw extrusion pelletizing.

[0019] Preferably, the modified nano-aluminum nitride-polyaryletherketone composite comprises, by weight, 40-50 parts of nano-aluminum nitride, 20-30 parts of polyaryletherketone, 5-8 parts of KH-570, and 20-30 parts of anhydrous ethanol.

[0020] Using the above technical solution, nano-aluminum nitride provides the composite with high thermal conductivity and wear resistance, polyaryletherketone imparts high temperature resistance to the material, KH-570 grafts double bonds onto the surface of nano-aluminum nitride through the reaction of its siloxane groups with the -OH group, and anhydrous ethanol promotes the uniform dispersion of each raw material to ensure sufficient reaction. The modified nano-aluminum nitride-polyaryletherketone composite obtained by the above method has wear resistance, thermal conductivity and high temperature resistance. Moreover, the double bonds introduced by KH-570 can react with the -NH2 of amino-terminated polyethersulfone grafted modified polycarbonate to achieve synergistic effect between components.

[0021] Preferably, the particle size of the nano-aluminum nitride is 40-70 nm, and the number average molecular weight of the polyarylether ketone is 3500-4500 Da.

[0022] Using the above technical solution, nano-aluminum nitride with a particle size of 40-70nm has good dispersibility and can give full play to its high thermal conductivity and wear resistance; polyaryletherketone with a number average molecular weight of 3500-4500Da can be efficiently melt-composite with modified nano-aluminum nitride to ensure stable performance of high temperature resistance.

[0023] Preferably, the preparation method of the modified nano-aluminum nitride-polyaryletherketone composite includes the following steps: (1) Add nano aluminum nitride to anhydrous ethanol and ultrasonically disperse it at a power of 350-450W for 40-60min to form a uniform suspension; (2) Add KH-570 to the suspension, heat to 80-90℃ and reflux for 2-3 hours, then add polyarylether ketone and stir until uniformly dispersed, heat to 130-140℃ and react under vacuum of -0.08MPa to -0.095MPa for 1.5-2.5 hours; (3) After the system obtained in (2) is cooled to room temperature, it is pulverized by an ultra-micro pulverizer to an average particle size of 20-40 μm to obtain the modified nano aluminum nitride-polyaryletherketone composite.

[0024] Using the above technical solution, ultrasonic dispersion ensures uniform dispersion of nano-aluminum nitride in anhydrous ethanol, avoiding agglomeration and fully utilizing its high thermal conductivity and wear resistance properties; KH-570 and nano-aluminum nitride are grafted and modified through reflux reaction, introducing double bond active sites; under vacuum conditions, polyaryletherketone and modified nano-aluminum nitride are melt-composite, ensuring stable high-temperature resistance; finally, after pulverization, a modified nano-aluminum nitride-polyaryletherketone composite with uniform particle size is obtained, which has wear resistance, thermal conductivity, and high-temperature resistance properties.

[0025] The beneficial effects of this invention are as follows: Bisphenol A polycarbonate forms the basic mechanical framework, while amino-terminated polyethersulfone-grafted modified polycarbonate and compatibilizer synergistically enhance the interfacial bonding of each component. Polyolefin elastomer grafted with maleic anhydride improves the material's impact resistance, and modified nano-aluminum nitride-polyaryletherketone composite imparts good thermal conductivity and wear resistance. Antioxidants and light stabilizers work together to delay material aging, flame retardants ensure the material's flame retardant safety, antistatic agents reduce the material's surface resistivity, and lubricants optimize processing fluidity. Through pretreatment, uniform mixing, precise extrusion granulation, and injection molding processes, the finished product possesses excellent mechanical properties, processing stability, aging resistance, flame retardancy, antistatic properties, and wear resistance and thermal conductivity, making it suitable for automotive parts packaging applications related to non-metallic additive materials.

