High-toughness recycled ABS materials and their application in respiratory protective equipment

Abstract

This invention discloses a high-toughness recycled ABS material and its application in respiratory protective equipment, belonging to the field of recycled ABS material preparation technology. The high-toughness recycled ABS material comprises the following components by weight: 70-80 parts recycled ABS resin, 10-20 parts modified toughening agent, 2-7 parts composite additives, 0.5-1.3 parts lubricant, 0.2-0.8 parts antioxidant, and 1.2-2.3 parts colorant. The recycled ABS resin consists of 80-90 parts recycled ABS and 5-10 parts polyethylene terephthalate-1,4-cyclohexanediol ester. The recycled ABS material prepared using the above substances exhibits excellent toughness, chemical resistance, and wide temperature range applicability, thereby effectively improving its application in respiratory protective equipment.

Description

Technical Field

[0001] This invention belongs to the field of recycled material preparation technology, specifically relating to high-toughness recycled ABS material and its application in respiratory protective equipment. Background Technology

[0002] Recycled ABS material, as a recycled modified product of acrylonitrile-butadiene-styrene copolymer, has become a research hotspot due to environmental protection demands and the trend of material recycling. Given that construction sites generate a large number of discarded helmets primarily made of ABS, recycling these helmets and processing them professionally as raw materials for recycled ABS not only achieves effective waste reuse and reduces environmental pollution but also lowers raw material costs. However, the current limitations in the basic properties of this type of recycled ABS material restrict its direct application in high-end fields such as respiratory protective equipment. While traditional ABS materials, thanks to the toughness advantage provided by the butadiene component, can maintain elasticity in low-temperature environments, the breakage and recombination of molecular chains during recycling significantly reduces their toughness, making them prone to embrittlement and fracture, especially in low-temperature scenarios. This makes it difficult to meet the stringent impact resistance requirements of respiratory protective equipment. Meanwhile, due to its high styrene content, ABS material generally has a heat distortion temperature of around 80℃. The reduced molecular weight after recycling further weakens its high-temperature resistance, making it prone to softening and deformation in high-temperature environments. Conversely, its reduced toughness at low temperatures leads to insufficient impact resistance. This dual weakness in temperature resistance makes it difficult to cope with the wide temperature range of -20℃ to 60℃ encountered in respiratory protective equipment applications. For example, in outdoor operations in cold regions or industrial protective scenarios in high-temperature workshops, breathing valve shells or filter supports made of traditional recycled ABS material are prone to cracking due to thermal stress, affecting the equipment's sealing performance and service life.

[0003] Patent CN120230369A discloses a high-toughness recycled ABS composite material and its preparation method, belonging to the field of material recycling technology. It addresses the technical problem that the tensile strength and flame retardant properties of recycled ABS materials in the prior art need further improvement. The invention comprises the following raw material components by weight: 70-80 parts recycled ABS, 10-12 parts modified toughening agent, 15-18 parts composite whiskers, and 3-6 parts auxiliary materials. The invention involves protecting the active groups in the ABS chain segments using a protective agent and a temperature-regulating agent during the waste ABS recycling process, obtaining recycled ABS through solvent purification, and preparing the modified toughening agent and composite whiskers. After melt extrusion of these three components with the auxiliary materials, cross-linking is achieved through the irradiation promoting effect of titanium dioxide, ultimately yielding a high-toughness composite ABS. Although the composite ABS prepared by the above method uses protective agents and temperature agents to protect the active groups, the recycling system is complex and it is difficult to completely avoid damage to the active groups, resulting in weakened inter-chain forces. The compatibility of the modified toughening agent and composite whiskers with recycled ABS is limited, and a uniform and effective toughening network structure cannot be fully formed. Therefore, there is still room to improve the toughness of the composite ABS material, thereby broadening its application range in respiratory protection equipment. Summary of the Invention

[0004] The purpose of this invention is to provide high-toughness recycled ABS material and its application in respiratory protective equipment, in order to solve the technical problem of poor toughness in the prior art.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a high-toughness recycled ABS material, which is composed of the following components by weight: 70-80 parts recycled ABS resin, 10-20 parts modified toughening agent, 2-7 parts composite additive, 0.5-1.3 parts lubricant, 0.2-0.8 parts antioxidant and 1.2-2.3 parts colorant, wherein the recycled ABS resin is composed of 80-90 parts recycled ABS and 5-10 parts polyethylene terephthalate-1,4-cyclohexanediol ester.

