High-toughness regenerated ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof

Abstract

The invention discloses a high-toughness regenerated ABS (Acrylonitrile Butadiene Styrene) composite material and a preparation method thereof, belongs to the technical field of material regeneration, and is used for solving the technical problem that the tensile resistance and flame retardance of a regenerated ABS material in the prior art need to be further improved. The regenerated ABS composite material comprises the following raw materials in parts by weight: 70-80 parts of regenerated ABS, 10-12 parts of a modified toughening agent, 15-18 parts of composite whiskers and 3-6 parts of auxiliary materials, in the process of recycling waste ABS, active groups in ABS chain segments are protected by using a protective agent and a temperature agent, regenerated ABS is obtained by using a solvent purification method, a modified toughening agent and composite whiskers are prepared, and after the regenerated ABS, the modified toughening agent and the composite whiskers are subjected to melt extrusion with auxiliary materials, through the promotion effect of a titanium dioxide component on electron irradiation and through irradiation crosslinking, the modified toughening agent, the composite whiskers and the auxiliary materials are subjected to melt extrusion. Finally, the high-toughness composite ABS is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of material recycling, and particularly relates to a high-toughness recycled ABS composite material and a preparation method thereof. Background Art

[0002] Driven by the demand for sustainable and durable materials, the development of high-toughness recycled ABS has been steadily progressing. Early efforts in the 1990s focused on simply mechanically grinding waste ABS, but this process led to chain degradation, compromising toughness and strength. By the early 2000s, advancements in chemical recycling introduced solvent-based purification and stabilizer additives, restoring molecular integrity and laying the foundation for improved performance. Innovations in the mid-2000s witnessed the addition of elastomeric modifiers and impact additives to enhance flexibility and impact absorption, marking a shift towards tougher recycled ABS. In the 2010s, nanotechnology emerged, adding inorganic fillers and surface-treated reinforcements to improve tensile and compressive strength, addressing early limitations. Current research explores bio-based additives and hybrid reinforcement strategies to further improve mechanical properties and environmental compatibility.

[0003] For example, the prior art CN118638383B discloses a preparation method of a modified ABS material, which includes the following steps: 1) preparing modified silica; 2) preparing a modified mixture; 3) preparing a mixed material; 4) preparing a modified ABS material. The silane coupling agent can perform surface modification on the polymer system and other components, ensuring the contact effect between the modified mixture and other components in the polymer system, so that it can be uniformly filled in the polymer system. Graphene and TPU can improve the toughness of the polymer system, enhancing the adhesion between the polymer system, graphene and other components, thereby improving the mechanical properties of the modified ABS material. The stabilizer can improve the antioxidant performance of the modified ABS material, increase the stability of the components in the system, and prevent the modified ABS material from aging and decomposing.

[0004] However, the above invention only improves the filler dispersion by vapor deposition modification of silica. However, the material lacks the support of a strong and tough structure, and the formation of an intermolecular flexible network is insufficient, making it difficult to effectively dissipate energy, resulting in limited elongation at break and impact resistance. Although the modified silica treated with aluminate coupling agent enhances the interfacial compatibility, the adhesion is limited and the stress transfer efficiency is low, making it difficult to effectively inhibit crack propagation, affecting the tensile strength and toughness. Although microwave treatment improves the material uniformity, it does not form a high-strength molecular cross-linking network, and the binding force between molecular chains is weak, resulting in insufficient overall deformation resistance. These factors together lead to poor flexibility and crack resistance when the material is subjected to external forces, and the toughness and other properties need to be further improved. Summary of the Invention

[0005] The object of the present invention is to provide a highly tough recycled ABS composite material and its preparation method, aiming to solve the technical problem that the tensile resistance and flame retardancy of recycled ABS materials in the prior art need to be further improved.

[0006] The object of the present invention can be achieved by the following technical solutions: A highly tough recycled ABS composite material, comprising the following raw materials by weight: 70 - 80 parts of recycled ABS, 10 - 12 parts of modified toughening agent, 15 - 18 parts of composite whiskers, and 3 - 6 parts of auxiliary materials;

[0007] The preparation method of the modified toughening agent is as follows: Under the protection of nitrogen, add 4,6 - triamino - 1,3,5 - triazine, triethylamine, and anhydrous dichloromethane into the reaction kettle and stir. After the temperature of the reaction kettle drops to 10 - 15 °C, dropwise add 1,4 - benzenedisulfonyl chloride solution into the reaction kettle. After continuously dropwise adding for 1 - 2 h, keep the temperature for reaction for 30 - 40 min, then continue to dropwise add acryloyl chloride solution. After continuously dropwise adding for 20 - 30 min, keep the temperature for reaction for 15 - 20 min, and then perform post - treatment to obtain the modified toughening agent.

[0008] The reaction equation for preparing the modified toughening agent is:

[0009]

[0010] Wherein: 。

[0011] The principle of preparing the modified toughening agent is as follows: Under the protection of nitrogen and at low temperature, the amino group of 4,6 - triamino - 1,3,5 - triazine acts as a nucleophilic reagent. Under the action of triethylamine, it attacks the sulfonyl chloride group of 1,4 - benzenedisulfonyl chloride. The sulfonyl chloride group undergoes a substitution reaction, releasing hydrogen chloride, forming an intermediate containing a sulfonamide bond. Triethylamine and hydrogen chloride form triethylamine salt to maintain the reaction balance. The reaction repeats to form a long - chain structure. After dropping acryloyl chloride, the remaining amino or hydroxyl group of the intermediate reacts with the carbonyl chloride of acryloyl chloride to form a capping structure, and finally the modified toughening agent is prepared.

[0012] Furthermore, the auxiliary materials include the following raw materials by weight: 1 - 2 parts of stabilizer, 1 - 2 parts of lubricant, 0.5 - 1 part of antioxidant, and 0.5 - 1 part of light stabilizer; The stabilizer is one or more of tribasic lead sulfate, calcium stearate, and dibutyltin dilaurate; The lubricant is one or two of calcium stearate and montan wax; The antioxidant is one or two of triphenyl phosphite and dilauryl sulfide; The light stabilizer is methyl 4 - hydroxy - 5 - methoxybenzoate.