[0026] Bisphenol A polycarbonate oligomers provide the basic framework for graft modification, while amino-terminated polyethersulfones provide aromatic ring structures, flexible ether bonds, and amino active sites. Toluene diisocyanate achieves grafting by reacting its -NCO groups with the -OH groups of bisphenol A polycarbonate oligomers and the -NH2 groups of amino-terminated polyethersulfones. Dibutyltin dilaurate acts as a catalyst to promote efficient reaction, and anhydrous toluene acts as a solvent to promote uniform dispersion and dissolution of the raw materials. The amino-terminated polyethersulfone graft-modified polycarbonate obtained by the combination of these components can improve the rigidity, high temperature resistance, and impact resistance of polycarbonate, while providing active sites for subsequent chemical bonding with other components. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1: This embodiment discloses a method for manufacturing a PC composition for automotive parts packaging materials. The PC composition comprises, by weight, 65 parts of bisphenol A polycarbonate with a number average molecular weight of 20,000 Da, 3 parts of amino-terminated polyethersulfone grafted modified polycarbonate, 2 parts of modified nano-aluminum nitride-polyaryletherketone composite, 4 parts of polyolefin elastomer grafted with maleic anhydride, 0.5 parts of KH-550, 0.3 parts of antioxidant 1076, 5 parts of bisphenol A-bis(diphenyl phosphate), 0.4 parts of N,N'-ethylene bisstearamide, 0.6 parts of quaternary ammonium salt antistatic agent HT-300, and 0.2 parts of ultraviolet absorber UV-327. The grafting rate of the polyolefin elastomer grafted with maleic anhydride is 1.0%, and the number average molecular weight is 15,000 Da.

[0029] The method for manufacturing the PC composition includes the following steps: S1. Preprocessing: Bisphenol A polycarbonate, amino-terminated polyethersulfone grafted modified polycarbonate, and modified nano-aluminum nitride-polyaryletherketone composite were vacuum dried at 100℃ for 4 h, with the moisture content controlled to be ≤0.03%. The quaternary ammonium salt type antistatic agent HT-300 and anhydrous ethanol were mixed evenly at a mass ratio of 1:3 to form an antistatic agent solution. Other raw materials were dried at 70℃ for 2 hours, with the moisture content controlled to be ≤0.1%; S2, Mixing: Add the pretreated solid components to a high-speed mixer and mix at 500 r / min for 15 min. Add the antistatic agent solution in two portions, and continue mixing for 6 min after each addition, while controlling the mixing temperature to ≤60℃. S3, Extrusion granulation: The mixture is fed into a co-rotating twin-screw extruder for extrusion. The temperature of the extruder is 220℃ in zone 1, 240℃ in zone 2, 250℃ in zone 3, 260℃ in zone 4, and 250℃ at the die head. The screw speed is 300 r / min, the feeding speed is 20 kg / h, and the vacuum degree is -0.07 MPa. The extruded strip is granulated after being cooled in water at 25℃, with an average particle size of 2 mm. S4, Molding: After drying the masterbatch obtained from S3 at 100℃ for 3 hours, it was molded using an injection molding machine with a barrel temperature of 240℃, a mold temperature of 70℃, an injection pressure of 80MPa, a holding pressure of 50MPa, and a holding time of 10s to obtain the finished product.

[0030] The raw materials of the amino-terminated polyethersulfone grafted modified polycarbonate, by weight, include: 75 parts of bisphenol A polycarbonate oligomer with a number average molecular weight of 2500 Da, 10 parts of amino-terminated polyethersulfone with a number average molecular weight of 3000 Da, 2 parts of toluene diisocyanate, 0.1 parts of dibutyltin dilaurate, and 50 parts of anhydrous toluene.

[0031] The preparation method of amino-terminated polyethersulfone grafted modified polycarbonate includes the following steps: 1) Add bisphenol A polycarbonate oligomer to anhydrous toluene and stir at 200 r / min at 80℃ to dissolve it, controlling the water content of the system to ≤0.02%; then purge with nitrogen for protection, add amino-terminated polyethersulfone and dibutyltin dilaurate and stir evenly, raise the temperature to 100℃ and keep the reaction at this temperature for 1.5 h; 2) Slowly add toluene diisocyanate dropwise to the reaction system obtained in 1), and continue to keep the reaction at the temperature for 2.5 h after the addition is complete; 3) The reactants obtained in 2) were heated to 120°C and toluene was removed under a vacuum of -0.08 MPa. The molten material was then extruded through a twin-screw extruder (barrel temperature 200°C, screw speed 250 r / min). The extruded material was cooled to 50°C and then pelletized to obtain amino-terminated polyethersulfone grafted modified polycarbonate with an average particle size of 1 mm.

[0032] The modified nano-aluminum nitride-polyaryletherketone composite is composed of the following raw materials by weight: 40 parts of nano-aluminum nitride with a particle size of 40 nm, 20 parts of polyaryletherketone with a number average molecular weight of 3500 Da, 5 parts of KH-570, and 20 parts of anhydrous ethanol.

