High-toughness regenerated ABS (Acrylonitrile Butadiene Styrene) material and application thereof in respiratory protection equipment

Abstract

The invention discloses a high-toughness regenerated ABS (Acrylonitrile Butadiene Styrene) material and application thereof in respiratory protection equipment, and belongs to the technical field of preparation of regenerated ABS materials. The high-toughness regenerated ABS material is prepared from the following components in parts by weight: 70 to 80 parts of regenerated ABS resin, 10 to 20 parts of a modified toughening agent, 2 to 7 parts of a compound additive, 0.5 to 1.3 parts of a lubricating agent, 0.2 to 0.8 part of an antioxidant and 1.2 to 2.3 parts of a coloring agent, and the regenerated ABS resin is prepared from 80 to 90 parts of recycled ABS and 5 to 10 parts of polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester. The regenerated ABS material prepared from the substances has excellent toughness, chemical resistance and wide temperature range applicability, so that the application of the regenerated ABS material in respiratory protection equipment is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of recycled material preparation, and in particular relates to a high-toughness recycled ABS material and an application thereof in respiratory protection equipment. Background Art

[0002] Recycled ABS, a modified form of acrylonitrile-butadiene-styrene copolymer, has become a research hotspot driven by environmental concerns and the trend toward material recycling. Construction sites generate a large number of discarded helmets primarily made of ABS. Recycling these discarded helmets and using them as raw material for recycled ABS after professional processing not only effectively reuses waste, reduces environmental pollution, but also lowers raw material costs. However, the current limitations of the basic performance of this type of recycled ABS material restrict its direct application in high-end applications such as respiratory protective equipment. While traditional ABS materials retain their elasticity at low temperatures thanks to the toughness imparted by the butadiene component, the breakage and recombination of molecular chains during the regeneration process significantly reduces their toughness. Brittle fracture is particularly common in low-temperature environments, making it difficult to meet the stringent impact resistance requirements of respiratory protective equipment. At the same time, due to its high styrene content, ABS material generally has a heat deformation temperature of around 80°C. The reduced molecular weight after recycling further weakens its high-temperature resistance, making it prone to softening and deformation in high-temperature environments. Meanwhile, the loss of toughness in low-temperature environments leads to insufficient impact resistance. This dual shortcoming in heat resistance makes it difficult to cope with the wide temperature range of -20°C to 60°C required for respiratory protection equipment. For example, in outdoor operations in cold regions or industrial protection scenarios in high-temperature workshops, breathing valve housings or filter material brackets made of traditional recycled ABS materials are prone to cracking due to temperature stress, affecting the sealing and service life of the equipment.

[0003] Patent CN120230369A discloses a high-toughness recycled ABS composite material and its preparation method, belonging to the field of material recycling technology, and is used to solve the technical problem in the prior art that the tensile strength and flame retardancy of recycled ABS materials need to be further improved. The invention comprises the following raw materials, in parts by weight: 70-80 parts of recycled ABS, 10-12 parts of a modified toughening agent, 15-18 parts of composite whiskers, and 3-6 parts of auxiliary materials. The invention obtains recycled ABS by using a protective agent and a temperature regulator to protect the active groups in the ABS chain segments during the waste ABS recycling process, and utilizes a solvent purification method to prepare the modified toughening agent and composite whiskers. After the three are melt-extruded with the auxiliary materials, the titanium dioxide component promotes electron irradiation, and the composite whiskers are finally prepared through irradiation crosslinking to obtain a high-toughness composite ABS. Although the composite ABS prepared by the above method uses protective agents and temperature regulators to protect the active groups, the recovery system is complex, making it difficult to completely avoid damage to the active groups, resulting in weakened intermolecular chain forces. The modified toughening agent and composite whiskers have limited compatibility with the recycled ABS, failing to fully form a uniform and effective toughening network structure. Therefore, there is still room for improvement in the toughness of the composite ABS material, thereby broadening its application range in respiratory protective equipment. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-toughness recycled ABS material and its application in respiratory protection equipment, so as to solve the technical problem of poor toughness in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a high-toughness recycled ABS material, which is composed of the following components in parts by weight: 70-80 parts of recycled ABS resin, 10-20 parts of a modified toughening agent, 2-7 parts of a composite auxiliary agent, 0.5-1.3 parts of a lubricant, 0.2-0.8 parts of an antioxidant, and 1.2-2.3 parts of a colorant. The recycled ABS resin is composed of 80-90 parts of recycled ABS and 5-10 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol.

[0006] Preferably, the lubricant is composed of one or more of polypropylene wax, polyethylene wax, butyl stearate and zinc stearate; the antioxidant is composed of one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 626; and the colorant is composed of one or more of titanium dioxide, carbon black, iron oxide red, iron oxide yellow and phthalocyanine basket.