[0013] Further, in the process of preparing the modified toughening agent, the dosage ratio of 4,6-triamino-1,3,5-triazine, triethylamine, anhydrous dichloromethane and 1,4-benzenedisulfonyl chloride solution is 5-6 g: 1-2 g: 20-24 mL: 20-24 mL: 10-12 mL. Among them, the 1,4-benzenedisulfonyl chloride solution is obtained by mixing 1,4-benzenedisulfonyl chloride and anhydrous dichloromethane according to the dosage ratio of 3-4 g: 20-24 mL, and the acryloyl chloride solution is obtained by mixing acryloyl chloride and anhydrous dichloromethane according to the dosage ratio of 1-2 g: 10-12 mL. The post-treatment includes: after the reaction kettle is cooled to room temperature, the reaction solution is added into a rotary evaporator with a salt bath temperature of 80-100 °C, and vacuum distillation is carried out until no liquid is collected to obtain the modified toughening agent.

[0014] Further, the preparation method of recycled ABS includes the following steps:

[0015] A1. Using a wall breaker at a temperature of -10 °C, the waste ABS is crushed into particles with a particle size of 3-5 mm, and then the particles are successively transferred to two ultrasonic devices with 3-5 wt% sodium alkylbenzene sulfonate aqueous solution and deionized water as the dispersion media. After soaking and ultrasonicating 3-5 times in the ultrasonic device at 40 °C, post-treatment is carried out to obtain clean ABS particles;

[0016] A2. Under the protection of nitrogen, the clean ABS particles, composite solvent and protective agent are added to a closed stainless steel dissolution kettle and stirred. The temperature of the closed stainless steel dissolution kettle rises to 40-45 °C, and after heat preservation and stirring for 80-100 min, a mixed solution is obtained. After the mixed solution passes through a filter with a pore size of 10 μm, a purified ABS solution is obtained;

[0017] A3. Deionized water and stabilizer are added to a precipitation tank equipped with a stirrer, an ultrasonic generator and a cooling system and stirred. The stirring rate is set to 120-150 rpm, the frequency of the ultrasonic generator is set to 40 kHz, and it is switched on and off at intervals of 5 s. Then the purified ABS solution is dropped into the precipitation tank and added dropwise within 2-3 h, and post-treatment is carried out to obtain recycled ABS.

[0018] The principle of preparing the purified ABS solution is as follows: at -10 °C, the molecular chain flexibility of ABS decreases and approaches a brittle state, thereby reducing plastic deformation and mechanical shear during crushing, reducing mechanical damage, protecting the butadiene double bond, and using low-concentration sodium alkylbenzene sulfonate to reduce the surface tension of water, emulsify oil stains, dust and label adhesives, promote their detachment from the ABS surface, and then drying to obtain clean ABS particles;

[0019] By using N,N-dimethylformamide to enhance the phase dissolution effect, reduce the solution viscosity, decrease local overheating and the molecular chain entanglement energy, 2,6-di-tert-butyl-4-methylphenol terminates the oxidation chain reaction by providing hydrogen atoms, inhibiting the oxidation of the double bonds of butadiene initiated by oxygen or heat, and 2,2,6,6-tetramethylpiperidine-1-oxyl radical captures the carbon radicals generated during the dissolution process, preventing the crosslinking or breaking of double bonds, thereby protecting the active double bond structure in ABS and obtaining a purified ABS solution;

[0020] Then, deionized water is used to reduce the solubility of ABS, triggering the precipitation of ABS molecular chains from the solution. The 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2,6-di-tert-butyl-4-methylphenol in the system continuously inhibit the oxidation of the double bonds exposed during the precipitation process. Under the action of ultrasonic waves, tiny cavitation bubbles are generated, promoting the uniform precipitation of ABS molecular chains to form fine particles. Intermittent operation avoids overheating and increases the surface roughness of the particles, exposing more double bond sites, and obtaining reactive recycled ABS.

[0021] Furthermore, in step A1, the solid-liquid ratio of both ultrasonic devices is 1:10, and the ultrasonic frequency is 40 kHz. The post-treatment includes: feeding the particles into a hot air dryer and drying them under nitrogen protection. The temperature of the hot air dryer is raised to 80 °C, and drying is carried out until the particles reach a constant weight to obtain clean ABS particles;

[0022] Furthermore, in step A2, the dosage ratio of clean ABS particles, composite solvent, and protective agent is 1.0 - 1.2 g:10 mL:0.05 - 0.08 g. Among them, the composite solvent is obtained by mixing methyl ethyl ketone and N,N-dimethylformamide in a dosage ratio of 8 - 9 mL:1 - 2 mL, and the protective agent is obtained by mixing 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2,6-di-tert-butyl-4-methylphenol in a dosage ratio of 8 g:1 - 2 g;

[0023] Furthermore, in step A3, the dosage ratio of deionized water, stabilizer, and purified ABS solution is 10 mL:0.1 - 0.2 g:1 - 2 mL. The stabilizer is obtained by mixing 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2,6-di-tert-butyl-4-methylphenol in a dosage ratio of 8 g:1 - 2 g. The post-treatment includes: after the reaction is completed, when the temperature and pressure of the reaction kettle drop to room temperature and atmospheric pressure, filter the reaction solution to collect the filter cake. After washing the filter cake 3 - 5 times with absolute ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry it to a constant weight to obtain recycled ABS.

[0024] Furthermore, the preparation method of the composite whiskers includes the following steps:

[0025] B1. Add tetrabutyl titanate, absolute ethanol, 3-(methacryloyloxy)propyltrimethoxysilane, and sodium hydroxide aqueous solution into a reaction kettle. After the reaction kettle is sealed, raise the temperature to 160 - 180 °C, keep the temperature for reaction for 16 - 18 h, and perform post-treatment to obtain modified whiskers;

[0026] B2. Under the protection of nitrogen, add the modified whiskers, diphenylphosphine, aluminum chloride, and N,N-dimethylformamide into a reaction kettle. Raise the temperature of the reaction kettle to 30 - 50 °C, keep the temperature for reaction for 1 - 3 h, and perform post-treatment to obtain composite whiskers.

[0027] The reaction principle for preparing the modified whiskers is as follows: In the reaction kettle, tetrabutyl titanate undergoes hydrolysis under the action of absolute ethanol and sodium hydroxide aqueous solution to generate active titanium alcohol. The methoxy groups of 3-(methacryloyloxy)propyltrimethoxysilane are also hydrolyzed to silanol. After hydrothermal reaction, whiskers are obtained, and the methacryloyloxy double bonds on the surface of the modified whiskers are activated under the catalysis of aluminum chloride to enhance their electrophilicity. The P-H bond of phenylphosphine breaks, and the lone pair electrons of the phosphorus atom attack the double bond to form a C-P bond, introducing a phosphorus functional group. Finally, composite whiskers are prepared.

