ABS-based composite packaging material and preparation method thereof

Abstract

The invention discloses an ABS-based composite packaging material and a preparation method thereof, and belongs to the technical field of ABS packaging materials. The weather-resistant ABS plastic disclosed by the invention is prepared from the following raw material components in parts by mass: 75 to 85 parts of ABS raw material, 15 to 25 parts of modified regenerated ABS, 4 to 6 parts of toughening agent, 0.2 to 1 part of lubricating agent and 0.1 to 0.3 part of antioxidant, the modified regenerated ABS is obtained by carrying out melt blending modification on 3, 9-bis (2-hydroxy-2-propyl)-2, 4, 8, 10-tetraoxo-3, 9-diphosphospiro [5, 5] undecane-3, 9-dioxo and the regenerated ABS; the flexibilizer acrylate copolymer wraps a polysiloxane elastomer; the ABS-based composite packaging material prepared by the preparation method disclosed by the invention is relatively good in flame retardance and mechanical property.

Description

Technical Field

[0001] The invention relates to an ABS-based composite packaging material and a preparation method thereof. Background Art

[0002] As a thermoplastic engineering plastic with excellent comprehensive performance, ABS resin occupies an important position in the fields of electronic product packaging, industrial equipment protection, etc. due to its excellent rigidity, processing stability and surface smoothness.

[0003] According to statistics, the world generates over 5 million tons of ABS waste annually, of which packaging materials account for over 35%. Establishing an effective recycling and utilization system has become a key issue for the industry's sustainable development. However, after repeated processing, waste ABS is often accompanied by problems such as molecular chain breakage, rubber phase agglomeration, and antioxidant loss. In particular, when recycled materials are blended with virgin materials, the interfacial compatibility between the two phases deteriorates, leading to a significant decrease in mechanical properties. This seriously restricts the industrial application of high-value recycling technologies.

[0004] In order to solve the above problems, the applicant prepared an ABS-based composite packaging material. Summary of the Invention

[0005] The purpose of the present invention is to provide an ABS-based composite packaging material and a preparation method thereof, so as to solve the technical problems mentioned in the above background technology.

[0006] The technical solution for achieving the purpose of the present invention is: In a first aspect, an ABS-based composite packaging material comprises, by weight, 75-85 parts of virgin ABS, 15-25 parts of modified recycled ABS, 4-6 parts of a toughening agent, 0.2-1 parts of a lubricant, 0.1-0.3 parts of an antioxidant, and 0.16-0.3 parts of a vulcanizing agent.

[0007] Furthermore, the modified recycled ABS is obtained by melt-blending and modifying 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide with waste ABS.

[0008] Furthermore, the toughening agent is an acrylic ester copolymer wrapped with a polysiloxane elastomer.

[0009] Furthermore, the acrylate copolymer-wrapped polysiloxane elastomer is obtained by first polymerizing siloxane monomers octamethylcyclotetrasiloxane, hexamethyldisiloxane, and γ-methacryloxypropyltrimethoxysilane using an emulsion polymerization method, and then sequentially grafting butyl acrylate, ethylene glycol dimethacrylate, methyl methacrylate, 1,3,5-triacryloyl-s-triazine, and 2-propylene-1-thiol.

[0010] In a second aspect, the present invention provides an ABS-based composite packaging material as described in the first aspect, comprising the following preparation steps: (1) Weigh and mix the raw materials according to their mass fractions and dry them; (2) The weighed ABS raw material, modified recycled ABS, toughening agent, and vulcanizing agent are mixed, poured into a twin-screw extruder for extrusion and granulation, and then dried to obtain a premix; (3) The premix obtained in step (2) is mixed with the lubricant and antioxidant weighed in step (1), poured into a twin-screw extruder for extrusion granulation, and then dried and injection molded to obtain an ABS-based composite packaging material.

[0011] Furthermore, the preparation method of the modified recycled ABS is as follows: Waste ABS and 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide were mixed uniformly according to the mass ratio and poured into a torque rheometer for melt blending at 208-212°C and 30 rpm for 9-11 minutes. The mixture was then crushed and dried in a crusher to obtain modified recycled ABS with a particle size of 7.8-8.5 mm.