[0007] Preferably, the preparation method of the modified toughening agent comprises the following steps: Q1: Vanillin, 1,4-dibromobutane, potassium carbonate, and potassium iodide were added to a container in sequence, and then N,N-dimethylformamide was added. After stirring and mixing, the mixture was heated and refluxed under nitrogen. After the reaction was completed, the mixture was cooled and added to deionized water for precipitation. The mixture was filtered, recrystallized, and dried in vacuo to obtain intermediate 1. Q2: Add intermediate 1 and 4-aminophenol to a container containing N,N-dimethylformamide, stir and dissolve, heat, and reflux under nitrogen. After the reaction is complete, cool, add to deionized water, precipitate, and vacuum dry to obtain intermediate 2; Q3: Add polymethylhydrogensiloxane to a container containing isopropanol, then add N,N-dimethylformamide containing intermediate 2, heat and stir, add chloroplatinic acid isopropanol solution, continue heating and react, cool after the reaction, add sodium hydroxide solution, heat and dry, and obtain intermediate 3; Q4: Add intermediate 3 and isophorone diisocyanate to a container, heat and stir, then add 2,2-dihydroxymethylpropionic acid to react, cool down and add 1,4-butanediol and dibutyltin dilaurate, stir and react, continue to cool down, add triethylamine and stir, and after stirring, obtain a modified toughening agent.

[0008] In the above process, the synthesis reaction formula of intermediate 3 is as follows:

[0009] The results of mass spectrometry analysis of intermediate 1 were: m / z: 358.14 (100.0%), 359.14 (21.6%), 360.15 (3.6%); the results of mass spectrometry analysis of intermediate 2 were: m / z: 540.23 (100.0%), 541.23 (35.2%), 542.23 (7.4%).

[0010] Preferably, in Q1, the amount ratio of vanillin, 1,4-dibromobutane, potassium carbonate, potassium iodide and N,N-dimethylformamide is (8.98-9.24) g: (6.12-6.68) g: (11.82-15.63) g: (0.42-0.58) g: (90-110) mL, the heating temperature is 80-82°C, and the reflux reaction time is 5-7 h. In Q2, the amount ratio of the intermediate 1, 4-aminophenol and N,N-dimethylformamide is (3.82-4.06) g: (2.02-2.36) g: (100-150) mL, the heating temperature is 60-70°C, and the reflux reaction time is 4-6 h.

[0011] As preferred, in the Q3, the amount ratio of polymethylhydrogen siloxane, isopropyl alcohol, intermediate 2, N,N-dimethylformamide, isopropyl alcohol solution of chloroplatinic acid and sodium hydroxide solution is (1.32-1.68) g:(20-35) mL:(0.98-1.12) g:(10-15) mL:(0.12-0.18) mL:(0.08-0.12) mL, the heating and stirring temperature is 70-73℃, the time is 10-20 min, the heating continues to 90-92℃ for 6-8 h, the concentration of isopropyl alcohol solution of chloroplatinic acid is 0.5 g / L, and the concentration of sodium hydroxide solution is 0.002 mol / L.

[0012] As preferred, in the Q4, the amount ratio of intermediate 3, isophorone diisocyanate, 2,2-dimethylol propionic acid, 1,4-butanediol, dibutyl tin dilaurate and triethylamine is (10.08-18.12) g:(5.01-5.28) g:(0.58-0.74) g:(0.38-0.52) g:(0.22-0.38) g:(0.42-0.65) g, heating to 90-92℃ and stirring for 1-1.5 h, adding 2,2-dimethylol propionic acid and stirring for 1-2 h, cooling to 80-82℃, stirring for 4-6 h, continuously cooling to 30-35℃, adding triethylamine and stirring for 0.5-1 h.

[0013] As preferred, the preparation method of the composite adjuvant comprises the following steps: S1: adding carbazole into a container containing N,N-dimethylformamide, adding N,N-dimethylformamide solution dissolving N-bromosuccinimide under stirring at room temperature, after the addition is completed, reacting at room temperature, after the reaction is completed, adding into ice water, extracting, drying the organic phase, filtering, rotary evaporation, recrystallization, vacuum drying, obtaining product a; S2: adding product a, 2-methoxy-5-pyrimidine boronic acid and tetrakis(triphenylphosphine)palladium into a container, adding 1,4-dioxane and potassium carbonate aqueous solution under nitrogen environment, refluxing, after the reaction is completed, adding into ice water, extracting, drying the organic phase, filtering, rotary evaporation, recrystallization, filtering, drying, obtaining product b; S3: adding product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide and tetrahydrofuran into a container, heating and refluxing under nitrogen protection, adding bromohexane during the refluxing, after the refluxing is completed, adding into ice water, extracting, drying the organic phase, filtering, rotary evaporation, recrystallization, filtering, drying, obtaining product c; S4: product c and dichloromethane are added into a container, the reaction is stirred under nitrogen protection, then boron tribromide is slowly added, the reaction is stirred in an ice bath environment, then the temperature is increased to room temperature, after the reaction is completed, it is poured into ice water, extracted, dried, purified, and product d is obtained; product d, 4,4'-difluorobenzophenone, sulfolane, potassium carbonate and toluene are added into a container, the reaction is heated under nitrogen protection, after the reaction is completed, it is washed, and the composite additive is obtained.