[0028] Further, in step B1, the dosage ratio of tetrabutyl titanate, absolute ethanol, 3-(methacryloyloxy)propyltrimethoxysilane, and sodium hydroxide aqueous solution is 3 - 4 g : 4 - 5 mL : 0.3 - 0.5 g : 40 - 50 mL. Among them, the concentration of the sodium hydroxide aqueous solution is 8 - 10 moL / L, and the pressure of the reaction kettle is 4.5 - 6.3 MPa. The post-treatment includes: after the reaction is completed, wait for the temperature and pressure of the reaction kettle to drop to room temperature and atmospheric pressure, filter the reaction solution to collect the filter cake, wash the filter cake 3 - 5 times with absolute ethanol and deionized water, then transfer the filter cake to a vacuum drying oven at 80 °C, and vacuum dry to constant weight to obtain the modified whiskers;

[0029] Further, in step B2, the dosage ratio of the modified whiskers, diphenylphosphine, aluminum chloride, and N,N-dimethylformamide is 2 - 3 g : 0.5 - 0.6 g : 0.1 - 0.2 g : 10 - 12 mL. The post-treatment includes: after the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake 3 - 5 times with absolute ethanol and deionized water, then transfer the filter cake to a vacuum drying oven at 80 °C, and vacuum dry to constant weight to obtain the composite whiskers.

[0030] The present invention also discloses a preparation method of a high-toughness recycled ABS composite material, including the following steps:

[0031] S1. Add recycled ABS, modified toughening agent, composite whiskers, stabilizer, lubricant, antioxidant, and light stabilizer into a twin-screw extruder, and melt and extrude to obtain an ABS matrix;

[0032] S2. Place the ABS matrix in an electron beam irradiation device. After electron irradiation, a composite ABS is obtained.

[0033] Further, in step S1, the temperatures of the eight temperature zones of the twin-screw extruder from the feed port towards the discharge port are 210 °C, 215, 215 °C, 220 °C, 225 °C, 230 °C, 240 °C, and 240 °C in sequence. The main machine speed of the twin-screw extruder is 120 - 160 rpm, and the pressure is 80 - 120 bar.

[0034] Further, in step S2, the operation of electron irradiation is as follows: Nitrogen is introduced into the electron irradiation device at a flow rate of 15 - 18 L / min for protection. The electron beam energy is set to 2 - 4 MeV, the power is 24 - 28 kW, the radiation dose is 100 - 120 kGy, and the conveyor belt speed is set to 2 - 3 m / min.

[0035] The present invention has the following beneficial effects:

[0036] 1. The recycled ABS prepared by the present invention retains chain activity, forms a stable matrix, ensures a consistent stress distribution during tensile loading. The modified toughening agent has a long-chain structure with reactive double bonds, which can form a flexible entanglement network within the ABS matrix, enhance the deformation ability, and achieve a greater elongation before fracture. The composite whiskers form strong interfacial bonds with the phosphate groups and with the ABS matrix. Titanium dioxide provides high hardness, improves stress transfer, and enhances the material's resistance to tensile force. Under the catalysis of titanium dioxide and driven by the electron beam, the double bonds are opened into free radicals, and radiation crosslinking forms a dense three-dimensional network, strengthening the molecular chain interaction and improving the tensile resistance. Finally, through the synergistic work of the flexibility of the toughening agent, the rigid support of the whiskers, and the structure of the crosslinked network, the composite material ABS can withstand high tensile loads while maintaining significant ductility, thus effectively balancing strength and elongation.

[0037] 2. The composite ABS prepared by the present invention exhibits significant impact resistance through the synergistic mechanism of recycled ABS, modified toughening agent and composite whiskers, which are unified by radiation crosslinking. The recycled ABS retains molecular activity to form a cohesive matrix that can effectively distribute the stress caused by impact. The modified toughening agent utilizes its long chain structure and reactive double bonds to interweave with the ABS matrix to form a flexible network that can absorb impact energy, thereby improving toughness. The composite whiskers, phosphate groups ensure a strong interface bond, and the hardness of titanium dioxide provides structural reinforcement, redirects and dissipates impact force, and prevents the generation of cracks. Under the catalytic action of titanium dioxide, through radiation crosslinking, the electron beam activates the double bonds into free radicals to form a dense, interconnected network, which enhances the stability of the molecular chain to impact loads. The synergistic effect of the energy-absorbing flexibility of the toughening agent, the stress-dispersing stiffness of the whiskers, and the structural elasticity of the crosslinked network ensures that the composite ABS effectively manages impact energy, inhibits crack propagation, and maintains integrity, achieving excellent impact resistance and wear resistance through a unique collaborative framework.

[0038] 3. The cyclic nitrogen structure in the modified toughening agent prepared by the present invention decomposes at high temperature to form a nitrogen-rich carbon layer, which acts as an insulator, prevents heat transfer and flame propagation by limiting the entry of oxygen into the material. The sulfur component is added to the toughening agent and releases sulfur-containing gas when heated, diluting the oxygen concentration in the combustion zone and destroying the sustainability of the fire through the gas phase inhibition mechanism. At the same time, the phosphate groups on the composite whiskers decompose under thermal stress to produce phosphoric acid, which catalyzes the dehydration and carbonization of the polymer matrix, thereby forming a carbonized layer, which further protects the material from the influence of heat and oxygen. The carbonization of the triazine ring structure formed by carbonization, the sulfur release by gas phase inhibition and the phosphate-induced carbonization enhancement are combined to make the material effectively resist ignition, minimize the spread of flames, and maintain structural integrity during fire exposure, providing a comprehensive flame retardant effect through coordinated protection. DETAILED DESCRIPTION

[0039] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] The waste ABS used in the present invention comes from waste materials generated and recycled in the production of the company;

[0041] The montan wax used in the present invention was purchased from Shanghai Dingfen Chemical Technology Co., Ltd., with the product number being P35015;

[0042] The calcium stearate used in the present invention was purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd. with a product number of 1085910.

[0043] Example 1

[0044] This example provides a preparation method of recycled ABS for preparing a high-toughness recycled ABS composite material, including the following steps:

[0045] Step ①, prepare clean ABS particles

[0046] Using a wall breaker at a temperature of -10°C, weigh: 30.0 g of waste ABS is crushed into particles with a particle size of 3 mm, and then the particles are successively transferred to two ultrasonic devices with 3 wt% sodium alkylbenzene sulfonate aqueous solution and deionized water as the dispersion media. After soaking and ultrasonicating 3 times in the ultrasonic device at 40°C, the particles are sent to a hot air dryer and dried under nitrogen protection. The temperature of the hot air dryer is raised to 80°C and kept warm and dried until the particles reach a constant weight to obtain clean ABS particles. Among them, the solid-liquid ratio of the two ultrasonic devices is 1:10, and the ultrasonic frequency is 40 kHz.