[0033] The preparation method of the modified nano-aluminum nitride-polyaryletherketone composite includes the following steps: (1) Add nano aluminum nitride to anhydrous ethanol and ultrasonically disperse at 350W for 40min to form a uniform suspension; (2) Add KH-570 to the suspension, heat to 80℃ and reflux for 2h, then add polyarylether ketone and stir until uniformly dispersed, heat to 130℃ and react for 1.5h under vacuum of -0.08MPa; (3) After the system obtained in (2) is cooled to room temperature, it is pulverized by an ultra-micro pulverizer to an average particle size of 20 μm to obtain the modified nano aluminum nitride-polyaryletherketone composite.

[0034] Example 2: This embodiment discloses a method for manufacturing a PC composition for automotive parts packaging materials. The PC composition comprises, by weight, 80 parts of bisphenol A polycarbonate with a number average molecular weight of 30,000 Da, 8 parts of amino-terminated polyethersulfone grafted modified polycarbonate, 6 parts of modified nano-aluminum nitride-polyaryletherketone composite, 9 parts of polyolefin elastomer grafted with maleic anhydride, 1.5 parts of KH-560, 0.9 parts of antioxidant 168, 12 parts of ammonium polyphosphate, 1.2 parts of N,N'-ethylene bis-stearamide, 1.4 parts of antistatic agent SN, and 0.7 parts of ultraviolet absorber UV-531. The grafting rate of the polyolefin elastomer grafted with maleic anhydride is 1.5%, and the number average molecular weight is 25,000 Da.

[0035] The method for manufacturing the PC composition includes the following steps: S1. Preprocessing: Bisphenol A polycarbonate, amino-terminated polyethersulfone grafted modified polycarbonate, and modified nano-aluminum nitride-polyaryletherketone composite were vacuum dried at 120℃ for 6 h, with the moisture content controlled to be ≤0.03%. Antistatic agent SN and anhydrous ethanol are mixed evenly at a mass ratio of 1:3 to form an antistatic agent solution. Other raw materials were dried at 80℃ for 3 hours, with the moisture content controlled to be ≤0.1%; S2, Mixing: Add the pretreated solid components to a high-speed mixer and mix at 700 r / min for 20 min. Add the antistatic agent solution in two portions, and continue mixing for 8 min after each addition, while controlling the mixing temperature to ≤60℃. S3, Extrusion granulation: The mixture is fed into a co-rotating twin-screw extruder for extrusion. The temperature of the extruder is 240℃ in zone 1, 260℃ in zone 2, 270℃ in zone 3, 280℃ in zone 4, and 270℃ at the die head. The screw speed is 450 r / min, the feeding speed is 35 kg / h, and the vacuum degree is -0.09 MPa. The extruded strip is granulated after being cooled in water at 35℃, with an average particle size of 3 mm. S4, Molding: After drying the masterbatch obtained from S3 at 110℃ for 5 hours, it was molded using an injection molding machine with a barrel temperature of 270℃, a mold temperature of 90℃, an injection pressure of 110MPa, a holding pressure of 70MPa, and a holding time of 18s to obtain the finished product.

[0036] By weight, the raw materials of the amino-terminated polyethersulfone graft-modified polycarbonate include: 85 parts of bisphenol A polycarbonate oligomer with a number average molecular weight of 3500 Da, 18 parts of amino-terminated polyethersulfone with a number average molecular weight of 4000 Da, 4 parts of toluene diisocyanate, 0.3 parts of dibutyltin dilaurate, and 70 parts of anhydrous toluene.

[0037] The preparation method of amino-terminated polyethersulfone grafted modified polycarbonate includes the following steps: 1) Add bisphenol A polycarbonate oligomer to anhydrous toluene and stir at 300 r / min at 90℃ to dissolve it, controlling the water content of the system to ≤0.02%; then purge with nitrogen for protection, add amino-terminated polyethersulfone and dibutyltin dilaurate and stir evenly, raise the temperature to 110℃ and keep the reaction at this temperature for 2.5 h; 2) Slowly add toluene diisocyanate dropwise to the reaction system obtained in 1), and continue to keep the reaction at the temperature for 3.5 h after the addition is complete; 3) The reactants obtained in 2) were heated to 130°C and toluene was removed under a vacuum of -0.095 MPa. The molten material was then extruded through a twin-screw extruder (barrel temperature 220°C, screw speed 300 r / min). The extruded material was cooled to 60°C and then pelletized to obtain amino-terminated polyethersulfone grafted modified polycarbonate with an average particle size of 2 mm.

[0038] The modified nano-aluminum nitride-polyaryletherketone composite is composed of the following raw materials by weight: 50 parts of nano-aluminum nitride with a particle size of 70 nm, 30 parts of polyaryletherketone with a number average molecular weight of 4500 Da, 8 parts of KH-570, and 30 parts of anhydrous ethanol.