[0007] 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 blue.

[0008] Preferably, the method for preparing the modified toughening agent includes the following steps:

[0009] 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, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1.

[0010] Q2: Add intermediate 1 and 4-aminophenol to a container containing N,N-dimethylformamide, stir to dissolve, heat, reflux under nitrogen atmosphere, after the reaction is completed, cool, add to deionized water, precipitate, and vacuum dry to obtain intermediate 2;

[0011] Q3: Add polymethylhydrosiloxane to a container containing isopropanol, then add N,N-dimethylformamide containing intermediate 2, heat and stir, add isopropanol chloroplatinate solution, continue heating and reacting, after the reaction is complete, cool, add sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3;

[0012] Q4: Add intermediate 3 and isophorone diisocyanate to a container, heat and stir, then add 2,2-dimethylolpropionic acid to react, cool down and add 1,4-butanediol and dibutyltin dilaurate, stir and react, continue to cool down, add triethylamine and stir, after stirring, the modified toughening agent is obtained.

[0013] The synthesis reaction formula for intermediate 3 in the above process is as follows:

[0014]

[0015] The mass spectrometry analysis results of intermediate 1 were: m / z: 358.14 (100.0%), 359.14 (21.6%), 360.15 (3.6%); the mass spectrometry analysis results of intermediate 2 were: m / z: 540.23 (100.0%), 541.23 (35.2%), 542.23 (7.4%).

[0016] Preferably, in Q1, the 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℃, and the reflux reaction time is 5-7 h; in Q2, the ratio of 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℃, and the reflux reaction time is 4-6 h.

[0017] Preferably, in Q3, the ratio of polymethylhydrosiloxane, isopropanol, intermediate 2, N,N-dimethylformamide, isopropanol chloroplatinate 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. The heating and stirring temperature is 70-73℃, the time is 10-20 min, and the reaction is continued at 90-92℃ for 6-8 h. The concentration of isopropanol chloroplatinate solution is 0.5 g / L, and the concentration of sodium hydroxide solution is 0.002 mol / L.

[0018] Preferably, in Q4, the ratio of intermediate 3, isophorone diisocyanate, 2,2-dimethylolpropionic 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. The mixture is heated to 90-92°C and stirred for 1-1.5 h. 2,2-dimethylolpropionic acid is added and reacted for 1-2 h. The mixture is then cooled to 80-82°C and stirred for 4-6 h. The mixture is further cooled to 30-35°C and triethylamine is added and stirred for 0.5-1 h.

[0019] Preferably, the preparation method of the composite additive includes the following steps:

[0020] S1: Carbazole was added to a container containing N,N-dimethylformamide. N,N-dimethylformamide solution containing N-bromosuccinimide was added while stirring at room temperature. After the addition was complete, the reaction was allowed to proceed at room temperature. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a.

[0021] S2: Add product a, 2-methoxy-5-pyrimidineboronic acid and tetra(triphenylphosphine)palladium to a container. Under nitrogen atmosphere, add 1,4-dioxane and potassium carbonate aqueous solution, reflux the reaction. After the reaction is complete, add ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product b.

[0022] S3: Add product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide and tetrahydrofuran into a container, heat under nitrogen protection and reflux, add bromohexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c;

[0023] S4: Add product c and dichloromethane to a container and stir under nitrogen protection. Then slowly add boron tribromide and stir under an ice bath. Then heat to room temperature and react. After the reaction is complete, pour into ice water, extract, dry, and purify to obtain product d. Add product d, 4,4'-difluorobenzophenone, sulfolane, potassium carbonate, and toluene to a container and heat under nitrogen protection. After the reaction is complete, wash to obtain the composite auxiliary agent.

[0024] The synthesis reaction formula for the composite additive in the above process is as follows:

[0025]

[0026] The mass spectrometry analysis results for product a were: 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%); for product b: m / z: 383.14 (100.0%), 384.14 (25.9%), 385.14 (3.6%); for product c: m / z: 467.23 (100.0%), 468.24 (30.7%), 469.24 (5.0%), 468.23 (1.8%); and for product d: m / z: 439.20. (100.0%), 440.20 (30.0%), 441.21 (4.3%).