[0047] Step ②, prepare a purified ABS solution

[0048] Weigh: 160.0 mL of methyl ethyl ketone and 40.0 mL of N,N-dimethylformamide are mixed to obtain a composite solvent;

[0049] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl and 1.0 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a protective agent;

[0050] Under nitrogen protection, weigh: 20.0 g of clean ABS particles, 200.0 mL of composite solvent and 1.0 protective agent are added to a closed stainless steel dissolution kettle and stirred. The temperature of the closed stainless steel dissolution kettle rises to 40°C, and after keeping warm and stirring for 80 min, a mixed solution is obtained. After passing the mixed solution through a filter with a pore size of 10 μm, a purified ABS solution is obtained.

[0051] Step ③, prepare recycled ABS

[0052] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl and 1.0 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a stabilizer;

[0053] Weigh: 100.0 mL of deionized water and 1.0 g of stabilizer are added to a precipitation tank equipped with a stirrer, an ultrasonic generator and a cooling system and stirred. The stirring rate is set to 120 rpm, the frequency of the ultrasonic generator is set to 40 kHz, and it is switched on and off at intervals of 5 s. Then, 10.0 mL of the purified ABS solution is added dropwise to the precipitation tank. After adding dropwise within 2 h, recycled ABS is obtained after post-treatment.

[0054] Example 2

[0055] This embodiment provides a preparation method of recycled ABS for preparing a high-toughness recycled ABS composite material, including the following steps:

[0056] Step ①: Prepare clean ABS particles

[0057] Using a wall breaker at a temperature of -10°C, weigh: 30.0 g of waste ABS is crushed into particles with a particle size of 5 mm, and then the particles are successively transferred to two ultrasonic devices with 5 wt% sodium alkylbenzenesulfonate aqueous solution and deionized water as the dispersion media. After soaking and ultrasonicating 5 times in the ultrasonic device at 40°C, the particles are sent into a hot air dryer and dried under nitrogen protection. The temperature of the hot air dryer is raised to 80°C and kept warm and dried until the particles reach a constant weight, obtaining clean ABS particles. Among them, the solid-liquid ratio of the two ultrasonic devices is 1:10, and the ultrasonic frequency is 40 kHz.

[0058] Step ②: Prepare a purified ABS solution

[0059] Weigh: 180.0 mL of methyl ethyl ketone and 20.0 mL of N,N-dimethylformamide are mixed to obtain a composite solvent;

[0060] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2.0 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a protective agent;

[0061] Under nitrogen protection, weigh: 24.0 g of clean ABS particles, 200.0 mL of composite solvent, and 1.6 g of protective agent are added to a closed stainless steel dissolution kettle and stirred. The temperature of the closed stainless steel dissolution kettle rises to 45°C, and after keeping warm and stirring for 100 min, a mixed solution is obtained. After passing the mixed solution through a filter with a pore size of 10 μm, a purified ABS solution is obtained.

[0062] Step ③: Prepare recycled ABS

[0063] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2.0 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a stabilizer;

[0064] Weigh: 100.0 mL of deionized water and 2.0 g of stabilizer are added to a precipitation tank equipped with a stirrer, an ultrasonic generator, and a cooling system and stirred. The stirring rate is set to 150 rpm, the frequency of the ultrasonic generator is set to 40 kHz, and it is switched on and off at intervals of 5 s. Then, 20.0 mL of the purified ABS solution is dropped into the precipitation tank. After dropping it within 3 h, recycled ABS is obtained through post-treatment.

[0065] Example 3

[0066] This embodiment provides a preparation method of recycled ABS for preparing a high-toughness recycled ABS composite material, including the following steps:

[0067] Step ①: Prepare clean ABS particles

[0068] Using a wall breaker at a temperature of -10°C, weigh: 30.0 g of waste ABS is crushed into particles with a particle size of 4 mm, and then the particles are successively transferred to two ultrasonic devices with 4 wt% sodium alkylbenzene sulfonate aqueous solution and deionized water as the dispersion media. After soaking and ultrasonicating 4 times in the ultrasonic device at 40°C, the particles are sent into a hot air dryer and dried under nitrogen protection. The temperature of the hot air dryer is raised to 80°C and kept warm and dried until the particles reach a constant weight, obtaining clean ABS particles. Among them, the solid-liquid ratio of the two ultrasonic devices is 1:10, and the ultrasonic frequency is 40 kHz.

[0069] Step ②: Prepare a purified ABS solution

[0070] Weigh: 180.0 mL of methyl ethyl ketone and 30.0 mL of N,N-dimethylformamide are mixed to obtain a composite solvent;

[0071] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 2.0 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a protective agent;

[0072] Under the protection of nitrogen, weigh: 21.0 g of clean ABS particles, 200.0 mL of the composite solvent and 1.2 g of the protective agent are added to a closed stainless steel dissolution kettle and stirred. The temperature of the closed stainless steel dissolution kettle rises to 40°C, and after keeping warm and stirring for 90 min, a mixed solution is obtained. After passing the mixed solution through a filter with a pore size of 10 μm, a purified ABS solution is obtained.

[0073] Step ③: Prepare recycled ABS

[0074] Weigh: 8.0 g of 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 1.6 g of 2,6-di-tert-butyl-4-methylphenol are mixed to obtain a stabilizer;

[0075] Weigh: 100.0 mL of deionized water and 1.6 g of the stabilizer are added to a precipitation tank equipped with a stirrer, an ultrasonic generator and a cooling system and stirred. The stirring rate is set to 120 rpm, the frequency of the ultrasonic generator is set to 40 kHz, and it is switched on and off at intervals of 5 s. Then, 16.0 mL of the purified ABS solution is added dropwise to the precipitation tank. After adding dropwise within 3 h, recycled ABS is obtained after post-treatment.