[0039] The preparation method of the modified nano-aluminum nitride-polyaryletherketone composite includes the following steps: (1) Add nano aluminum nitride to anhydrous ethanol and ultrasonically disperse at 450W for 60min to form a uniform suspension; (2) Add KH-570 to the suspension, heat to 90℃ and reflux for 3h, then add polyarylether ketone and stir until uniformly dispersed, heat to 140℃ and react under vacuum of -0.095MPa for 2.5h; (3) After the system obtained in (2) is cooled to room temperature, it is pulverized by an ultra-micro pulverizer to an average particle size of 40 μm to obtain the modified nano aluminum nitride-polyaryletherketone composite.

[0040] Example 3: This embodiment discloses a method for manufacturing a PC composition for automotive parts packaging materials. The PC composition comprises, by weight, 72 parts of bisphenol A polycarbonate with a number average molecular weight of 25000 Da, 5 parts of amino-terminated polyethersulfone grafted modified polycarbonate, 4 parts of modified nano-aluminum nitride-polyaryletherketone composite, 7 parts of polyolefin elastomer grafted with maleic anhydride, 1 part of KH-570, 0.6 parts of antioxidant 626, 8 parts of ammonium polyphosphate, 0.8 parts of calcium stearate, 1 part of antistatic agent SN, and 0.4 parts of hindered amine light stabilizer 770. The grafting rate of the polyolefin elastomer grafted with maleic anhydride is 1.2%, and the number average molecular weight is 20000 Da.

[0041] The method for manufacturing the PC composition includes the following steps: S1. Preprocessing: Bisphenol A polycarbonate, amino-terminated polyethersulfone grafted modified polycarbonate, and modified nano-aluminum nitride-polyaryletherketone composite were vacuum dried at 110℃ for 5 h, with the moisture content controlled to be ≤0.03%. Mix the antistatic agent with anhydrous ethanol at a mass ratio of 1:3 to form an antistatic agent solution. Other raw materials were dried at 75℃ for 2.5 hours, with the moisture content controlled to be ≤0.1%; S2, Mixing: Add the pretreated solid components to a high-speed mixer and mix at 500-700 r / min for 17 min. Add the antistatic agent solution in two portions, and continue mixing for 7 min after each addition, while controlling the mixing temperature to ≤60℃. S3, Extrusion granulation: The mixture is fed into a co-rotating twin-screw extruder for extrusion. The temperature of the extruder is 230℃ in zone 1, 250℃ in zone 2, 260℃ in zone 3, 270℃ in zone 4, and 260℃ at the die head. The screw speed is 380 r / min, the feeding speed is 30 kg / h, and the vacuum degree is -0.08 MPa. The extruded strip is granulated after being cooled in water at 30℃, with an average particle size of 2.5 mm. S4, Molding: After drying the masterbatch obtained from S3 at 105℃ for 4 hours, it was molded using an injection molding machine with a barrel temperature of 255℃, a mold temperature of 80℃, an injection pressure of 95MPa, a holding pressure of 60MPa, and a holding time of 14s to obtain the finished product.

[0042] The raw materials of the amino-terminated polyethersulfone graft-modified polycarbonate, by weight, include: 80 parts of bisphenol A polycarbonate oligomer with a number average molecular weight of 3000 Da, 14 parts of amino-terminated polyethersulfone with a number average molecular weight of 3500 Da, 3 parts of toluene diisocyanate, 0.2 parts of dibutyltin dilaurate, and 60 parts of anhydrous toluene.

[0043] The preparation method of amino-terminated polyethersulfone grafted modified polycarbonate includes the following steps: 1) Add bisphenol A polycarbonate oligomer to anhydrous toluene and stir at 250 r / min at 85℃ to dissolve it, controlling the water content of the system to ≤0.02%; then purge with nitrogen for protection, add amino-terminated polyethersulfone and dibutyltin dilaurate and stir evenly, raise the temperature to 105℃ and keep the reaction at this temperature for 2 h; 2) Slowly add toluene diisocyanate dropwise to the reaction system obtained in 1), and continue to keep the reaction at the temperature for 3 hours after the addition is complete; 3) The reactants obtained in 2) were heated to 125°C and toluene was removed under a vacuum of -0.09 MPa. The molten material was then extruded through a twin-screw extruder (barrel temperature 210°C, screw speed 275 r / min). The extruded material was cooled to 55°C and then pelletized to obtain amino-terminated polyethersulfone grafted modified polycarbonate with an average particle size of 1.5 mm.