[0027] Preferably, in S1, the ratio of carbazole to N-bromosuccinimide is (16.12-17.28) g: (32.38-40.12) g, and the reaction is carried out at room temperature for 6-8 h; in S2, the 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, the concentration of potassium carbonate aqueous solution is 0.6 g / mL, and the reflux reaction time is 10-12 h.

[0028] Preferably, in step S3, the 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, and the reflux time is 3-5 h; in step S4, the ratio of product c, dichloromethane, and boron tribromide is (8.678-9.211) g : (40-50) mL : ( 4.12-4.88) mL, stir the reaction under nitrogen protection for 0.5-1 h, continue the reaction for 6-8 h, and react at room temperature for 10-12 h; the ratio 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, the heating reaction process is: react at 140℃, 160℃ and 180℃ for 1 h each, and react at 190℃ for 3 h.

[0029] Preferably, the method for preparing the high-toughness recycled ABS material includes the following steps:

[0030] Step 1: Add lubricant, antioxidant and colorant to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch;

[0031] Step 2: Add the uniform masterbatch and composite additives to 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] Preferably, the prepared high-toughness recycled ABS material is used in the mask shell, filter cartridge and frame structure of respiratory protective equipment.

[0033] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0034] 1. This invention first prepares a modified toughening agent using vanillin, 1,4-dibromobutane, 4-aminophenol, polymethylhydrosiloxane, isophorone diisocyanate, and 1,4-butanediol as raw materials. Subsequently, a composite additive is prepared using carbazole, N-bromosuccinimide, 2-methoxy-5-pyrimidineboronic acid, hexane, boron tribromide, and 4,4'-difluorobenzophenone as raw materials. Applying the modified toughening agent and the composite additive to the preparation process of recycled ABS material made from recycled helmets can effectively improve its toughness, chemical resistance, and wide temperature range applicability, thereby effectively expanding the application range of recycled ABS material in respiratory protective equipment.

[0035] 2. The present invention adds the prepared modified toughening agent to the preparation process of recycled ABS material, which can effectively improve its impact toughness and chemical resistance. The polyurethane blocks contained in the modified toughening agent form a dispersed phase in the ABS matrix. Its flexible chain undergoes large deformation under impact, absorbing and dissipating impact energy. The siloxane segments contained in the agent form micro-regions in the material, inducing crazes or shear bands, further dispersing stress. The synergistic effect of the two significantly improves its toughness. At the same time, the siloxane segments contained in the modified toughening agent have hydrophobicity and low surface energy, which can reduce the penetration of chemical substances and improve its chemical resistance.

[0036] 3. This invention adds the prepared composite additive to the preparation process of recycled ABS material, which can effectively improve its mechanical properties, chemical resistance, and wide temperature range applicability. The carbazole-pyrimidine biaryl structure contained in the composite additive has a rigid aromatic ring, which can enhance the intermolecular forces and improve the rigidity of the material through π-π stacking. The hexyl side chain, as a flexible segment, absorbs energy and improves toughness when subjected to impact. The polyaryletherketone structure has hydrophobicity and chemical inertness, which can block the penetration of chemical substances. The carbazole and pyrimidine aromatic rings stabilize the molecular chain through electronic effects to reduce chemical attack, and together improve the material's resistance to chemicals such as sweat and oil. At the same time, the polyaryletherketone and carbazole-pyrimidine conjugated system can maintain the structural stability of the ABS material at high temperatures, and the flexibility of the hexyl side chain allows the ABS to absorb impact energy through chain segment movement at low temperatures to prevent brittle fracture and improve its wide temperature range applicability. Detailed Implementation

[0037] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] Example 1: This example discloses a method for preparing a modified toughening agent, including the following steps:

[0039] Q1: 9.13g vanillin, 6.41g 1,4-dibromobutane, 13.42g potassium carbonate and 0.51g potassium iodide were added to a container in sequence, followed by 100mL N,N-dimethylformamide. After stirring and mixing, the mixture was heated to 80℃ and refluxed under nitrogen for 6 hours. After the reaction was completed, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1.