[0076] Example 4

[0077] This embodiment provides a preparation method of a modified toughening agent for preparing a high-toughness recycled ABS composite material, including the following steps:

[0078] Weigh: 30.0 g of 1,4-benzenedisulfonyl chloride and 200.0 mL of anhydrous dichloromethane are mixed to obtain a 1,4-benzenedisulfonyl chloride solution;

[0079] Weigh: 10.0 g of acryloyl chloride and 100.0 mL of anhydrous dichloromethane are mixed to obtain an acryloyl chloride solution;

[0080] Under the protection of nitrogen, weigh: 50.0 g of 4,6-triamino-1,3,5-triazine, 10.0 g of triethylamine and 200.0 mL of anhydrous dichloromethane are added to the reaction kettle and stirred. After the temperature of the reaction kettle drops to 10 °C, 200.0 mL of the 1,4-benzenedisulfonyl chloride solution is added dropwise to the reaction kettle. After continuously adding dropwise for 1 h, keep the temperature for reaction for 30 min, then continue to add dropwise 100.0 mL of the acryloyl chloride solution. After continuously adding dropwise for 20 min, keep the temperature for reaction for 15 min. After the reaction kettle is cooled to room temperature, the reaction solution is added to a rotary evaporator with a salt bath temperature of 80 °C, and distilled under reduced pressure until no liquid is collected to obtain the modified toughening agent.

[0081] Example 5

[0082] This embodiment provides a preparation method of a modified toughening agent for preparing a high-toughness recycled ABS composite material, including the following steps:

[0083] Weigh: 40.0 g of 1,4-benzenedisulfonyl chloride and 240.0 mL of anhydrous dichloromethane are mixed to obtain a 1,4-benzenedisulfonyl chloride solution;

[0084] Weigh: 20.0 g of acryloyl chloride and 120.0 mL of anhydrous dichloromethane are mixed to obtain an acryloyl chloride solution;

[0085] Under the protection of nitrogen, weigh: 60.0 g of 4,6-triamino-1,3,5-triazine, 20.0 g of triethylamine and 240.0 mL of anhydrous dichloromethane are added to the reaction kettle and stirred. After the temperature of the reaction kettle drops to 15 °C, 240.0 mL of the 1,4-benzenedisulfonyl chloride solution is added dropwise to the reaction kettle. After continuously adding dropwise for 2 h, keep the temperature for reaction for 40 min, then continue to add dropwise 120.0 mL of the acryloyl chloride solution. After continuously adding dropwise for 30 min, keep the temperature for reaction for 20 min. After the reaction kettle is cooled to room temperature, the reaction solution is added to a rotary evaporator with a salt bath temperature of 100 °C, and distilled under reduced pressure until no liquid is collected to obtain the modified toughening agent.

[0086] Example 6

[0087] This embodiment provides a preparation method of a modified toughening agent for preparing a high-toughness recycled ABS composite material, including the following steps:

[0088] Weigh: 36.0 g of 1,4-benzenedisulfonyl chloride and 210.0 mL of anhydrous dichloromethane are mixed to obtain a 1,4-benzenedisulfonyl chloride solution;

[0089] Weigh: 16.0 g of acryloyl chloride and 120.0 mL of anhydrous dichloromethane are mixed to obtain an acryloyl chloride solution;

[0090] Under the protection of nitrogen, weigh: 54.0 g of 4,6-triamino-1,3,5-triazine, 16.0 g of triethylamine and 210.0 mL of anhydrous dichloromethane are added to the reaction kettle and stirred. After the temperature of the reaction kettle drops to 12 °C, 210.0 mL of the 1,4-benzenedisulfonyl chloride solution is added dropwise to the reaction kettle. After continuous dropping for 2 h, keep the temperature for reaction for 36 min, then continue to add dropwise 100.0 mL of the acryloyl chloride solution. After continuous dropping for 25 min, keep the temperature for reaction for 18 min. After the reaction kettle is cooled to room temperature, the reaction solution is added to a rotary evaporator with a salt bath temperature of 90 °C, and distilled under reduced pressure until no liquid is collected to obtain a modified toughening agent.

[0091] Example 7

[0092] This example provides a preparation method of composite whiskers for preparing a high-toughness recycled ABS composite material, including the following steps:

[0093] Step Ⅰ, prepare modified whiskers

[0094] Weigh: 30.0 g of tetrabutyl titanate, 40.0 mL of anhydrous ethanol, 3.0 g of 3-(methacryloyloxy)propyltrimethoxysilane and 400.0 mL of 8 moL / L sodium hydroxide aqueous solution are added to the reaction kettle. After the reaction kettle is sealed, the temperature is raised to 160 °C, the pressure of the reaction kettle is 4.5 MPa, and keep the temperature for reaction for 16 h. After the reaction is completed, wait for the temperature and pressure of the reaction kettle to drop to room temperature and atmospheric pressure, filter the reaction solution to collect the filter cake. After washing the filter cake 3 times with anhydrous ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry to constant weight to obtain modified whiskers.

[0095] Step Ⅱ, prepare composite whiskers

[0096] Under the protection of nitrogen, weigh: 20.0 g of modified whiskers, 5.0 g of diphenylphosphine, 1.0 g of aluminum chloride and 100.0 mL of N,N-dimethylformamide are added to the reaction kettle. The temperature of the reaction kettle is raised to 30 °C and keep the temperature for reaction for 1 h. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution to collect the filter cake. After washing the filter cake 3 times with anhydrous ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry to constant weight to obtain composite whiskers.

[0097] Example 8

[0098] This embodiment provides a preparation method of composite whiskers for preparing a high-toughness recycled ABS composite material, including the following steps:

[0099] Step I. Prepare modified whiskers

[0100] Weigh: 40.0 g of tetrabutyl titanate, 50.0 mL of absolute ethanol, 5.0 g of 3-(methacryloyloxy)propyltrimethoxysilane, and 500.0 mL of 10.0 moL / L sodium hydroxide aqueous solution and add them to a reaction kettle. After the reaction kettle is sealed, the temperature is raised to 180 °C, the pressure in the reaction kettle is 6.3 MPa, and keep the temperature for reaction for 18 h. After the reaction is completed, wait for the temperature and pressure in the reaction kettle to drop to room temperature and atmospheric pressure. Filter the reaction solution by suction to collect the filter cake. After washing the filter cake 5 times with absolute ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry it to constant weight to obtain modified whiskers.

[0101] Step II. Prepare composite whiskers

[0102] Under the protection of nitrogen, weigh: 30.0 g of modified whiskers, 6.0 g of diphenylphosphine, 2.0 g of aluminum chloride, and 120.0 mL of N,N-dimethylformamide and add them to a reaction kettle. Raise the temperature of the reaction kettle to 50 °C and keep the temperature for reaction for 3 h. After the reaction is completed, wait for the temperature in the reaction kettle to drop to room temperature. Filter the reaction solution by suction to collect the filter cake. After washing the filter cake 5 times with absolute ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry it to constant weight to obtain composite whiskers.