[0014] In the above process, the synthesis reaction formula of the composite additive is as follows:

[0015] The mass spectrometric analysis result of product a is: m / z: 324.89 (100.0%), 322.89 (51.4%), 326.89 (48.7%), 325.90 (13.1%), 323.90 (6.7%), 327.89 (6.5%); the mass spectrometric analysis result of product b is: m / z: 383.14 (100.0%), 384.14 (25.9%), 385.14 (3.6%); the mass spectrometric analysis result of product c is: m / z: 467.23 (100.0%), 468.24 (30.7%), 469.24 (5.0%), 468.23 (1.8%); and the mass spectrometric analysis result of product d is: m / z: 439.20 (100.0%), 440.20 (30.0%), 441.21 (4.3%).

[0016] Preferably, in S1, the amount ratio of carbazole to N-bromosuccinimide is (16.12-17.28) g:(32.38-40.12) g, and the reaction is performed at room temperature for 6-8 h; in S2, the amount ratio of product a, 2-methoxy-5-pyrimidine boronic acid, tetrakis(triphenylphosphine)palladium, 1,4-dioxane and potassium carbonate aqueous solution is (20.12-24.78) g:(21.11-26.32) g:(5.12-5.53) g:(120-150) mL:(70-90) mL, the concentration of the potassium carbonate aqueous solution is 0.6 g / mL, and the reflux reaction time is 10-12 h.

[0017] As preferred, in the S3, the ratio of the amounts of product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide, tetrahydrofuran and bromohexane is (4.128-4.984) g:(1.22-1.58) g:(0.168-0.186) g:(0.312-0.422) g:(50-70) mL:(2.5-3.2) mL, and the reflux time is 3-5 h; in the S4, the ratio of the amounts of product c, dichloromethane and boron tribromide is (8.678-9.211) g:(40-50) mL:(4.12-4.88) mL, and the stirring reaction is carried out under nitrogen protection for 0.5-1 h, the reaction is continued for 6-8 h, and the reaction is carried out at room temperature for 10-12 h; the ratio of the amounts of product d, 4,4'-difluorobenzophenone, sulfolane, potassium carbonate and toluene is (3.217-3.389) g:(0.99-1.18) g:(7.2-8.5) mL:(0.78-0.88) g:(10-15) mL, and the heating reaction process is as follows: reaction at 140 DEG C, 160 DEG C and 180 DEG C for 1 h each, and reaction at 190 DEG C for 3 h.

[0018] As preferred, the preparation method of the high-toughness regenerated ABS material comprises the following steps: Step one: the lubricant, antioxidant and colorant are added to the dried regenerated ABS resin, and after mixing and stirring, a uniform masterbatch is obtained; Step two: the uniform masterbatch and the composite auxiliary agent are added to a mixer, mixed, then the modified toughening agent is added, continuously mixed, then melted, extruded, granulated, dried, and the high-toughness regenerated ABS material is obtained.

[0019] As preferred, the prepared high-toughness regenerated ABS material is applied to the mask shell, filter box and frame structure of respiratory protection equipment.

[0020] As above, due to the adoption of the above technical scheme, the beneficial effects of the present application are: 1. The modified toughening agent is prepared by taking vanillin, 1,4-dibromobutane, 4-aminophenol, polymethylhydrogen siloxane, isophorone diisocyanate and 1,4-butanediol as raw materials, and then the composite auxiliary agent is prepared by taking carbazole, N-bromosuccinimide, 2-methoxy-5-pyrimidine boronic acid, bromohexane, boron tribromide and 4,4'-difluorobenzophenone as raw materials, and the modified toughening agent and the composite auxiliary agent are applied to the preparation process of the regenerated ABS material taking the recycled helmet as raw material, which can effectively improve the toughness, chemical resistance and wide temperature range applicability of the regenerated ABS material, and effectively improve the application range of the regenerated ABS material in respiratory protection equipment.

[0021] 2. The modified toughening agent prepared in the application is added to the preparation process of the recycled ABS material, which can effectively improve the impact toughness and chemical resistance of the recycled ABS material. The polyurethane block contained in the modified toughening agent forms a dispersed phase in the ABS matrix, and the flexible chain of the polyurethane block can deform greatly under impact, absorb and dissipate impact energy. The siloxane segment contained in the modified toughening agent forms microzones in the material, inducing crazing or shear bands, further dispersing stress, and the synergistic effect of the two can significantly improve the toughness of the material. At the same time, the siloxane segment contained in the modified toughening agent has hydrophobicity and low surface energy, which can reduce the penetration of chemicals and improve the chemical resistance of the material.