[0012] Furthermore, the preparation method of the toughening agent is as follows: A1.1 Mix 1.3-1.5 parts by mass of dodecylbenzenesulfonic acid and 100 parts by mass of deionized water. Heat to 75-85°C and stir until evenly combined. Add a mixture of 6-8 parts by mass of octamethylcyclotetrasiloxane and 0.5-1.5 parts by mass of γ-methacryloxypropyltrimethoxysilane dropwise at a rate of 1-3 seconds. Mix and react for 1-2 hours. A1.2: Mix 100 parts by mass of deionized water, 1.3-1.5 parts by mass of dodecylbenzenesulfonic acid, 32-34 parts by mass of octamethylcyclotetrasiloxane, 2-3 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 1-2 parts by mass of hexamethyldisiloxane at room temperature. Homogenize using a high-dispersion homogenizer for 8-12 minutes. Add the mixture to the emulsion obtained in step A1.1 at a rate of 1-3 seconds per drop. Continue reacting at 75-85°C for 2-4 hours after addition. Cool to room temperature to obtain a polysiloxane core emulsion. A2. The pH value of the polysiloxane core emulsion obtained in step A1.2 was adjusted to 8 to 10 with 3.0wt% sodium hydroxide solution and nitrogen was introduced for 15 to 30min; A3. 13~14 butyl acrylate, 0.4~0.5 ethylene glycol dimethacrylate, 0.15~0.25 dodecanethiol were mixed and then added dropwise to the emulsion obtained in step A2 at a rate of 1~3s / drop. 0.51~0.53 parts by mass of a 10% aqueous potassium persulfate solution was added dropwise at a rate of 1~3s / drop. After the addition was complete, the temperature was raised to 78~82°C and the reaction was allowed to proceed for 2.5~3.5h. A4. Add 31-32 parts by weight of methyl methacrylate, 0.4-0.6 parts by weight of 1,3,5-triacryloyl-s-triazine, and 0.4-0.6 parts by weight of propylene-1-mercaptan to the emulsion obtained in A3. Add 2.4-2.5 parts by weight of a 10% aqueous potassium persulfate solution dropwise at a rate of 1-3 seconds per drop. After the addition is complete, react at 78-82°C for 2.5-3.5 hours. Add 5.0 wt% calcium chloride solution to break the emulsion, wash with water, and centrifuge. Then, dry the mixture in a vacuum drying oven at 80°C for 23-24 hours. Extract with acetone for 23-25 ​​hours, then with methanol for 23-25 ​​hours. Dry the mixture in a vacuum drying oven at 80°C to constant weight to obtain a toughening agent.

[0013] Furthermore, the vulcanizing agent is dibenzoyl peroxide.

[0014] By adopting the above technical solution, the present invention has the following beneficial effects: (1) The raw material components of the ABS-based composite packaging material of the present invention include: virgin ABS, modified recycled ABS, a toughening agent, a lubricant, an antioxidant, and a vulcanizing agent. By modifying the recycled ABS and adding the toughening agent, the ABS-based composite packaging material has better mechanical properties.

[0015] (2) The modified recycled ABS of the present invention is obtained by melt-blending and modifying 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide with waste ABS, wherein the waste ABS ages during use, processing and recycling, and the chain segments break during the aging process. Under light, heat and oxygen conditions, some oxygen-containing groups such as -COOH and -OH are generated in the waste ABS; 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide reacts and cross-links with some oxygen-containing groups in the waste ABS through hydroxyl groups, and introduces a rigid structure of spirocyclic phosphate into the waste ABS, which reduces the fluidity of the chain segments in the waste ABS when stress is applied, and can effectively improve the tensile properties and flame retardant properties of the modified recycled ABS.

[0016] (3) The toughening agent of the present invention is obtained by first polymerizing the siloxane monomers octamethylcyclotetrasiloxane, hexamethyldisiloxane, and γ-methacryloxypropyltrimethoxysilane by emulsion polymerization to form a polysiloxane core material, and then grafting butyl acrylate, ethylene glycol dimethacrylate, methyl methacrylate, 1,3,5-triacryloyl-s-triazine, and 2-propylene-1-thiol in sequence to form an elastomer with polysiloxane as the core and a hyperbranched acrylate copolymer as the shell, which can effectively enhance the toughness of ABS-based composite packaging materials.