[0103] Example 9

[0104] This embodiment provides a preparation method of composite whiskers for preparing a high-toughness recycled ABS composite material, including the following steps:

[0105] Step I. Prepare modified whiskers

[0106] Weigh: 36.0 g of tetrabutyl titanate, 50.0 mL of absolute ethanol, 4.0 g of 3-(methacryloyloxy)propyltrimethoxysilane, and 450.0 mL of 9 moL / L sodium hydroxide aqueous solution and add them to a reaction kettle. After the reaction kettle is sealed, the temperature is raised to 180 °C, the pressure in the reaction kettle is 5.4 MPa, and keep the temperature for reaction for 18 h. After the reaction is completed, wait for the temperature and pressure in the reaction kettle to drop to room temperature and atmospheric pressure. Filter the reaction solution by suction to collect the filter cake. After washing the filter cake 4 times with absolute ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry it to constant weight to obtain modified whiskers.

[0107] Step II. Prepare composite whiskers

[0108] Under the protection of nitrogen, weigh: 25.0 g of modified whiskers, 5.4 g of diphenylphosphine, 1.6 g of aluminum chloride, and 120.0 mL of N,N-dimethylformamide and add them to a reaction kettle. Raise the temperature of the reaction kettle to 40 °C, keep the temperature for reaction for 2 h. After the reaction is completed, wait for the temperature of the reaction kettle to drop to room temperature, filter the reaction solution by suction to collect the filter cake. After washing the filter cake 4 times with absolute ethanol and deionized water, transfer the filter cake to a vacuum drying oven at 80 °C and vacuum dry to constant weight to obtain composite whiskers.

[0109] Example 10

[0110] This example provides a preparation method of a high-toughness recycled ABS composite material, including the following steps:

[0111] Step 1. Prepare the ABS matrix

[0112] Weigh: 70 parts of the recycled ABS prepared in Example 1, 10 parts of the modified toughening agent prepared in Example 4, 15 parts of the composite whiskers prepared in Example 7, 1 part of calcium stearate, 1 part of montan wax, 0.5 part of triphenyl phosphite, and 0.5 part of methyl 4-hydroxy-5-methoxybenzoate and add them to a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port are 210 °C, 215, 215 °C, 220 °C, 225 °C, 230 °C, 240 °C, 240 °C in sequence. The main machine speed of the twin-screw extruder is 120 rpm, the pressure is 80 bar, and melt extrusion is carried out to obtain the ABS matrix.

[0113] Step 2. Prepare the composite ABS

[0114] Place the ABS matrix in an electron beam irradiation device, introduce nitrogen for protection into the electron irradiation device at a flow rate of 15 L / min, set the electron beam energy to 2 MeV, the power to 24 kW, the radiation dose to 100 kGy, and the conveyor belt speed to 2 m / min to obtain the composite ABS.

[0115] Example 11

[0116] This example provides a preparation method of a high-toughness recycled ABS composite material, including the following steps:

[0117] Step 1. Prepare the ABS matrix

[0118] Weigh: 80 parts of the recycled ABS prepared in Example 2, 12 parts of the modified toughening agent prepared in Example 4, 18 parts of the composite whiskers prepared in Example 9, 2 parts of calcium stearate, 2 parts of montan wax, 1 part of triphenyl phosphite, and 1 part of methyl 4-hydroxy-5-methoxybenzoate and add them to a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 210 °C, 215, 215 °C, 220 °C, 225 °C, 230 °C, 240 °C, 240 °C in sequence. The main machine speed of the twin-screw extruder is 160 rpm, the pressure is 120 bar, and melt extrusion is carried out to obtain an ABS matrix.

[0119] Step Two: Prepare Composite ABS

[0120] Place the ABS matrix in an electron beam irradiation device, introduce nitrogen for protection into the electron irradiation device at a flow rate of 18 L / min, set the electron beam energy to 4 MeV, the power to 28 kW, the radiation dose to 120 kGy, and the conveyor belt speed to 3 m / min to obtain composite ABS.

[0121] Example 12

[0122] This example provides a preparation method of a high-toughness recycled ABS composite material, including the following steps:

[0123] Step One: Prepare ABS Matrix

[0124] Weigh: 72 parts of the recycled ABS prepared in Example 3, 12 parts of the modified toughening agent prepared in Example 6, 18 parts of the composite whiskers prepared in Example 9, 1.5 parts of calcium stearate, 1.5 parts of montan wax, 0.8 part of triphenyl phosphite, and 0.8 part of methyl 4-hydroxy-5-methoxybenzoate and add them to a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 210 °C, 215, 215 °C, 220 °C, 225 °C, 230 °C, 240 °C, 240 °C in sequence. The main machine speed of the twin-screw extruder is 120 rpm, the pressure is 100 bar, and melt extrusion is carried out to obtain an ABS matrix.

[0125] Step Two: Prepare Composite ABS

[0126] Place the ABS matrix in an electron beam irradiation device, introduce nitrogen for protection into the electron irradiation device at a flow rate of 16 L / min, set the electron beam energy to 3 MeV, the power to 28 kW, the radiation dose to 100 kGy, and the conveyor belt speed to 3 m / min to obtain composite ABS.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 12 is that during the preparation of the recycled ABS used in Step 1, the use of the protective agent and stabilizer was cancelled.

[0129] Comparative Example 2

[0130] The difference between this comparative example and Example 12 is that during the preparation of the modified toughening agent used in Step 1, the use of the acryloyl chloride solution was cancelled.

[0131] Comparative Example 3

[0132] The difference between this comparative example and Example 12 is that during the preparation of the composite whiskers used in Step 1, Step II was cancelled.

[0133] Performance Test:

[0134] With reference to the standard GB / T 1040.1-2018 "Plastics - Determination of tensile properties - Part 1: General principles", the tensile strength and elongation at break of the composite ABS prepared in Examples 10 - 12 were determined;

[0135] With reference to the standard GB / T 1843-2008 "Plastics - Determination of Izod impact strength", the Izod impact strength of the composite ABS prepared in Examples 10 - 12 and Comparative Examples 1 - 3 was determined;

[0136] With reference to the standard GB / T 9867-2008 "Rubber, vulcanized or thermoplastic - Determination of abrasion resistance (rotary roller abrader method)", the volume abrasion loss of the composite ABS prepared in Examples 10 - 12 and Comparative Examples 1 - 3 was tested;

[0137] With reference to the standard GB / T 26526-2011 "Plastics - Determination of combustion behavior by the oxygen index method - Part 2: Room temperature test", the limiting oxygen index of the composite ABS prepared in Examples 10 - 12 and Comparative Examples 1 - 3 was tested. The specific data are shown in Table 1.