[0040] Q2: Add 3.94g of intermediate 1 and 2.19g of 4-aminophenol to a container containing 125mL of N,N-dimethylformamide, stir to dissolve, heat at 65℃ and reflux under nitrogen for 6h. After the reaction is completed, cool, add to deionized water, precipitate, and dry under vacuum to obtain intermediate 2.

[0041] Q3: Add 1.45g of polymethylhydrosiloxane to a container containing 27.5mL of isopropanol, then add 12.5mL of N,N-dimethylformamide containing 1.05g of intermediate 2, heat and stir at 70℃ for 20min, add 0.15mL of 0.5g / L isopropanol chloroplatinate solution, continue heating to 90℃ and react for 6h. After the reaction is complete, cool, add 0.1mL of 0.002mol / L sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3;

[0042] Q4: Add 14.11g of intermediate 3 and 5.14g of isophorone diisocyanate to a container, heat to 90℃ and stir for 1.5h, then add 0.66g of 2,2-dimethylolpropionic acid and react for 2h. After cooling to 80℃, add 0.45g of 1,4-butanediol and 0.31g of dibutyltin dilaurate and stir for 4h. Then continue to cool to 30℃ and add 0.57g of triethylamine and stir for 1h. After stirring, the modified toughening agent is obtained.

[0043] This embodiment discloses a method for preparing a composite additive, including the following steps:

[0044] S1: 16.65 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of N,N-dimethylformamide solution containing 36.25 g of N-bromosuccinimide was added while 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, the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a.

[0045] S2: 22.45g of product a, 23.71g of 2-methoxy-5-pyrimidineboronic acid and 5.33g of tetrakis(triphenylphosphine)palladium were added to a container. Under nitrogen atmosphere, 135mL of 1,4-dioxane and 80mL of potassium carbonate aqueous solution with a concentration of 0.6g / mL were added. The mixture was refluxed for 12h. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b.

[0046] S3: Add 4.552g of product b, 1.41g of sodium hydroxide, 0.174g of sodium iodide, 0.372g of tetrabutylammonium bromide and 60mL of tetrahydrofuran to a container, heat under nitrogen protection and reflux for 4h, add 2.7mL of bromhexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c;

[0047] S4: 8.942 g of product c and 45 mL of dichloromethane were added to a container and stirred for 1 h under nitrogen protection. Then, 4.51 mL of boron tribromide was slowly added and stirred for 8 h under an ice bath. The mixture was then heated to room temperature and reacted for 12 h. After the reaction was completed, 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 sulfolane, 0.83 g of potassium carbonate, and 12.5 mL of toluene were added to a container and heated for 1 h each at 140 °C, 160 °C, and 180 °C, and then at 190 °C for 3 h. After the reaction was completed, the mixture was washed to obtain the composite auxiliary agent.

[0048] This embodiment discloses a high-toughness recycled ABS material, which is composed of the following components by weight: 75 parts recycled ABS resin, 15 parts modified toughening agent, 4.5 parts composite additive, 0.9 parts polypropylene wax, 0.5 parts antioxidant 1010 and 1.75 parts titanium dioxide, wherein the recycled ABS resin is composed of 85 parts recycled ABS and 7.5 parts polyethylene terephthalate-1,4-cyclohexanediol ester.

[0049] This embodiment discloses a method for preparing high-toughness recycled ABS material, including the following steps:

[0050] Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch;

[0051] Step 2: Add the uniform masterbatch and composite additives to the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0052] Example 2: This example discloses a method for preparing a modified toughening agent, including the following steps:

[0053] Q1: 8.98g vanillin, 6.12g 1,4-dibromobutane, 11.82g potassium carbonate and 0.42g potassium iodide were added to a container in sequence, followed by 90mL N,N-dimethylformamide. After stirring and mixing, the mixture was heated to 80℃ and refluxed under nitrogen for 6 hours. After the reaction was completed, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1.

[0054] Q2: Add 3.82g of intermediate 1 and 2.02g of 4-aminophenol to a container containing 100mL of N,N-dimethylformamide, stir to dissolve, heat at 65℃ and reflux under nitrogen for 6h. After the reaction is completed, cool, add to deionized water, precipitate, and dry under vacuum to obtain intermediate 2.