[0017] (4) The present invention first premixes virgin ABS, modified recycled ABS, a toughening agent, and a vulcanizing agent. During this process, the toughening agent reacts with the sulfhydryl groups on the hyperbranched acrylate copolymer of the shell layer to form a click reaction with some olefin bonds in the virgin ABS and the modified recycled ABS to form a covalent bond connection. The covalent bond connection and the physical connection between the virgin ABS, the modified recycled ABS and the cavity of the hyperbranched structure shell layer of the toughening agent are used to make the toughening agent serve as a compatible medium to improve the compatibility between the virgin ABS and the modified recycled ABS, thereby further enhancing the toughness and tensile strength of the ABS-based composite packaging material. DETAILED DESCRIPTION

[0018] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0019] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0020] The following examples are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0021] The raw materials of the embodiments and comparative examples are as follows: Waste ABS was collected from Jieshou Shuangte New Materials Co., Ltd. The preparation method of 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide is as follows: [Zhang Yuhua. Synthesis and Application Research of Spirocyclic Phosphate (Phosphonate) Flame Retardants [D]. Jiangsu: Nanjing University of Technology, 2007. DOI: 10.7666 / d.y2084506.] The specific method is as follows: 13.6 parts by mass of pentaerythritol, 0.4 parts by mass of pyridine and 34.4 parts by mass of toluene are mixed and stirred, and 32.9 parts by mass of phosphorus trichloride are added dropwise at room temperature within 1 hour, and then the temperature is raised to 55 ℃, then heating and reflux until no hydrogen chloride gas is discharged, removing the remaining solvent by distillation under reduced pressure, standing and cooling to room temperature to obtain dichloropentaerythritol phosphite; adding 24.3 parts by mass of acetone and 0.4 parts by mass of pyridine to 24.9 parts by mass of dichloropentaerythritol phosphorous acid, adding 10.1 parts by mass of formic acid dropwise within 65 minutes, controlling the temperature at 39℃ during the addition, heating to 55℃ after the addition is completed, stirring at this temperature for 1 hour, filtering, washing and drying to obtain 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxo.

[0022] Antioxidant 1010 was used as the antioxidant.

[0023] (Example 1) An ABS-based composite packaging material comprises the following preparation steps: (1) Weigh and mix the raw material components according to the following mass parts and dry them: 75 mass parts of virgin ABS, 25 mass parts of modified recycled ABS, 4 mass parts of toughening agent, 0.2 mass parts of lubricant, and 0.1 mass parts of antioxidant; (2) The weighed ABS raw material, modified recycled ABS, toughening agent, and vulcanizing agent dibenzoyl peroxide are mixed, poured into a twin-screw extruder for extrusion and granulation, and then dried to obtain a premix; the twin-screw extruder temperature is 200°C, 210°C, 215°C, 220°C, 220°C, 230°C, 230°C, 235°C, and 235°C, the main screw speed is 200 rpm, and the feed screw speed is 20 rpm; (3) The premix obtained in step (2) is mixed with the lubricant and antioxidant weighed in step (1), poured into a twin-screw extruder for continued extrusion and granulation, and then injection molded after drying to obtain an ABS-based composite packaging material; the injection molding machine has an injection molding temperature of 200°C, 210°C, 220°C, and 235°C, an injection speed of 55 mm / s, an injection pressure of 55 MPa, a holding pressure of 45 MPa, and a mold temperature of 55°C.

[0024] The preparation method of the modified regenerated ABS is as follows: Waste ABS and 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide were mixed evenly according to the mass ratio and poured into a torque rheometer for melt blending at 208°C and 30 rpm for 9 minutes. Then, the mixture was placed in a crusher for crushing and drying to obtain modified recycled ABS with a particle size of 8 mm.