[0044] The modified nano-aluminum nitride-polyaryletherketone composite is composed of the following raw materials by weight: 45 parts of nano-aluminum nitride with a particle size of 55 nm, 25 parts of polyaryletherketone with a number average molecular weight of 4000 Da, 7 parts of KH-570, and 25 parts of anhydrous ethanol.

[0045] The preparation method of the modified nano-aluminum nitride-polyaryletherketone composite includes the following steps: (1) Add nano aluminum nitride to anhydrous ethanol and ultrasonically disperse at 400W for 50min to form a uniform suspension; (2) Add KH-570 to the suspension, heat to 85℃ and reflux for 2.5h, then add polyarylether ketone and stir until uniformly dispersed, heat to 135℃ and react for 2h under vacuum of -0.09MPa; (3) After the system obtained in (2) is cooled to room temperature, it is pulverized by an ultra-micro pulverizer to an average particle size of 30 μm to obtain the modified nano aluminum nitride-polyaryletherketone composite.

[0046] Comparative Example 1: A method for manufacturing a PC composition for automotive parts packaging materials, differing from Example 3 only in that: no amino-terminated polyethersulfone grafted modified polycarbonate is added.

[0047] Comparative Example 2: A method for manufacturing a PC composition for automotive parts packaging materials, which differs from Example 3 only in that the modified nano-aluminum nitride-polyaryletherketone complex is not added.

[0048] Comparative Example 3: A method for manufacturing a PC composition for automotive parts packaging materials, differing from Example 3 only in that: no polyolefin elastomer grafted with maleic anhydride is added.

[0049] Comparative Example 4: A method for manufacturing a PC composition for automotive parts packaging materials, which differs from Example 3 only in that no compatibilizer (KH-570) is added.

[0050] Comparative Example 5: A method for manufacturing a PC composition for automotive parts packaging materials, which differs from Example 3 only in that no flame retardant (ammonium polyphosphate) is added.

[0051] Comparative Example 6: A method for manufacturing a PC composition for automotive parts packaging materials, which differs from Example 3 only in that no antistatic agent (antistatic agent SN) is added.

[0052] Comparative Example 7: A method for manufacturing a PC composition for automotive parts packaging materials, differing from Example 3 only in that: ordinary polycarbonate is used instead of amino-terminated polyethersulfone grafted modified polycarbonate.

[0053] Comparative Example 8: A method for manufacturing a PC composition for automotive parts packaging materials, differing from Example 3 only in that: ordinary nano-aluminum nitride is used instead of the modified nano-aluminum nitride-polyaryletherketone composite.

[0054] The PC compositions obtained in Examples 1-3 and Comparative Examples 1-8 were subjected to performance tests for tensile strength, notched impact strength, surface resistivity, abrasion resistance (volume abrasion), flame retardancy, heat distortion temperature, melt flow rate, and aging resistance. The test methods and standards are as follows: 1. Tensile strength: According to "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics" (GB / T 1040.2-2006), prepare type 1A specimens (150 mm in length, 10 mm in width, and 4 mm in thickness), and test them on a universal testing machine at a tensile speed of 50 mm / min. Five specimens are tested in each group, and the arithmetic mean is taken as the test result.

[0055] 2. Notched impact strength: According to the "Determination of impact strength of plastic cantilever beam" (GB / T 1843-2021), type A notched specimens (notch depth 2mm, specimen size 80mm×10mm×4mm) were prepared and tested at 23℃ with an impact velocity of 3.5m / s. Five specimens were tested in each group, and the arithmetic mean was taken as the test result.

[0056] 3. Surface resistivity: According to the "Test Method for Volume Resistivity and Surface Resistivity of Solid Insulating Materials" (GB / T1410-2006), a three-electrode system (electrode diameter 50mm, guard ring diameter 70mm) was used. A DC voltage of 500V was applied, and the reading was taken after stabilizing for 30s. The test environment was 23℃ and 50% relative humidity. Three samples were tested in each group, and the arithmetic mean was taken as the test result.

[0057] 4. Wear Resistance (Volume Wear): According to the "Test Method for Sliding Friction and Wear of Plastics" (GB / T 3960-2016), an MM-200 friction and wear testing machine was used. The friction pair was made of 45# steel (hardness HRC45-50). A load of 50N was applied, the sliding speed was 0.5m / s, and the sliding distance was 1000m. The volume wear was calculated by the change in mass and material density of the sample before and after the test. The calculation formula is: Volume wear (mm) 3 = Mass loss (g) / Material density (g / cm³) 3 )×1000, 3 samples were tested in each group, and the arithmetic mean was taken.