[0055] Q3: Add 1.32g of polymethylhydrosiloxane to a container containing 20mL of isopropanol, then add 10mL of N,N-dimethylformamide containing 1.12g of intermediate 2, heat and stir at 70℃ for 20min, add 0.12mL of 0.5g / L isopropanol chloroplatinate solution, continue heating to 90℃ and react for 6h. After the reaction is completed, cool, add 0.08mL of 0.002mol / L sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3;

[0056] Q4: Add 10.08g of intermediate 3 and 5.01g of isophorone diisocyanate to a container, heat to 90℃ and stir for 1.5h, then add 0.58g of 2,2-dimethylolpropionic acid and react for 2h. After cooling to 80℃, add 0.38g of 1,4-butanediol and 0.22g of dibutyltin dilaurate and stir for 4h. Then continue to cool to 30℃ and add 0.42g of triethylamine and stir for 1h. After stirring, the modified toughening agent is obtained.

[0057] This embodiment discloses a method for preparing a composite additive, including the following steps:

[0058] S1: 16.12 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of N,N-dimethylformamide solution containing 32.38 g of N-bromosuccinimide was added while stirring at room temperature. After the addition was complete, the mixture was reacted at room temperature for 8 h. After the reaction was complete, the mixture was added to ice water, extracted, the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a.

[0059] 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 nitrogen atmosphere, 120 mL of 1,4-dioxane and 70 mL of potassium carbonate aqueous solution with a concentration of 0.6 g / mL were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b.

[0060] S3: Add 4.128g of product b, 1.22g of sodium hydroxide, 0.168g of sodium iodide, 0.312g of tetrabutylammonium bromide and 50mL of tetrahydrofuran to a container, heat under nitrogen protection and reflux for 4h, add 2.5mL of bromohexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c;

[0061] S4: 8.678 g of product c and 40 mL of dichloromethane were added to a container and stirred for 1 h under nitrogen protection. Then, 4.12 mL of boron tribromide was slowly added and stirred for 8 h under an ice bath. The mixture was then heated to room temperature and reacted for 12 h. After the reaction was completed, 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 sulfolane, 0.78 g of potassium carbonate, and 10 mL of toluene were added to a container and heated for 1 h each at 140 °C, 160 °C, and 180 °C, and then at 190 °C for 3 h. After the reaction was completed, the mixture was washed to obtain the composite auxiliary agent.

[0062] This embodiment discloses a high-toughness recycled ABS material, which is composed of the following components by weight: 70 parts recycled ABS resin, 20 parts modified toughening agent, 2 parts composite additive, 1.3 parts polypropylene wax, 0.2 parts antioxidant 1010 and 1.2 parts titanium dioxide, wherein the recycled ABS resin is composed of 80 parts recycled ABS and 10 parts polyethylene terephthalate-1,4-cyclohexanediol ester.

[0063] This embodiment discloses a method for preparing high-toughness recycled ABS material, including the following steps:

[0064] Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch;

[0065] Step 2: Add the uniform masterbatch and composite additives to the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0066] Example 3: This example discloses a method for preparing a modified toughening agent, including the following steps:

[0067] Q1: 9.24g vanillin, 6.68g 1,4-dibromobutane, 15.63g potassium carbonate and 0.58g potassium iodide were added to a container in sequence, followed by 110mL N,N-dimethylformamide. After stirring and mixing, the mixture was heated to 80℃ and refluxed under nitrogen for 6 hours. After the reaction was completed, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1.

[0068] Q2: Add 4.06g of intermediate 1 and 2.36g of 4-aminophenol to a container containing 150mL of N,N-dimethylformamide, stir to dissolve, heat at 65℃ and reflux under nitrogen for 6h. After the reaction is completed, cool, add to deionized water, precipitate, and dry under vacuum to obtain intermediate 2.

[0069] Q3: Add 1.68g of polymethylhydrosiloxane to a container containing 35mL of isopropanol, then add 15mL of N,N-dimethylformamide containing 0.98g of intermediate 2, heat and stir at 70℃ for 20min, add 0.18mL of 0.5g / L isopropanol chloroplatinate solution, continue heating to 90℃ and react for 6h, after the reaction is completed, cool, add 0.12mL of 0.002mol / L sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3;

[0070] Q4: Add 18.12g of intermediate 3 and 5.28g of isophorone diisocyanate to a container, heat to 90℃ and stir for 1.5h, then add 0.74g of 2,2-dimethylolpropionic acid and react for 2h. After cooling to 80℃, add 0.52g of 1,4-butanediol and 0.38g of dibutyltin dilaurate and stir for 4h. Then continue to cool to 30℃ and add 0.65g of triethylamine and stir for 1h. After stirring, the modified toughening agent is obtained.