[0022] 3. The composite additive prepared in the application is added to the preparation process of the recycled ABS material, which can effectively improve the mechanical properties, chemical resistance and wide temperature range applicability of the recycled ABS material. The carbazole-pyrimidine biaryl structure contained in the composite additive has a rigid aromatic ring, which can enhance the intermolecular force through π-π stacking to improve the rigidity of the material. The hexyl side chain acts as a flexible segment, which can absorb energy and improve toughness when impacted. The polyaryletherketone structure has hydrophobicity and chemical inertness, which can block the penetration of chemicals. The carbazole and pyrimidine aromatic rings can stabilize the molecular chain through electronic effect to reduce chemical attack, and together improve the resistance of the material to sweat, grease and other chemicals. At the same time, the polyaryletherketone and carbazole-pyrimidine conjugated system contained in the composite additive can maintain the stability of the structure of the ABS material at high temperature, and the flexible hexyl side chain can absorb impact energy through chain segment motion at low temperature to prevent brittle fracture and improve the wide temperature range applicability of the ABS material. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0024] Embodiment 1: The embodiment discloses a preparation method of a modified toughening agent, comprising the following steps: Q1: 9.13g of vanillin, 6.41g of 1,4-dibromobutane, 13.42g of potassium carbonate and 0.51g of potassium iodide are sequentially added to a container, then 100mL of N,N-dimethylformamide is added, stirred and mixed, heated at 80℃, refluxed for 6h under nitrogen atmosphere, cooled after reaction, added to deionized water, precipitated, suction filtered, recrystallized and vacuum dried to obtain intermediate 1; Q2: 3.94 g of intermediate 1 and 2.19 g of 4-aminophenol were added to a container containing 125 mL of N,N-dimethylformamide. After stirring to dissolve, the mixture was heated at 65°C under nitrogen atmosphere and refluxed for 6 h. After the reaction, the mixture was cooled, added to deionized water, precipitated, and dried in vacuo to obtain intermediate 2. Q3: 1.45 g of polymethylhydrogensiloxane was added to a container containing 27.5 mL of isopropanol, followed by the addition of 12.5 mL of N,N-dimethylformamide containing 1.05 g of intermediate 2. The mixture was heated and stirred at 70°C for 20 min. 0.15 mL of a 0.5 g / L chloroplatinic acid isopropanol solution was added, and the mixture was heated to 90°C for 6 h. After the reaction was completed, the mixture was cooled, 0.1 mL of a 0.002 mol / L sodium hydroxide solution was added, and the mixture was heated and dried in a spin-drying machine to obtain intermediate 3. Q4: 14.11 g of intermediate 3 and 5.14 g of isophorone diisocyanate were added to a container, heated to 90°C and stirred for 1.5 h, then 0.66 g of 2,2-dihydroxymethylpropionic acid was added and reacted for 2 h. After cooling to 80°C, 0.45 g of 1,4-butanediol and 0.31 g of dibutyltin dilaurate were added and stirred for 4 h. The temperature was further cooled to 30°C, 0.57 g of triethylamine was added and stirred for 1 h. After stirring, a modified toughening agent was obtained.

[0025] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps: S1: 16.65 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of an N,N-dimethylformamide solution containing 36.25 g of N-bromosuccinimide was added under stirring at room temperature. After the addition was complete, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, and vacuum dried to obtain product a. S2: 22.45 g of product a, 23.71 g of 2-methoxy-5-pyrimidineboronic acid, and 5.33 g of tetrakis(triphenylphosphine)palladium were added to a container. Under a nitrogen atmosphere, 135 mL of 1,4-dioxane and 80 mL of a 0.6 g / mL potassium carbonate aqueous solution were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b. S3: 4.552 g of product b, 1.41 g of sodium hydroxide, 0.174 g of sodium iodide, 0.372 g of tetrabutylammonium bromide, and 60 mL of tetrahydrofuran were added to a container, and the mixture was heated under reflux for 4 h under nitrogen. 2.7 mL of bromohexane was added during the reflux process. After the reflux period, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product c; S4: 8.942 g of product c and 45 mL of dichloromethane were added to a container, stirred and reacted for 1 hour under nitrogen protection, and then 4.51 mL of boron tribromide was slowly added. In an ice bath environment, the mixture was stirred and reacted for 8 hours, and then the temperature was raised to room temperature and reacted for 12 hours. After the reaction, the mixture was poured into ice water, extracted, dried, and purified to obtain product d; 3.301 g of product d, 1.09 g of 4,4'-difluorobenzophenone, 7.9 mL of cyclopentane sulfone, 0.83 g of potassium carbonate and 12.5 mL of toluene were added to a container, and heated to react under nitrogen protection. The process was: react at 140°C, 160°C and 180°C for 1 hour each, and react at 190°C for 3 hours. After the reaction, the mixture was washed to obtain a composite auxiliary agent.

[0026] This embodiment discloses a high-toughness recycled ABS material, composed of the following components by weight: 75 parts of recycled ABS resin, 15 parts of a modified toughening agent, 4.5 parts of a composite additive, 0.9 parts of polypropylene wax, 0.5 parts of an antioxidant 1010, and 1.75 parts of titanium dioxide, wherein the recycled ABS resin is composed of 85 parts of recycled ABS and 7.5 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol.