[0138] Table 1 - Performance test data table of each specimen

[0139]

[0140] Data Analysis:

[0141] After comparative analysis of the data in Table 1, it can be found that the tensile strength of the composite ABS prepared by the present invention is 48.1 MPa, the elongation at break is 37.2%, the Izod impact strength is 57 kJ·m -2 ³, the volume abrasion loss is 21 mm 3 ³, and the limiting oxygen index is 39.0% at the same time. All data are better than those of the comparative examples;

[0142] After comparative analysis of the data in Table 1, it can be found that the tensile strength and elongation at break of the composite ABS prepared in Comparative Examples 1-3 are significantly lower than those of the composite ABS prepared in Example 12, indicating that:

[0143] In Comparative Example 1, due to the cancellation of the stabilizer and protective agent in the preparation of recycled ABS, the active groups were not effectively protected, the chain segment structure was damaged, resulting in a decrease in the mechanical properties of the recycled ABS as the matrix, a reduction in the stress transfer efficiency between molecules, and a weakening of the tensile strength and elongation at break. Compared with the example, the lack of protection makes the matrix lack flexibility and strength, and it is difficult to withstand tensile loads or maintain ductility;

[0144] In Comparative Example 2, due to the cancellation of the acryloyl chloride solution capping in the preparation of the modified toughening agent, the number of active double bonds decreased, the entanglement and crosslinking potential between molecular chains decreased, the formation of the flexible network was limited, and the tensile strength and elongation at break decreased. Compared with the example, the lack of the strengthening effect of double bonds makes the deformation ability of the material weakened during stretching and the toughness insufficient;

[0145] In Comparative Example 3, due to the cancellation of the phosphorus structure modification in the preparation of the composite whiskers, the chemical bonding between the interface and the matrix decreased, the stress transfer efficiency decreased, and the rigid support effect of the whiskers weakened, resulting in a decrease in the tensile strength and elongation at break. Compared with the example, the lack of interface optimization by phosphorus modification makes the material prone to crack propagation during stretching and the ductility is limited;

[0146] Therefore, all three cases lead to insufficient flexibility of the matrix, interfacial adhesion, and molecular network strength due to the lack of modification steps, and the tensile strength and elongation at break are significantly weaker than those of Example 12.

[0147] After comparative analysis of the data in Table 1, it can be found that the impact resistance and wear resistance of the composite ABS prepared in Comparative Examples 1-3 are significantly lower than those of the composite ABS prepared in Example 12, indicating that:

[0148] In Comparative Example 1, due to the cancellation of the stabilizer and protective agent in the preparation of recycled ABS, the active groups were not protected, the chain segment structure was damaged, resulting in a decrease in the stability of the matrix molecular network, and both the impact resistance and wear resistance were significantly weakened. During impact, the matrix is difficult to effectively disperse energy and is prone to brittle fracture. In terms of wear resistance, the damage of molecular chains reduces the surface hardness and durability of the material, making it easy to wear. Compared with the example, the matrix lacking protection cannot withstand impact or friction;

[0149] In Comparative Example 2, due to the cancellation of acryloyl chloride capping in the preparation of the modified toughening agent, the number of active double bonds decreased, the formation of the flexible network was limited, and the impact energy absorption ability decreased, resulting in a weakening of the impact resistance; at the same time, the reduction of double bonds weakens the crosslinking density, the surface hardness is insufficient, and the wear resistance decreases. Compared with the example, the lack of the toughening effect of double bonds makes the material lack impact resistance and wear resistance;

[0150] In Comparative Example 3, due to the cancellation of phosphorus structure modification in the preparation of composite whiskers, the interfacial bonding force between the whiskers and the matrix decreases, the stress dispersion during impact is uneven, cracks are easily initiated, and the impact resistance decreases; in terms of wear resistance, the weakening of the interface reduces the rigid protection effect of the whiskers, and the surface is easily worn. Compared with the examples, the lack of phosphorus-modified interface optimization results in significantly lower impact resistance and wear resistance than the examples.

[0151] After comparative analysis of the data in Table 1, it can be found that the flame retardancy of the composite ABS prepared in Comparative Examples 1-3 is significantly lower than that of the composite ABS prepared in Example 12, indicating that:

[0152] In Comparative Example 1, due to the cancellation of stabilizers and protectants in the preparation of recycled ABS, the active groups were not protected, the chain segment structure was damaged, resulting in a decrease in the thermal stability of the matrix and a weakening of the flame retardancy. During thermal decomposition, the molecular chains of the matrix were more severely broken, and a protective carbon layer could not be effectively formed, easily releasing combustible gases and accelerating combustion. Compared with the examples, the unprotected matrix could not inhibit flame propagation;

[0153] In Comparative Example 2, due to the cancellation of acryloyl chloride capping in the preparation of the modified toughening agent, the number of active double bonds decreased, the formation of the crosslinked network was limited, and it was difficult to release enough non-combustible gases to dilute oxygen during thermal decomposition, resulting in a decrease in the flame retardancy effect. At the same time, the decrease in network density led to insufficient carbon layer formation and weakened thermal insulation effect. Compared with the examples, the lack of double bond crosslinking and gas-phase flame retardancy in Comparative Example 2 significantly reduced the flame retardancy performance;

[0154] In Comparative Example 3, due to the cancellation of phosphorus structure modification in the preparation of composite whiskers, the lack of the catalytic action of phosphate groups made it impossible to effectively promote the dehydration and carbonization of the matrix during thermal decomposition, the carbon layer was sparse, and it was difficult to isolate oxygen and heat, resulting in a decrease in flame retardancy. Compared with the examples, the lack of the carbonization promotion effect of phosphorus modification made the flame retardancy of the material significantly lower than that of the examples.

[0155] After overall comparative analysis of the data of Example 12 and Comparative Examples 1-3, it is found that in the process of recycling waste ABS, the present invention uses protectants and temperature agents to protect the active groups in the ABS chain segments, obtains recycled ABS by solvent purification, and uses the reaction of 4,6-triamino-1,3,5-triazine and 1,4-benzenedisulfonyl chloride solution to prepare a long-chain structure polymer. Finally, after acryloyl chloride capping, a modified toughening agent is obtained, and then a modified whisker composed of titanium dioxide components is prepared by hydrothermal method. The double bond structure on its surface is modified by phosphine addition and combined with phosphoric acid. Finally, a composite whisker is prepared. After the three are melt-extruded with auxiliary materials, through the promotion of electron irradiation by titanium dioxide components and irradiation crosslinking, a high-toughness composite ABS is finally prepared.