[0071] This embodiment discloses a method for preparing a composite additive, including the following steps:

[0072] S1: 17.28 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of N,N-dimethylformamide solution containing 40.12 g of N-bromosuccinimide was added while 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, the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a.

[0073] 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 nitrogen atmosphere, 150 mL of 1,4-dioxane and 90 mL of potassium carbonate aqueous solution with a concentration of 0.6 g / mL were added. The mixture was refluxed for 12 h. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b.

[0074] S3: Add 4.984g of product b, 1.58g of sodium hydroxide, 0.186g of sodium iodide, 0.422g of tetrabutylammonium bromide and 70mL of tetrahydrofuran to a container, heat under nitrogen protection and reflux for 4h, add 3.2mL of bromohexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c;

[0075] S4: 9.211 g of product c and 50 mL of dichloromethane were added to a container and stirred for 1 h under nitrogen protection. Then, 4.88 mL of boron tribromide was slowly added and stirred for 8 h under an ice bath. The mixture was then heated to room temperature and reacted for 12 h. After the reaction was completed, 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 sulfolane, 0.88 g of potassium carbonate, and 15 mL of toluene were added to a container and heated for 1 h each at 140 °C, 160 °C, and 180 °C, and then at 190 °C for 3 h. After the reaction was completed, the mixture was washed to obtain the composite auxiliary agent.

[0076] This embodiment discloses a high-toughness recycled ABS material, which is composed of the following components by weight: 80 parts recycled ABS resin, 10 parts modified toughening agent, 7 parts composite additive, 0.5 parts polypropylene wax, 0.8 parts antioxidant 1010 and 2.3 parts titanium dioxide, wherein the recycled ABS resin is composed of 90 parts recycled ABS and 5 parts polyethylene terephthalate-1,4-cyclohexanediol ester.

[0077] This embodiment discloses a method for preparing high-toughness recycled ABS material, including the following steps:

[0078] Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch;

[0079] Step 2: Add the uniform masterbatch and composite additives to the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0080] Example 4: This example discloses a method for preparing a modified toughening agent, including the following steps:

[0081] Q1: 9.07g vanillin, 6.23g 1,4-dibromobutane, 12.71g potassium carbonate and 0.46g potassium iodide were added to a container in sequence, followed by 95mL N,N-dimethylformamide. After stirring and mixing, the mixture was heated to 80℃ and refluxed under nitrogen for 6 hours. After the reaction was completed, the mixture was cooled, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1.

[0082] Q2: Add 3.88g of intermediate 1 and 2.11g of 4-aminophenol to a container containing 110mL of N,N-dimethylformamide, stir to dissolve, heat at 65℃ and reflux under nitrogen for 6h. After the reaction is completed, cool, add to deionized water, precipitate, and dry under vacuum to obtain intermediate 2.

[0083] Q3: Add 1.38g of polymethylhydrosiloxane to a container containing 25mL of isopropanol, then add 11mL of N,N-dimethylformamide containing 1.01g of intermediate 2, heat and stir at 70℃ for 20min, add 0.13mL of 0.5g / L isopropanol chloroplatinate solution, continue heating to 90℃ and react for 6h, after the reaction is completed, cool, add 0.09mL of 0.002mol / L sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3;

[0084] Q4: Add 12.27g of intermediate 3 and 5.07g of isophorone diisocyanate to a container, heat to 90℃ and stir for 1.5h, then add 0.62g of 2,2-dimethylolpropionic acid and react for 2h. After cooling to 80℃, add 0.41g of 1,4-butanediol and 0.28g of dibutyltin dilaurate and stir for 4h. After cooling to 30℃, add 0.48g of triethylamine and stir for 1h. After stirring, the modified toughening agent is obtained.