[0027] This embodiment discloses a method for preparing a high-toughness recycled ABS material, comprising the following steps: Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch; Step 2: Add the uniform masterbatch and compound additives into the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0028] Example 2: This example discloses a method for preparing a modified toughening agent, comprising the following steps: Q1: 8.98 g of vanillin, 6.12 g of 1,4-dibromobutane, 11.82 g of potassium carbonate, and 0.42 g of potassium iodide were added to a container in sequence, followed by the addition of 90 mL of N,N-dimethylformamide. After stirring, the mixture was heated at 80°C under a nitrogen atmosphere and refluxed for 6 h. After the reaction, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried in vacuo to obtain intermediate 1. Q2: Add 3.82 g of intermediate 1 and 2.02 g of 4-aminophenol to a container containing 100 mL of N,N-dimethylformamide, stir to dissolve, heat at 65°C, reflux under nitrogen for 6 h, cool, add to deionized water, precipitate, and dry in vacuo to obtain intermediate 2; Q3: 1.32 g of polymethylhydrogensiloxane was added to a container containing 20 mL of isopropanol, followed by the addition of 10 mL of N,N-dimethylformamide containing 1.12 g of intermediate 2. The mixture was heated and stirred at 70°C for 20 min. 0.12 mL of a 0.5 g / L chloroplatinic acid isopropanol solution was added, and the mixture was heated to 90°C for 6 h. After the reaction was completed, the mixture was cooled, 0.08 mL of a 0.002 mol / L sodium hydroxide solution was added, and the mixture was heated and spin-dried to obtain intermediate 3. Q4: 10.08 g of intermediate 3 and 5.01 g of isophorone diisocyanate were added to a container, heated to 90 ° C and stirred for 1.5 hours, then 0.58 g of 2,2-dihydroxymethylpropionic acid was added and reacted for 2 hours. After cooling to 80 ° C, 0.38 g of 1,4-butanediol and 0.22 g of dibutyltin dilaurate were added and stirred for 4 hours. The temperature was further lowered to 30 ° C, 0.42 g of triethylamine was added and stirred for 1 hour. After stirring, a modified toughening agent was obtained.

[0029] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps: S1: 16.12 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of an N,N-dimethylformamide solution containing 32.38 g of N-bromosuccinimide was added under stirring at room temperature. After the addition was complete, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried in vacuo to obtain product a. S2: 20.12 g of product a, 21.11 g of 2-methoxy-5-pyrimidineboronic acid, and 5.12 g of tetrakis(triphenylphosphine)palladium were added to a container. Under a nitrogen atmosphere, 120 mL of 1,4-dioxane and 70 mL of a 0.6 g / mL potassium carbonate aqueous solution were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b. S3: 4.128 g of product b, 1.22 g of sodium hydroxide, 0.168 g of sodium iodide, 0.312 g of tetrabutylammonium bromide, and 50 mL of tetrahydrofuran were added to a container, and the mixture was heated under reflux for 4 h under nitrogen protection. 2.5 mL of bromohexane was added during the reflux process. After the reflux period, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product c; S4: 8.678 g of product c and 40 mL of dichloromethane were added to a container, stirred and reacted for 1 hour under nitrogen protection, and then 4.12 mL of boron tribromide was slowly added. In an ice bath environment, the mixture was stirred and reacted for 8 hours, and then the temperature was raised to room temperature and reacted for 12 hours. After the reaction, the mixture was poured into ice water, extracted, dried, and purified to obtain product d; 3.217 g of product d, 1.18 g of 4,4'-difluorobenzophenone, 7.2 mL of cyclopentane sulfone, 0.78 g of potassium carbonate and 10 mL of toluene were added to a container, and heated to react under nitrogen protection. The process was: react at 140°C, 160°C and 180°C for 1 hour each, and react at 190°C for 3 hours. After the reaction, the mixture was washed to obtain a composite auxiliary agent.

[0030] This embodiment discloses a high-toughness recycled ABS material, composed of the following components by weight: 70 parts of recycled ABS resin, 20 parts of a modified toughening agent, 2 parts of a composite additive, 1.3 parts of polypropylene wax, 0.2 parts of an antioxidant 1010, and 1.2 parts of titanium dioxide, wherein the recycled ABS resin is composed of 80 parts of recycled ABS and 10 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol.

[0031] This embodiment discloses a method for preparing a high-toughness recycled ABS material, comprising the following steps: Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch; Step 2: Add the uniform masterbatch and compound additives into the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0032] Example 3: This example discloses a method for preparing a modified toughening agent, comprising the following steps: Q1: 9.24 g of vanillin, 6.68 g of 1,4-dibromobutane, 15.63 g of potassium carbonate, and 0.58 g of potassium iodide were added to a container in sequence, followed by the addition of 110 mL of N,N-dimethylformamide. After stirring and mixing, the mixture was heated at 80°C under a nitrogen atmosphere and refluxed for 6 h. After the reaction was completed, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried in vacuo to obtain intermediate 1. Q2: 4.06 g of intermediate 1 and 2.36 g of 4-aminophenol were added to a container containing 150 mL of N,N-dimethylformamide. After stirring to dissolve, the mixture was heated at 65°C under nitrogen atmosphere and refluxed for 6 h. After the reaction, the mixture was cooled, added to deionized water, precipitated, and dried in vacuo to obtain intermediate 2. Q3: 1.68 g of polymethylhydrogensiloxane was added to a container containing 35 mL of isopropanol, followed by the addition of 15 mL of N,N-dimethylformamide containing 0.98 g of intermediate 2. The mixture was heated and stirred at 70°C for 20 min. 0.18 mL of a 0.5 g / L chloroplatinic acid isopropanol solution was added, and the mixture was heated to 90°C for 6 h. After the reaction was completed, the mixture was cooled, 0.12 mL of a 0.002 mol / L sodium hydroxide solution was added, and the mixture was heated and spin-dried to obtain intermediate 3. Q4: 18.12 g of intermediate 3 and 5.28 g of isophorone diisocyanate were added to a container, heated to 90 ° C and stirred for 1.5 hours, then 0.74 g of 2,2-dihydroxymethylpropionic acid was added and reacted for 2 hours. After cooling to 80 ° C, 0.52 g of 1,4-butanediol and 0.38 g of dibutyltin dilaurate were added and stirred for 4 hours. The temperature was further lowered to 30 ° C, 0.65 g of triethylamine was added and stirred for 1 hour. After stirring, a modified toughening agent was obtained.