[0025] The preparation method of the toughening agent is as follows: A1.1 Mix 1.3 parts by mass of dodecylbenzenesulfonic acid and 100 parts by mass of deionized water, heat to 75°C, and stir until uniform. Then, add a mixture of 6 parts by mass of octamethylcyclotetrasiloxane and 0.5 parts by mass of γ-methacryloxypropyltrimethoxysilane at a rate of 1 drop per second. Mix and react for 1 hour. A1.2: Mix 100 parts by mass of deionized water, 1.3 parts by mass of dodecylbenzenesulfonic acid, 3,4-octamethylcyclotetrasiloxane, 3 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 1 part by mass of hexamethyldisiloxane at room temperature. Homogenize using a high-dispersion homogenizer for 8 minutes. Add the mixture to the emulsion obtained in step A1.1 at a rate of 1 drop per second. Continue the reaction at 75°C for 2 hours after addition. Cool to room temperature to obtain a polysiloxane core emulsion. A2. The pH value of the polysiloxane core emulsion obtained in step A1.2 was adjusted to 8 with 3.0wt% sodium hydroxide solution and nitrogen was introduced for 15min; A3. 13 butyl acrylate, 0.4 ethylene glycol dimethacrylate, 0.15 dodecanethiol were mixed and then added dropwise to the emulsion obtained in step A2 at a rate of 1s / drop, and 0.51 parts by mass of a 10% aqueous potassium persulfate solution was added dropwise at a rate of 1s / drop. After the addition was complete, the temperature was raised to 78 ° C and the reaction was allowed to proceed for 2.5h. A4. 31 parts by weight of methyl methacrylate, 0.4 parts by weight of 1,3,5-triacryloyl-s-triazine, and 0.4 parts by weight of propylene-1-mercaptan were added to the emulsion obtained in A3. 2.4 parts by weight of a 10% aqueous potassium persulfate solution were added dropwise at a rate of 1 second per drop. After the addition was complete, the mixture was reacted at 78°C for 2.5 hours. A 5.0 wt% calcium chloride solution was added to break the emulsion. The mixture was washed with water and centrifuged. The mixture was then dried in a vacuum drying oven at 80°C for 23 hours. The mixture was then extracted with acetone for 23 hours, then with methanol for 23 hours, and dried in a vacuum drying oven at 80°C to constant weight to obtain a toughening agent.

[0026] (Example 2) An ABS-based composite packaging material comprises the following preparation steps: (1) Weigh and mix the raw material components according to the following mass parts and dry them: 80 mass parts of virgin ABS, 20 mass parts of modified recycled ABS, 5 mass parts of toughening agent, 0.5 mass parts of lubricant, and 0.2 mass parts of antioxidant; (2) The weighed ABS raw material, modified recycled ABS, toughening agent, and vulcanizing agent dibenzoyl peroxide are mixed, poured into a twin-screw extruder for extrusion and granulation, and then dried to obtain a premix; the twin-screw extruder temperature is 200°C, 210°C, 215°C, 220°C, 220°C, 230°C, 230°C, 235°C, and 235°C, the main screw speed is 200 rpm, and the feed screw speed is 20 rpm; (3) The premix obtained in step (2) is mixed with the lubricant and antioxidant weighed in step (1), poured into a twin-screw extruder for continued extrusion and granulation, and then injection molded after drying to obtain an ABS-based composite packaging material; the injection molding machine has an injection molding temperature of 200°C, 210°C, 220°C, and 235°C, an injection speed of 55 mm / s, an injection pressure of 55 MPa, a holding pressure of 45 MPa, and a mold temperature of 55°C.

[0027] The preparation method of the modified regenerated ABS is as follows: Waste ABS and 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide were mixed evenly according to the mass ratio and poured into a torque rheometer for melt blending at 210°C and 30 rpm for 10 minutes. Then, the mixture was placed in a crusher for crushing and drying to obtain modified recycled ABS with a particle size of 8 mm.

[0028] The preparation method of the toughening agent is as follows: A1.1 Mix 1.4 parts by mass of dodecylbenzenesulfonic acid and 100 parts by mass of deionized water, heat to 80°C, and stir until uniform. Then, add a mixture of 7 parts by mass of octamethylcyclotetrasiloxane and 1 part by mass of γ-methacryloxypropyltrimethoxysilane dropwise at a rate of 2 seconds. Mix and react for 1.5 hours. A1.2: Mix 100 parts by mass of deionized water, 1.4 parts by mass of dodecylbenzenesulfonic acid, 3,3-octamethylcyclotetrasiloxane, 2.5 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 1.5 parts by mass of hexamethyldisiloxane at room temperature. Homogenize for 10 minutes using a high-dispersion homogenizer. Add the mixture to the emulsion obtained in step A1.1 at a rate of 12 seconds per drop. Continue the reaction at 80°C for 3 hours after addition. Cool to room temperature to obtain a polysiloxane core emulsion. A2. The pH value of the polysiloxane core emulsion obtained in step A1.2 was adjusted to 9 with 3.0wt% sodium hydroxide solution and nitrogen was introduced for 30min; A3. 13.5 butyl acrylate, 0.45 ethylene glycol dimethacrylate, 0.2 dodecanethiol were mixed and then added dropwise to the emulsion obtained in step A2 at 2s / drop, and 0.52 parts by mass of a 10% aqueous potassium persulfate solution was added dropwise at 2s / drop. After the addition was complete, the temperature was raised to 80 ° C and the reaction was allowed to react for 3h; A4. Add 31.5 parts by weight of methyl methacrylate, 0.5 parts by weight of 1,3,5-triacryloyl-s-triazine, and 0.5 parts by weight of propylene-1-mercaptan to the emulsion obtained in A3. After the addition is complete, add 2.45 parts by weight of a 10% aqueous potassium persulfate solution dropwise at a rate of 2 seconds per drop. After the addition is complete, react at 80°C for 3 hours. Add 5.0 wt% calcium chloride solution to break the emulsion, wash with water, and centrifuge. Then, place the mixture in a vacuum drying oven at 80°C for 23.5 hours. Then, extract with acetone for 24 hours, then with methanol for 24 hours, and dry it in a vacuum drying oven at 80°C to constant weight to obtain a toughening agent.