[0085] This embodiment discloses a method for preparing a composite additive, including the following steps:

[0086] S1: 16.37 g of carbazole was added to a container containing 30 mL of N,N-dimethylformamide. 120 mL of N,N-dimethylformamide solution containing 34.57 g of N-bromosuccinimide was added while 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, the organic phase was dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a.

[0087] S2: 21.57g of product a, 22.18g of 2-methoxy-5-pyrimidineboronic acid and 5.27g of tetrakis(triphenylphosphine)palladium were added to a container. Under nitrogen atmosphere, 130mL of 1,4-dioxane and 75mL of potassium carbonate aqueous solution with a concentration of 0.6g / mL were added. The mixture was refluxed for 12h. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, filtered, and dried to obtain product b.

[0088] S3: Add 4.371g of product b, 1.37g of sodium hydroxide, 0.172g of sodium iodide, 0.334g of tetrabutylammonium bromide and 65mL of tetrahydrofuran to a container, heat under nitrogen protection and reflux for 4h, add 2.6mL of bromohexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c;

[0089] S4: 8.738 g of product c and 42 mL of dichloromethane were added to a container and stirred for 1 h under nitrogen protection. Then, 4.23 mL of boron tribromide was slowly added and stirred for 8 h under an ice bath. The mixture was then heated to room temperature and reacted for 12 h. After the reaction was completed, 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 sulfolane, 0.81 g of potassium carbonate, and 11 mL of toluene were added to a container and heated for 1 h each at 140 °C, 160 °C, and 180 °C, and then at 190 °C for 3 h. After the reaction was completed, the mixture was washed to obtain the composite auxiliary agent.

[0090] This embodiment discloses a high-toughness recycled ABS material, which is composed of the following components by weight: 72 parts recycled ABS resin, 18 parts modified toughening agent, 3 parts composite additive, 0.7 parts polypropylene wax, 0.4 parts antioxidant 1010 and 1.5 parts titanium dioxide, wherein the recycled ABS resin is composed of 82 parts recycled ABS and 6 parts polyethylene terephthalate-1,4-cyclohexanediol ester.

[0091] This embodiment discloses a method for preparing high-toughness recycled ABS material, including the following steps:

[0092] Step 1: Add polypropylene wax, antioxidant 1010 and titanium dioxide to the dried recycled ABS resin, mix and stir to obtain a uniform masterbatch;

[0093] Step 2: Add the uniform masterbatch and composite additives to the mixer, add the modified toughening agent after mixing, continue mixing, then melt, extrude, granulate, and dry to obtain high-toughness recycled ABS material.

[0094] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not add composite additives during the preparation of high-toughness recycled ABS material, and all other conditions remained unchanged.

[0095] Comparative Example 2: Compared with Example 1, Comparative Example 2 did not add any modified toughening agent during the preparation of high-toughness recycled ABS material, and all other conditions remained unchanged.

[0096] Performance testing:

[0097] The recycled ABS materials prepared according to Examples 1-4 and Comparative Examples 1-2 were dried, injection molded, pressurized, cooled, and demolded to prepare the outer shell of a face mask for respiratory protective equipment. Performance tests were performed on the samples: impact strength according to GB / T 1843-2008; tensile properties according to GB / T 1040.2-2022; chemical resistance according to GB / T 11547-2008; heat distortion temperature according to GB / T 1634.2-2019; and low-temperature resistance according to GB / T 5470-2008. The test results are shown in Table 1.

[0098] Table 1

[0099]

[0100] As shown in Table 1, the test results indicate that recycled ABS materials with excellent toughness, chemical resistance, and wide temperature range applicability can be prepared using the methods described in Examples 1-4. A comparison between Comparative Example 1 and Examples 1-4 reveals that adding composite additives can effectively improve the toughness, chemical resistance, and wide temperature range applicability of recycled ABS materials. A comparison between Comparative Example 2 and Examples 1-4 shows that adding modified toughening agents can effectively improve the toughness and chemical resistance of recycled ABS materials.