[0033] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps: S1: 17.28 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of an N,N-dimethylformamide solution containing 40.12 g of N-bromosuccinimide was added under stirring at room temperature. After the addition was complete, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried in vacuo to obtain product a. S2: 24.78 g of product a, 26.32 g of 2-methoxy-5-pyrimidineboronic acid, and 5.53 g of tetrakis(triphenylphosphine)palladium were added to a container. Under a nitrogen atmosphere, 150 mL of 1,4-dioxane and 90 mL of a 0.6 g / mL potassium carbonate aqueous solution were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b. S3: 4.984 g of product b, 1.58 g of sodium hydroxide, 0.186 g of sodium iodide, 0.422 g of tetrabutylammonium bromide, and 70 mL of tetrahydrofuran were added to a container, and the mixture was heated under reflux for 4 h under nitrogen. 3.2 mL of bromohexane was added during the reflux process. After the reflux period, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product c; S4: 9.211 g of product c and 50 mL of dichloromethane were added to a container, stirred and reacted for 1 hour under nitrogen protection, and then 4.88 mL of boron tribromide was slowly added. In an ice bath environment, the mixture was stirred and reacted for 8 hours, and then the temperature was raised to room temperature and reacted for 12 hours. After the reaction, the mixture was poured into ice water, extracted, dried, and purified to obtain product d; 3.389 g of product d, 0.99 g of 4,4'-difluorobenzophenone, 8.5 mL of cyclopentane sulfone, 0.88 g of potassium carbonate and 15 mL of toluene were added to a container, and heated to react under nitrogen protection. The process was: react at 140°C, 160°C and 180°C for 1 hour each, and react at 190°C for 3 hours. After the reaction, the mixture was washed to obtain a composite auxiliary agent.

[0034] This embodiment discloses a high-toughness recycled ABS material, composed of the following components by weight: 80 parts of recycled ABS resin, 10 parts of a modified toughening agent, 7 parts of a composite additive, 0.5 parts of polypropylene wax, 0.8 parts of an antioxidant 1010, and 2.3 parts of titanium dioxide, wherein the recycled ABS resin is composed of 90 parts of recycled ABS and 5 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol.

[0035] This embodiment discloses a method for preparing a high-toughness recycled ABS material, comprising the following steps: Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch; Step 2: Add the uniform masterbatch and compound additives into the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0036] Example 4: This example discloses a method for preparing a modified toughening agent, comprising the following steps: Q1: 9.07 g of vanillin, 6.23 g of 1,4-dibromobutane, 12.71 g of potassium carbonate, and 0.46 g of potassium iodide were added to a container in sequence, followed by the addition of 95 mL of N,N-dimethylformamide. After stirring, the mixture was heated at 80°C under a nitrogen atmosphere and refluxed for 6 h. After the reaction, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried in vacuo to obtain intermediate 1. Q2: Add 3.88 g of intermediate 1 and 2.11 g of 4-aminophenol to a container containing 110 mL of N,N-dimethylformamide, stir to dissolve, heat at 65°C, reflux under nitrogen for 6 h, cool after completion of the reaction, add to deionized water, precipitate, and vacuum dry to obtain intermediate 2; Q3: 1.38 g of polymethylhydrogensiloxane was added to a container containing 25 mL of isopropanol, followed by the addition of 11 mL of N,N-dimethylformamide containing 1.01 g of intermediate 2. The mixture was heated and stirred at 70°C for 20 min. 0.13 mL of a 0.5 g / L chloroplatinic acid isopropanol solution was added, and the mixture was heated to 90°C for 6 h. After the reaction was completed, the mixture was cooled, 0.09 mL of a 0.002 mol / L sodium hydroxide solution was added, and the mixture was heated and dried in a spin-drying machine to obtain intermediate 3. Q4: 12.27 g of intermediate 3 and 5.07 g of isophorone diisocyanate were added to a container, heated to 90 ° C and stirred for 1.5 hours, then 0.62 g of 2,2-dihydroxymethylpropionic acid was added and reacted for 2 hours. After cooling to 80 ° C, 0.41 g of 1,4-butanediol and 0.28 g of dibutyltin dilaurate were added and stirred for 4 hours. The temperature was further lowered to 30 ° C, 0.48 g of triethylamine was added and stirred for 1 hour. After stirring, a modified toughening agent was obtained.