[0029] (Example 3) An ABS-based composite packaging material comprises the following preparation steps: (1) Weigh and mix the raw material components according to the following mass parts and dry them: 85 mass parts of virgin ABS, 15 mass parts of modified recycled ABS, 6 mass parts of toughening agent, 1 mass part of lubricant, and 0.3 mass part of antioxidant; (2) The weighed ABS raw material, modified recycled ABS, toughening agent, and vulcanizing agent dibenzoyl peroxide are mixed, poured into a twin-screw extruder for extrusion and granulation, and then dried to obtain a premix; the twin-screw extruder temperature is 200°C, 210°C, 215°C, 220°C, 220°C, 230°C, 230°C, 235°C, and 235°C, the main screw speed is 200 rpm, and the feed screw speed is 20 rpm; (3) The premix obtained in step (2) is mixed with the lubricant and antioxidant weighed in step (1), poured into a twin-screw extruder for continued extrusion and granulation, and then injection molded after drying to obtain an ABS-based composite packaging material; the injection molding machine has an injection molding temperature of 200°C, 210°C, 220°C, and 235°C, an injection speed of 55 mm / s, an injection pressure of 55 MPa, a holding pressure of 45 MPa, and a mold temperature of 55°C.

[0030] The preparation method of the modified regenerated ABS is as follows: Waste ABS and 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide were mixed evenly according to the mass ratio and poured into a torque rheometer for melt blending at 212°C and 30 rpm for 11 minutes. Then, the mixture was placed in a crusher for crushing and drying to obtain modified recycled ABS with a particle size of 8.5 mm.

[0031] The preparation method of the toughening agent is as follows: A1.1 Mix 1.5 parts by mass of dodecylbenzenesulfonic acid and 100 parts by mass of deionized water, heat to 85°C, and stir until evenly combined. Then, add a mixture of 8 parts by mass of octamethylcyclotetrasiloxane and 1.5 parts by mass of γ-methacryloxypropyltrimethoxysilane dropwise at a rate of 3 seconds. Mix and react for 2 hours. A1.2: Mix 100 parts by mass of deionized water, 1.5 parts by mass of dodecylbenzenesulfonic acid, 3,2-octamethylcyclotetrasiloxane, 2 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 2 parts by mass of hexamethyldisiloxane at room temperature. Homogenize using a high-dispersion homogenizer for 12 minutes. Add the mixture dropwise at a rate of 3 seconds to the emulsion obtained in step A1.1. Continue reacting at 85°C for 4 hours after addition. Cool to room temperature to obtain a polysiloxane core emulsion. A2. The pH of the polysiloxane core emulsion obtained in step A1.2 was adjusted to 10 with 3.0wt% sodium hydroxide solution and nitrogen was introduced for 30min; A3. 14 butyl acrylate, 0.5 ethylene glycol dimethacrylate, 0.25 dodecanethiol were mixed and then added dropwise to the emulsion obtained in step A2 at 3s / drop, and 0.53 parts by mass of a 10% aqueous potassium persulfate solution was added dropwise at 3s / drop. After the addition was complete, the temperature was raised to 82 ° C and the reaction was allowed to proceed for 3.5h. A4. 32 parts by weight of methyl methacrylate, 0.6 parts by weight of 1,3,5-triacryloyl-s-triazine, and 0.6 parts by weight of propylene-1-mercaptan were added to the emulsion obtained in A3. After the addition was complete, 2.5 parts by weight of a 10% aqueous potassium persulfate solution was added dropwise at a rate of 3 seconds per drop. After the addition was complete, the mixture was reacted at 82°C for 3.5 hours. A 5.0 wt% calcium chloride solution was added to break the emulsion. The mixture was washed with water and centrifuged. The mixture was then dried in a vacuum drying oven at 80°C for 24 hours. The mixture was then extracted with acetone for 25 hours, then with methanol for 25 hours, and dried in a vacuum drying oven at 80°C to constant weight to obtain a toughening agent.