[0058] 5. Flame retardant performance: ① Vertical burning rating: According to UL94 standard, a 1.6mm thick sample strip (125mm×13mm×1.6mm) was prepared and subjected to vertical burning test. The ignition time (10s / time, 2 times in total), afterflame time, afterglow time and dripping were recorded to determine the flame retardant rating; ② Limiting oxygen index (LOI): According to "Determination of flammability of plastics by oxygen index method - Part 2: Room temperature test" (GB / T 2406.2-2009), an 80mm×10mm×4mm sample strip was prepared. The oxygen-nitrogen mixture concentration was adjusted in the oxygen index meter to determine the minimum oxygen concentration required for the sample to maintain combustion. Three samples were tested in each group, and the arithmetic mean was taken.

[0059] 6. Heat distortion temperature (HDT): According to "Determination of heat distortion temperature of plastics - Part 2: Plastics, hard rubber and long fiber reinforced composites" (GB / T 1634.2-2004), a 120mm×10mm×4mm sample is prepared, a static load of 1.82MPa is applied, and the sample is heated at a heating rate of 120℃ / h. The temperature at which the deformation of the sample reaches 0.25mm is the heat distortion temperature. Three samples are tested in each group, and the arithmetic mean is taken.

[0060] 7. Melt Flow Rate (MFR): According to the "Determination of Mass Flow Rate and Volumetric Flow Rate of Plastic Melt" (GB / T 3682-2000), under the conditions of 300℃ and 1.2kg load, after preheating for 5min, a sample is cut every 10min for 3 consecutive times. The mass of the sample is weighed and the melt flow rate is calculated. The calculation formula is: MFR (g / 10min) = (sample mass × 10) / cutting time (min). The arithmetic mean of the 3 tests is taken.

[0061] 8. Aging resistance (tensile strength retention rate): According to "Laboratory Light Source Exposure Test Methods for Plastics - Part 2: Xenon Arc Lamp" (GB / T 16422.2-2014), the sample was placed in a xenon lamp aging chamber with an irradiance of 0.71 W / m². 2@340nm, blackboard temperature 65℃, relative humidity 50%, after aging for 1000h, the tensile strength of the aged specimens was tested according to the tensile strength test method, and the retention rate was calculated. The calculation formula is: tensile strength retention rate (%) = (tensile strength after aging / tensile strength before aging) × 100. Five samples were tested in each group, and the arithmetic mean was taken.

[0062] The results are shown in Table 1.

[0063] Table 1 Performance parameters of the PC compositions obtained in Examples 1-3 and Comparative Examples 1-8

[0064] Using Example 3 as the control group, the performance differences and causes of Comparative Examples 1-8 are analyzed as follows: Comparative Example 1 (polycarbonate without terminal amino-terminated polyethersulfone graft modification): tensile strength decreased from 75 MPa to 60 MPa, a decrease of 20%; notched impact strength decreased from 12.0 kJ / m 2 Reduced to 7.0 kJ / m 2 The decrease was 41.7%; the LOI decreased from 34% to 28%, a decrease of 17.6%. The reason is that the lack of the aromatic ring rigidity enhancement effect, ether bond toughening effect and amino interfacial bonding function of this component leads to loose bonding between components, resulting in a significant decrease in mechanical properties and flame retardant efficiency.

[0065] Comparative Example 2 (without modified nano-aluminum nitride-polyaryletherketone composite): surface resistivity increased from 6.8 × 10⁻⁶. 7 Ω increased to 1.2 × 10 9 Ω, an increase of 1664.7%; volumetric wear decreased from 0.65mm. 3 Increased to 1.85mm 3 The increase was 184.6%; HDT decreased from 150℃ to 132℃, a decrease of 12%; and the 1000h aging tensile retention rate decreased from 92% to 78%. This is because the high thermal conductivity and wear resistance of nano-aluminum nitride prevents effective static electricity dissipation, leading to increased friction and wear. Furthermore, the lack of the high-temperature resistant complementary effect of polyaryletherketone (PAK) results in a decrease in heat distortion temperature. The PAK in the modified nano-aluminum nitride-PAK composite possesses excellent aging resistance and synergistically delays material degradation with light stabilizers and antioxidants; its absence significantly reduces aging resistance.

[0066] Comparative Example 3 (without added polyolefin elastomer grafted maleic anhydride): Notched impact strength increased from 12.0 kJ / m 2 Reduced to 8.5 kJ / m 2 The decrease was 29.2%. The reason is that the elastic segments of the toughening agent are not absorbed by the impact energy, and the toughening relies only on the ether bonds of the amino-terminated polyethersulfone grafted modified polycarbonate, resulting in insufficient low-temperature impact resistance.