[0037] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps: S1: 16.37 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of an N,N-dimethylformamide solution containing 34.57 g of N-bromosuccinimide was added under stirring at room temperature. After the addition was complete, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried in vacuo to obtain product a. S2: 21.57 g of product a, 22.18 g of 2-methoxy-5-pyrimidineboronic acid, and 5.27 g of tetrakis(triphenylphosphine)palladium were added to a container. Under a nitrogen atmosphere, 130 mL of 1,4-dioxane and 75 mL of a 0.6 g / mL potassium carbonate aqueous solution were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b. S3: 4.371 g of product b, 1.37 g of sodium hydroxide, 0.172 g of sodium iodide, 0.334 g of tetrabutylammonium bromide, and 65 mL of tetrahydrofuran were added to a container, and the mixture was heated under reflux for 4 h under nitrogen protection. 2.6 mL of bromohexane was added during the reflux process. After the reflux period, the mixture was added to ice water, extracted, and the organic phase was dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product c; S4: 8.738 g of product c and 42 mL of dichloromethane were added to a container, stirred and reacted for 1 hour under nitrogen protection, and then 4.23 mL of boron tribromide was slowly added. In an ice bath environment, the mixture was stirred and reacted for 8 hours, and then the temperature was raised to room temperature and reacted for 12 hours. After the reaction, the mixture was poured into ice water, extracted, dried, and purified to obtain product d; 3.281 g of product d, 1.05 g of 4,4'-difluorobenzophenone, 7.5 mL of cyclopentane sulfone, 0.81 g of potassium carbonate and 11 mL of toluene were added to a container, and heated to react under nitrogen protection. The process was: react at 140°C, 160°C and 180°C for 1 hour each, and react at 190°C for 3 hours. After the reaction, the mixture was washed to obtain a composite auxiliary agent.

[0038] This embodiment discloses a high-toughness recycled ABS material, composed of the following components by weight: 72 parts of recycled ABS resin, 18 parts of a modified toughening agent, 3 parts of a composite additive, 0.7 parts of polypropylene wax, 0.4 parts of an antioxidant 1010, and 1.5 parts of titanium dioxide, wherein the recycled ABS resin is composed of 82 parts of recycled ABS and 6 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol.

[0039] This embodiment discloses a method for preparing a high-toughness recycled ABS material, comprising the following steps: Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch; Step 2: Add the uniform masterbatch and compound additives into the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0040] Comparative Example 1: Compared with Example 1, in the process of preparing the high-toughness recycled ABS material in Comparative Example 1, no composite auxiliary agent is added, and other conditions remain unchanged.

[0041] Comparative Example 2: Compared with Example 1, in Comparative Example 2, during the preparation of the high-toughness recycled ABS material, no modified toughening agent was added, and other conditions remained unchanged.

[0042] Performance testing: The recycled ABS materials prepared according to Examples 1-4 and Comparative Examples 1-2 were dried, injection molded, pressure maintained, cooled, and demolded to prepare mask shells for respiratory protective equipment. Performance tests were performed on the masks. The impact strength of the samples was tested according to GB / T 1843-2008, the tensile properties of the samples were tested according to GB / T 1040.2-2022, the chemical resistance of the samples was tested according to GB / T 11547-2008, the heat deformation temperature of the samples was tested according to GB / T 1634.2-2019, and the low temperature resistance of the samples was tested according to GB / T5470-2008. The test results are shown in Table 1:

[0043] Table 1

[0044]

[0045] The test results in Table 1 demonstrate that the methods of Examples 1-4 can produce recycled ABS materials with excellent toughness, chemical resistance, and wide temperature range applicability. A comparison of Comparative Example 1 with Examples 1-4 reveals that the addition of a composite additive effectively improves the toughness, chemical resistance, and wide temperature range applicability of the recycled ABS material. A comparison of Comparative Example 2 with Examples 1-4 reveals that the addition of a modified toughening agent effectively enhances the toughness and chemical resistance of the recycled ABS material.

[0046] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0047] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. High toughness recycled ABS material, characterized by: The invention comprises the following components in parts by weight: 70-80 parts of recycled ABS resin, 10-20 parts of modified toughening agent, 2-7 parts of composite auxiliary agent, 0.5-1.3 parts of lubricant, 0.2-0.8 parts of antioxidant and 1.2-2.3 parts of colorant, wherein the recycled ABS resin is composed of 80-90 parts of recycled ABS and 5-10 parts of polyethylene terephthalate-1,4-cyclohexanedimethanol ester; the modified toughening agent is prepared by taking vanillin, 1,4-dibromobutane, 4-aminophenol, polymethylhydrogensiloxane, isophorone diisocyanate and 1,4-butanediol as raw materials; and the composite auxiliary agent is prepared by taking carbazole, N-bromosuccinimide, 2-methoxy-5-pyrimidineboric acid, hexyl bromide, boron tribromide and 4,4'-difluorobenzophenone as raw materials.

2. The high-toughness recycled ABS material according to claim 1, characterized in that: The preparation method of the modified toughening agent comprises the following steps: Q1: Vanillin, 1,4-dibromobutane, potassium carbonate, and potassium iodide were added to a container in sequence, and then N,N-dimethylformamide was added. After stirring and mixing, the mixture was heated and refluxed under nitrogen. After the reaction was completed, the mixture was cooled and added to deionized water for precipitation. The mixture was filtered, recrystallized, and dried in vacuo to obtain intermediate 1. Q2: Add intermediate 1 and 4-aminophenol to a container containing N,N-dimethylformamide, stir and dissolve, heat, and reflux under nitrogen. After the reaction is complete, cool, add to deionized water, precipitate, and vacuum dry to obtain intermediate 2; Q3: Add polymethylhydrogensiloxane to a container containing isopropanol, then add N,N-dimethylformamide containing intermediate 2, heat and stir, add chloroplatinic acid isopropanol solution, continue heating and react, cool after the reaction, add sodium hydroxide solution, heat and dry, and obtain intermediate 3; Q4: Add intermediate 3 and isophorone diisocyanate to a container, heat and stir, then add 2,2-dihydroxymethylpropionic acid to react, cool down and add 1,4-butanediol and dibutyltin dilaurate, stir and react, continue to cool down, add triethylamine and stir, and after stirring, obtain a modified toughening agent.