[0032] (Comparative Example 1) The difference between Comparative Example 1 and Example 2 is that the raw material components of the ABS-based composite packaging material in Comparative Example 1 only use virgin ABS, recycled ABS, toughening agent, lubricant, antioxidant, and vulcanizing agent, and the remaining components and preparation steps are the same as those in Example 2.

[0033] (Comparative Example 2) The difference between Comparative Example 2 and Example 2 is that the toughening agent in Comparative Example 2 is first polymerized by emulsion polymerization of siloxane monomers octamethylcyclotetrasiloxane, hexamethyldisiloxane, and γ-methacryloxypropyltrimethoxysilane to form a polysiloxane core material, and then butyl acrylate, ethylene glycol dimethacrylate, methyl methacrylate, and 1,3,5-triacryloyl-s-triazine are grafted in sequence to obtain the remaining components and preparation steps, which are the same as those in Example 2.

[0034] (Comparative Example 3) The difference between Comparative Example 3 and Example 2 is that the toughening agent in Comparative Example 3 is first polymerized by emulsion polymerization of siloxane monomers octamethylcyclotetrasiloxane, hexamethyldisiloxane, and γ-methacryloxypropyltrimethoxysilane to form a polysiloxane core material, and then butyl acrylate, ethylene glycol dimethacrylate, methyl methacrylate, and 2-propylene-1-thiol are grafted in sequence to obtain the remaining components and preparation steps, which are the same as those in Example 2.

[0035] (Comparative Example 4) The difference between Comparative Example 4 and Example 2 is that the ABS-based composite packaging material of Comparative Example 4 is obtained by directly mixing ABS raw materials, modified recycled ABS, toughening agent, lubricant, and antioxidant and extruding and injection molding. The remaining components and preparation steps are the same as those of Example 2.

[0036] (Effect example) Table 1 below shows the performance test results of the ABS-based composite packaging materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4: Table 1

[0037] As shown in Table 1, the ABS-based composite packaging materials prepared in Examples 1 to 3 have good impact toughness, tensile properties, and flame retardancy.

[0038] The difference between Comparative Example 1 and Example 2 is that the ABS in Comparative Example 1 is not modified, and the impact toughness and tensile strength of the obtained ABS-based composite packaging material are weaker than those in Example 2, and the flame retardancy is poorer.

[0039] The difference between Comparative Example 2 and Example 2 is that 2-propylene-1-mercaptan is not introduced into the shell layer of the toughening agent in Comparative Example 2, and the tensile strength of the obtained ABS-based composite packaging material is weaker than that in Example 2 and the flame retardancy is poorer.

[0040] The difference between Comparative Example 3 and Example 2 is that the shell layer of the toughening agent in Comparative Example 3 does not introduce 1,3,5-triacryloyl-s-triazine, and the impact toughness of the obtained ABS-based composite packaging material is weaker than that in Example 2, the tensile strength is weaker than that in Example 2, and the flame retardancy is poor.

[0041] The difference between Comparative Example 4 and Example 2 is that the ABS-based composite packaging material of Comparative Example 4 is obtained by directly mixing ABS raw materials, modified recycled ABS, and toughening agent and extruding and injection molding. The tensile strength of the obtained ABS-based composite packaging material is weaker than that of Example 2 and the flame retardancy is poor.

[0042] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An ABS-based composite packaging material, characterized in that: The raw material components include, by weight: 75-85 parts by weight of virgin ABS, 15-25 parts by weight of modified recycled ABS, 4-6 parts by weight of toughening agent, 0.2-1 parts by weight of lubricant, 0.1-0.3 parts by weight of antioxidant, and 0.16-0.3 parts by weight of vulcanizing agent.

2. The ABS-based composite packaging material according to claim 1, characterized in that: The modified recycled ABS is obtained by melt-blending and modifying 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide with waste ABS.

3. The ABS-based composite packaging material according to claim 1, characterized in that: The toughening agent adopts an acrylic ester copolymer to wrap a polysiloxane elastomer.