[0067] Comparative Example 4 (without compatibilizer): Tensile strength decreased from 75 MPa to 58 MPa, a decrease of 22.7%; notched impact strength decreased from 12.0 kJ / m. 2 Reduced to 8.0 kJ / m 2 The decrease was 33.3%. The reason is that without the interfacial bridging effect of compatibilizer, the interfacial bonding between components is weak, and interfacial separation easily occurs under stress, resulting in a significant decline in mechanical properties.

[0068] Comparative Example 5 (without flame retardant): The flame retardant rating dropped from V-0 to HB, and the LOI decreased from 34% to 25%, a decrease of 26.5%. The reason is the lack of the condensed phase flame retardant effect of ammonium polyphosphate. When polycarbonate burns, it cannot form a dense char layer, resulting in the release of a large amount of combustible gas and complete failure of flame retardant performance.

[0069] Comparative Example 6 (without antistatic agent): Surface resistivity was significantly improved, from 6.8 × 10⁻⁶. 7 Ω increased to 5.5 × 10 12 Ω. The reason is that without an antistatic agent to form a conductive film on the material surface, the weak thermal conductivity of nano-aluminum nitride is insufficient to effectively dissipate static electricity, resulting in the loss of antistatic function.

[0070] Comparative Example 7 (using ordinary polycarbonate instead of amino-terminated polyethersulfone grafted modified polycarbonate): tensile strength decreased from 75 MPa to 65 MPa, a decrease of 13.3%; notched impact strength decreased from 12.0 kJ / m 2 Reduced to 9.0 kJ / m 2 The price dropped by 25%. This is because ordinary polycarbonate lacks aromatic ring reinforcement, ether bond toughening, and amino reactivity, resulting in significantly inferior interfacial compatibility and rigidity-toughness balance compared to amino-terminated polyethersulfone grafted modified polycarbonate.

[0071] Comparative Example 8 (using ordinary nano-aluminum nitride instead of the modified nano-aluminum nitride-polyaryletherketone composite): volumetric wear decreased from 0.65 mm. 3 Increased to 1.20mm 3 The increase was 84.6%; the surface resistivity increased from 6.8×10 7 Ω increased to 9.0 × 10 7 Ω, an increase of 32.4%. The reason is that ordinary nano aluminum nitride is prone to agglomeration, which reduces its thermal conductivity and wear resistance, and lacks the melt composite effect of polyarylether ketone, making it unable to form an effective synergy with other components.

[0072] In summary, amino-terminated polyethersulfone grafted modified polycarbonate achieves a balance between rigidity and toughness through aromatic rings and ether bonds, while amino sites strengthen interfacial bonding. The modified nano-aluminum nitride-polyaryletherketone composite imparts high thermal conductivity and wear resistance to the material, synergistically enhancing its high-temperature resistance. When combined with a compatibilizer, both form a three-dimensional cross-linked network, simultaneously improving rigidity and toughness by over 20%. In synergy with antistatic agents, static electricity discharge efficiency is significantly improved. And when combined with flame retardants, synergistic optimization of flame retardancy and high-temperature resistance is achieved.

[0073] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for manufacturing a PC composition for an automobile parts packaging material, characterized by, The composition of the PC composition includes, in parts by weight, bisphenol A polycarbonate 65-80 parts, amino-terminated polyether sulfone grafted polycarbonate 3-8 parts, modified nano-aluminum nitride-polyaryletherketone composite 2-6 parts, polyolefin elastomer grafted maleic anhydride 4-9 parts, compatibilizer 0.5-1.5 parts, antioxidant 0.3-0.9 parts, flame retardant 5-12 parts, lubricant 0.4-1.2 parts, antistatic agent 0.6-1.4 parts, light stabilizer 0.2-0.7 parts; The method for manufacturing the PC composition includes the following steps: S1, pretreatment: The bisphenol A polycarbonate, the amino-terminated polyether sulfone grafted polycarbonate, and the modified nano-aluminum nitride-polyaryletherketone composite are vacuum dried at 100-120℃ for 4-6h; The antistatic agent is mixed with anhydrous ethanol at a mass ratio of 1:3; The other raw materials are dried at 70-80℃ for 2-3h; S2, mixing: The pretreated solid components are added into a high-speed mixer, mixed at 500-700r / min for 15-20min, and the antistatic agent solution is added in two portions, and after each addition, the mixture is continuously mixed for 6-8min; S3, extrusion granulation: The mixed materials are added into a co-rotating twin-screw extruder for extrusion, and the extruded strip is cut into particles after water cooling; S4, molding: The master batch obtained in S3 is molded by an injection molding machine to obtain the finished product.