[0101] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0102] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-toughness recycled ABS material, characterized in that, It is composed of the following components by weight: 70-80 parts recycled ABS resin, 10-20 parts modified toughening agent, 2-7 parts composite additives, 0.5-1.3 parts lubricant, 0.2-0.8 parts antioxidant, and 1.2-2.3 parts colorant. The recycled ABS resin is composed of 80-90 parts recycled ABS and 5-10 parts polyethylene terephthalate-1,4-cyclohexanediethanol ester. The modified toughening agent is prepared from vanillin, 1,4-dibromobutane, 4-aminophenol, polymethylhydrosiloxane, isophorone diisocyanate, and 1,4-butanediol. The composite additives are prepared from carbazole, N-bromosuccinimide, 2-methoxy-5-pyrimidineboronic acid, bromohexane, boron tribromide, and 4,4'-difluorobenzophenone.

2. The high-toughness recycled ABS material according to claim 1, characterized in that, The preparation method of the modified toughening agent includes 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, added to deionized water, precipitated, filtered, recrystallized, and dried under vacuum to obtain intermediate 1. Q2: Add intermediate 1 and 4-aminophenol to a container containing N,N-dimethylformamide, stir to dissolve, heat, reflux under nitrogen atmosphere, after the reaction is completed, cool, add to deionized water, precipitate, and vacuum dry to obtain intermediate 2; Q3: Add polymethylhydrosiloxane to a container containing isopropanol, then add N,N-dimethylformamide containing intermediate 2, heat and stir, add isopropanol chloroplatinate solution, continue heating and reacting, after the reaction is complete, cool, add sodium hydroxide solution, heat and evaporate to dryness to obtain intermediate 3; Q4: Add intermediate 3 and isophorone diisocyanate to a container, heat and stir, then add 2,2-dimethylolpropionic acid to react, cool down and add 1,4-butanediol and dibutyltin dilaurate, stir and react, continue to cool down, add triethylamine and stir, after stirring, the modified toughening agent is obtained.

3. The high-toughness recycled ABS material according to claim 2, characterized in that, In Q1, the 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 Q2, the ratio of 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 ratio of polymethylhydrosiloxane, isopropanol, intermediate 2, N,N-dimethylformamide, isopropanol chloroplatinate 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 ratio of intermediate 3, isophorone diisocyanate, 2,2-dimethylolpropionic 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 additive includes the following steps: S1: Carbazole was added to a container containing N,N-dimethylformamide. N,N-dimethylformamide solution containing N-bromosuccinimide was added while stirring at room temperature. After the addition was complete, the reaction was allowed to proceed at room temperature. After the reaction was completed, the mixture was added to ice water, extracted, dried, filtered, rotary evaporated, recrystallized, and dried under vacuum to obtain product a. S2: Add product a, 2-methoxy-5-pyrimidineboronic acid and tetra(triphenylphosphine)palladium to a container. Under nitrogen atmosphere, add 1,4-dioxane and potassium carbonate aqueous solution, reflux the reaction. After the reaction is complete, add ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product b. S3: Add product b, sodium hydroxide, sodium iodide, tetrabutylammonium bromide and tetrahydrofuran into a container, heat under nitrogen protection and reflux, add bromohexane during reflux, after reflux is completed, add to ice water, extract, dry the organic phase, filter, rotary evaporate, recrystallize, filter, dry to obtain product c; S4: Add product c and dichloromethane to a container and stir under nitrogen protection. Then slowly add boron tribromide and stir under an ice bath. Then heat to room temperature and react. After the reaction is complete, pour into ice water, extract, dry, and purify to obtain product d. Add product d, 4,4'-difluorobenzophenone, sulfolane, potassium carbonate, and toluene to a container and heat under nitrogen protection. After the reaction is complete, wash to obtain the composite auxiliary agent.

7. The high-toughness recycled ABS material according to claim 6, characterized in that, In S1, the ratio of carbazole to N-bromosuccinimide is (16.12-17.28) g: (32.38-40.12) g; in S2, the 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 step S3, the 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 step S4, the ratio of product c, dichloromethane, and boron tribromide is... The ratio of the amounts of the product is (8.678-9.211) g: (40-50) mL: (4.12-4.88) mL; 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.

9. The method for preparing the high-toughness recycled ABS material according to any one of claims 1-8, characterized in that, Includes the following steps: 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 composite additives to 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, characterized in that, The high-toughness recycled ABS material according to any one of claims 1-8 is applied to the mask shell, filter cartridge and frame structure of respiratory protective equipment.

Images