4. The ABS-based composite packaging material according to claim 3, characterized in that: The acrylate copolymer-wrapped polysiloxane elastomer is obtained by first polymerizing siloxane monomers octamethylcyclotetrasiloxane, hexamethyldisiloxane, and γ-methacryloxypropyltrimethoxysilane using an emulsion polymerization method, and then sequentially grafting butyl acrylate, ethylene glycol dimethacrylate, methyl methacrylate, 1,3,5-triacryloyl-s-triazine, and 2-propylene-1-thiol.

5. An ABS-based composite packaging material according to any one of claims 1 to 3, characterized in that: The method comprises the following preparation steps: (1) Weigh and mix the raw materials according to their mass fractions and dry them; (2) The weighed ABS raw material, modified recycled ABS, toughening agent, and vulcanizing agent are mixed, poured into a twin-screw extruder for extrusion and granulation, and then dried to obtain a premix; (3) The premix obtained in step (2) is mixed with the lubricant and antioxidant weighed in step (1), poured into a twin-screw extruder for extrusion granulation, and then dried and injection molded to obtain an ABS-based composite packaging material.

6. The ABS-based composite packaging material according to claim 5, characterized in that: The preparation method of the modified regenerated ABS is as follows: Waste ABS and 3,9-bis(2-hydroxy-2-propyl)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5,5]undecane-3,9-dioxide were mixed uniformly according to the mass ratio and poured into a torque rheometer for melt blending at 208-212°C and 30 rpm for 9-11 minutes. The mixture was then crushed and dried in a crusher to obtain modified recycled ABS with a particle size of 7.8-8.5 mm.

7. The ABS-based composite packaging material according to claim 5, characterized in that: The preparation method of the toughening agent is as follows: A1.1 Mix 1.3-1.5 parts by mass of dodecylbenzenesulfonic acid and 100 parts by mass of deionized water. Heat to 75-85°C and stir until evenly combined. Add a mixture of 6-8 parts by mass of octamethylcyclotetrasiloxane and 0.5-1.5 parts by mass of γ-methacryloxypropyltrimethoxysilane dropwise at a rate of 1-3 seconds. Mix and react for 1-2 hours. A1.2: Mix 100 parts by mass of deionized water, 1.3-1.5 parts by mass of dodecylbenzenesulfonic acid, 32-34 parts by mass of octamethylcyclotetrasiloxane, 2-3 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 1-2 parts by mass of hexamethyldisiloxane at room temperature. Homogenize using a high-dispersion homogenizer for 8-12 minutes. Add the mixture to the emulsion obtained in step A1.1 at a rate of 1-3 seconds per drop. Continue reacting at 75-85°C for 2-4 hours after addition. Cool to room temperature to obtain a polysiloxane core emulsion. A2. The pH value of the polysiloxane core emulsion obtained in step A1.2 was adjusted to 8 to 10 with 3.0wt% sodium hydroxide solution and nitrogen was introduced for 15 to 30min; A3. 13~14 butyl acrylate, 0.4~0.5 ethylene glycol dimethacrylate, 0.15~0.25 dodecanethiol were mixed and then added dropwise to the emulsion obtained in step A2 at a rate of 1~3s / drop. 0.51~0.53 parts by mass of a 10% aqueous potassium persulfate solution was added dropwise at a rate of 1~3s / drop. After the addition was complete, the temperature was raised to 78~82°C and the reaction was allowed to proceed for 2.5~3.5h. A4. Add 31-32 parts by weight of methyl methacrylate, 0.4-0.6 parts by weight of 1,3,5-triacryloyl-s-triazine, and 0.4-0.6 parts by weight of propylene-1-mercaptan to the emulsion obtained in A3. Add 2.4-2.5 parts by weight of a 10% aqueous potassium persulfate solution dropwise at a rate of 1-3 seconds per drop. After the addition is complete, react at 78-82°C for 2.5-3.5 hours. Add 5.0 wt% calcium chloride solution to break the emulsion, wash with water, and centrifuge. Then, dry the mixture in a vacuum drying oven at 80°C for 23-24 hours. Extract with acetone for 23-25 ​​hours, then with methanol for 23-25 ​​hours. Dry the mixture in a vacuum drying oven at 80°C to constant weight to obtain a toughening agent.

8. The ABS-based composite packaging material according to claim 5, characterized in that: The vulcanizing agent is dibenzoyl peroxide.

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