3. The high-toughness recycled ABS material according to claim 2, characterized in that: In the Q1, the usage ratio of vanillin, 1,4-dibromobutane, potassium carbonate, potassium iodide and N,N-dimethylformamide is (8.98-9.24) g: (6.12-6.68) g: (11.82-15.63) g: (0.42-0.58) g: (90-110) mL; in the Q2, the usage ratio of the intermediate 1,4-aminophenol and N,N-dimethylformamide is (3.82-4.06) g: (2.02-2.36) g: (100-150) mL.

4. The high-toughness recycled ABS material according to claim 2, characterized in that: In Q3, the usage ratio of polymethylhydrogensiloxane, isopropyl alcohol, intermediate 2, N,N-dimethylformamide, chloroplatinic acid isopropyl alcohol solution and sodium hydroxide solution is (1.32-1.68) g: (20-35) mL: (0.98-1.12) g: (10-15) mL: (0.12-0.18) mL: (0.08-0.12) mL.

5. The high-toughness recycled ABS material according to claim 2, characterized in that: In Q4, the usage ratio of intermediate 3, isophorone diisocyanate, 2,2-dihydroxymethylpropionic acid, 1,4-butanediol, dibutyltin dilaurate and triethylamine is (10.08-18.12) g: (5.01-5.28) g: (0.58-0.74) g: (0.38-0.52) g: (0.22-0.38) g: (0.42-0.65) g.

6. The high-toughness recycled ABS material according to claim 1, characterized in that: The preparation method of the composite auxiliary agent comprises the following steps: S1: Carbazole is added to a container containing N,N-dimethylformamide, and a solution of N-bromosuccinimide dissolved in N,N-dimethylformamide is added under stirring at room temperature. After the addition is complete, the mixture is reacted at room temperature. After the reaction is complete, the mixture is added to ice water, extracted, and the organic phase is dried, filtered, rotary evaporated, recrystallized, and vacuum dried to obtain product a; S2: Add product a, 2-methoxy-5-pyrimidineboronic acid and tetrakis(triphenylphosphine)palladium to a container, add 1,4-dioxane and potassium carbonate aqueous solution under nitrogen environment, reflux reaction, add to ice water after the reaction, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, and dry to obtain product b; S3: Add product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide and tetrahydrofuran to a container, heat to reflux under nitrogen protection, add hexyl bromide during reflux, add ice water after reflux, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, and dry to obtain product c; S4: Add product c and dichloromethane to a container, stir and react under nitrogen protection, then slowly add boron tribromide, stir and react in an ice bath environment, then heat to room temperature to react, pour into ice water after the reaction, extract, dry, and purify to obtain product d; add product d, 4,4'-difluorobenzophenone, cyclopentane sulfone, potassium carbonate and toluene to a container, heat and react under nitrogen protection, wash after the reaction to obtain a composite auxiliary agent.

7. The high-toughness recycled ABS material according to claim 6, characterized in that: In S1, the usage ratio of carbazole and N-bromosuccinimide is (16.12-17.28) g: (32.38-40.12) g; in S2, the usage ratio of product a, 2-methoxy-5-pyrimidineboronic acid, tetrakis(triphenylphosphine)palladium, 1,4-dioxane and potassium carbonate aqueous solution is (20.12-24.78) g: (21.11-26.32) g: (5.12-5.53) g: (120-150) mL: (70-90) mL.

8. The high-toughness recycled ABS material according to claim 6, characterized in that: In S3, the usage ratio of product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide, tetrahydrofuran and bromohexane is (4.128-4.984) g: (1.22-1.58) g: (0.168-0.186) g: (0.312-0.422) g: (50-70) mL: (2.5-3.2) mL; in S4, the usage ratio of product c, dichloromethane and boron tribromide is (4.128-4.984) g: (1.22-1.58) g: (0.168-0.186) g: (0.312-0.422) g: (50-70) mL: (2.5-3.2) mL. The dosage ratio of is (8.678-9.211) g: (40-50) mL: (4.12-4.88) mL; the dosage ratio of product d, 4,4'-difluorobenzophenone, cyclopentane sulfone, potassium carbonate and toluene is (3.217-3.389) g: (0.99-1.18) g: (7.2-8.5) mL: (0.78-0.88) g: (10-15) mL.

9. The method for preparing a high-toughness recycled ABS material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Add lubricant, antioxidant and colorant to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch; Step 2: Add the uniform masterbatch and compound additives into the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

10. The application of high-toughness recycled ABS material is characterized by: The high-toughness recycled ABS material according to any one of claims 1 to 8 is applied to the mask shell, filter box and frame structure of respiratory protection equipment.

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