2. The method for manufacturing a PC composition for an automotive parts packaging material according to claim 1, characterized by, The number average molecular weight of the bisphenol A polycarbonate is 20000-30000Da; the grafting rate of the polyolefin elastomer grafted maleic anhydride is 1.0-1.5%, and the number average molecular weight is 15000-25000Da.

3. The method for manufacturing a PC composition for an automobile parts packaging material according to claim 1, characterized by, The compatibilizer is at least one of KH-550, KH-560, and KH-570, and the antioxidant is at least one of antioxidant 1076, antioxidant 168, and antioxidant 626.

4. The method for manufacturing a PC composition for an automobile parts packaging material according to claim 1, characterized by, The flame retardant is one of bisphenol A-bis(diphenyl phosphate) or ammonium polyphosphate, the lubricant is one of N,N'-ethylene bis-stearamide, pentaerythritol stearate, or calcium stearate, and the light stabilizer is one of ultraviolet absorber UV-327, ultraviolet absorber UV-531, or hindered amine light stabilizer 770.

5. The method for manufacturing a PC composition for an automobile parts packaging material according to claim 1, characterized by, The composition of the amino-terminated polyether sulfone grafted polycarbonate includes, in parts by weight, bisphenol A polycarbonate oligomer 75-85 parts, amino-terminated polyether sulfone 10-18 parts, toluene diisocyanate 2-4 parts, dibutyltin dilaurate 0.1-0.3 parts, and anhydrous toluene 50-70 parts.

6. The method for manufacturing a PC composition for an automotive parts packaging material according to claim 5, characterized by, The number average molecular weight of the bisphenol A polycarbonate oligomer is 2500-3500Da, and the number average molecular weight of the amino-terminated polyether sulfone is 3000-4000Da.

7. The method for manufacturing a PC composition for an automobile parts packaging material according to claim 5, characterized by, The method for preparing the amino-terminated polyether sulfone grafted polycarbonate includes the following steps: 1) The bisphenol A polycarbonate oligomer is added into anhydrous toluene, dissolved by stirring at 80-90℃ and a stirring speed of 200-300r / min, and the water content of the system is controlled to be ≤0.02%; then nitrogen is introduced for protection, the amino-terminated polyether sulfone and dibutyltin dilaurate are added and stirred uniformly, the temperature is raised to 100-110℃, and the system is kept at this temperature for 1.5-2.5h; 2) slowly adding toluene diisocyanate into the reaction system obtained in 1), and continuing to heat for 2.5-3.5 hours after the addition is completed; 3) heating the reaction obtained in 2) to 120-130℃, removing toluene under vacuum degree of -0.08MPa to -0.095MPa, and then extruding the melt into a strip through a double-screw extruder, and cutting the extruded strip into particles after cooling to 50-60℃, to obtain an amino-terminated polyether sulfone grafted modified polycarbonate.

8. The method for manufacturing a PC composition for an automotive parts packaging material according to claim 1, characterized by, The modified nano-aluminum nitride-polyaryletherketone composite comprises, in parts by weight, 40-50 parts of nano-aluminum nitride, 20-30 parts of polyaryletherketone, 5-8 parts of KH-570, and 20-30 parts of anhydrous ethanol.

9. The method for manufacturing the PC composition of the packaging material for automobile parts according to claim 8, wherein the nano-aluminum nitride has a particle size of 40-70 nm, and the polyaryletherketone has a number average molecular weight of 3500-4500 Da.

10. The method for manufacturing the PC composition of the packaging material for automobile parts according to claim 8, wherein the method for preparing the modified nano-aluminum nitride-polyaryletherketone composite comprises the following steps: (1) adding nano-aluminum nitride into anhydrous ethanol, and ultrasonically dispersing for 40-60 minutes at a power of 350-450 W to form a uniform suspension; (2) adding KH-570 into the suspension, heating to 80-90℃ to reflux for 2-3 hours, then adding polyaryletherketone and stirring until uniformly dispersed, and heating to 130-140℃, and reacting for 1.5-2.5 hours under vacuum degree of -0.08MPa to -0.095MPa; (3) after the system obtained in (2) is cooled to room temperature, grinding through a super micro grinder to an average particle size of 20-40 μm, to obtain the modified nano-aluminum nitride-polyaryletherketone composite.

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