[0156] The above content is only an example and explanation of the structure of the present invention. Those skilled in the art to which the present technology pertains may 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 structure of the invention or exceed the scope defined by this claims, they shall fall within the protection scope of the present invention.

Claims

1. A regenerated ABS composite material with high toughness, characterized in that, It comprises raw materials in the following parts by weight: 70 - 80 parts of recycled ABS, 10 - 12 parts of modified toughening agent, 15 - 18 parts of composite whiskers, and 3 - 6 parts of auxiliary materials; The preparation method of the modified toughening agent is as follows: Under the protection of nitrogen, add 4,6-triamino-1,3,5-triazine, triethylamine, and anhydrous dichloromethane into a reaction kettle and stir. After the temperature of the reaction kettle drops to 10 - 15 °C, dropwise add a 1,4-benzenedisulfonyl chloride solution into the reaction kettle. After continuously dropping for 1 - 2 h, keep the temperature for reaction for 30 - 40 min, then continue to dropwise add an acryloyl chloride solution. After continuously dropping for 20 - 30 min, keep the temperature for reaction for 15 - 20 min, and then perform post-treatment to obtain the modified toughening agent.

2. The high-toughness recycled ABS composite material according to claim 1, wherein The auxiliary materials comprise raw materials in the following parts by weight: 1 - 2 parts of stabilizer, 1 - 2 parts of lubricant, 0.5 - 1 part of antioxidant, and 0.5 - 1 part of light stabilizer; In the process of preparing the modified toughening agent, the dosage ratio of 4,6-triamino-1,3,5-triazine, triethylamine, anhydrous dichloromethane, and 1,4-benzenedisulfonyl chloride solution is 5 - 6 g: 1 - 2 g: 20 - 24 mL: 20 - 24 mL: 10 - 12 mL. Among them, the 1,4-benzenedisulfonyl chloride solution is obtained by mixing 1,4-benzenedisulfonyl chloride and anhydrous dichloromethane according to the dosage ratio of 3 - 4 g: 20 - 24 mL, and the acryloyl chloride solution is obtained by mixing acryloyl chloride and anhydrous dichloromethane according to the dosage ratio of 1 - 2 g: 10 - 12 mL.

3. The high-toughness recycled ABS composite material according to claim 1, wherein The preparation method of the recycled ABS comprises the following steps: A1. Use a wall breaker to break waste ABS into particles with a particle size of 3 - 5 mm at a temperature of -10 °C, and then transfer the particles to two ultrasonic devices with a dispersion medium of 3 - 5 wt% sodium alkylbenzenesulfonate aqueous solution and deionized water respectively. After soaking and ultrasonicating 3 - 5 times in the ultrasonic device at 40 °C, perform post-treatment to obtain clean ABS particles; A2. Under the protection of nitrogen, add clean ABS particles, a composite solvent, and a protective agent into a closed stainless steel dissolution kettle and stir. Raise the temperature of the closed stainless steel dissolution kettle to 40 - 45 °C, keep the temperature and stir for 80 - 100 min to obtain a mixed solution. After passing the mixed solution through a filter with a pore size of 10 μm, obtain a purified ABS solution; A3. Add deionized water and a stabilizer into a precipitation tank equipped with a stirrer, an ultrasonic generator, and a cooling system and stir, and then dropwise add the purified ABS solution into the precipitation tank. After dropping it within 2 - 3 h, perform post-treatment to obtain recycled ABS.

4. The high-toughness recycled ABS composite material according to claim 3, wherein, In step A1, the solid-liquid ratio of the two ultrasonic devices is both 1:10, and the ultrasonic frequency is both 40 kHz; In step A2, the dosage ratio of clean ABS particles, the composite solvent, and the protective agent is 1.0 - 1.2 g: 10 mL: 0.05 - 0.08 g. Among them, the composite solvent is obtained by mixing methyl ethyl ketone and N,N-dimethylformamide according to the dosage ratio of 8 - 9 mL: 1 - 2 mL, and the protective agent is obtained by mixing 2,2,6,6-tetramethylpiperidine-1-oxyl and 2,6-di-tert-butyl-4-methylphenol according to the dosage ratio of 8 g: 1 - 2 g.

5. The high-toughness recycled ABS composite material according to claim 3, wherein In step A3, the dosage ratio of deionized water, stabilizer and purified ABS solution is 10 mL: 0.1 - 0.2 g: 1 - 2 mL. The stabilizer is obtained by mixing 2,2,6,6 - tetramethylpiperidine - 1 - oxyl radical and 2,6 - di - tert - butyl - 4 - methylphenol in a dosage ratio of 8 g: 1 - 2 g.

6. A highly tough recycled ABS composite material according to claim 1, wherein The preparation method of the composite whiskers includes the following steps: B1. Add tetrabutyl titanate, absolute ethanol, 3 - (methacryloyloxy) propyltrimethoxysilane and sodium hydroxide aqueous solution into a reaction kettle. After the reaction kettle is sealed, the temperature is raised to 160 - 180 °C, and the reaction is carried out under insulation for 16 - 18 h. Then, post - treatment is carried out to obtain modified whiskers; B2. Under the protection of nitrogen, add the modified whiskers, diphenylphosphine, aluminum chloride and N,N - dimethylformamide into a reaction kettle. The temperature of the reaction kettle is raised to 30 - 50 °C, and the reaction is carried out under insulation for 1 - 3 h. Then, post - treatment is carried out to obtain composite whiskers.

7. The high-toughness recycled ABS composite material according to claim 6, characterized in that, In step B1, the dosage ratio of tetrabutyl titanate, absolute ethanol, 3 - (methacryloyloxy) propyltrimethoxysilane and sodium hydroxide aqueous solution is 3 - 4 g: 4 - 5 mL: 0.3 - 0.5 g: 40 - 50 mL. Among them, the concentration of the sodium hydroxide aqueous solution is 8 - 10 moL / L, and the pressure of the reaction kettle is 4.5 - 6.3 MPa. In step B2, the dosage ratio of the modified whiskers, diphenylphosphine, aluminum chloride and N,N - dimethylformamide is 2 - 3 g: 0.5 - 0.6 g: 0.1 - 0.2 g: 10 - 12 mL.

8. A method for preparing a highly tough recycled ABS composite material as described in any one of claims 1-7, characterized in that, It includes the following steps: S1. Add recycled ABS, modified toughening agent, composite whiskers, stabilizer, lubricant, antioxidant and light stabilizer into a twin - screw extruder, and melt - extrude to obtain an ABS matrix; S2. Place the ABS matrix in an electron beam irradiation device, and after electron irradiation, obtain composite ABS.

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