A high-impact ABS composite material and a preparation method thereof

Abstract

This invention discloses a high-impact ABS composite material and its preparation method, belonging to the field of polymer materials technology. Addressing the problem that existing ABS composite materials struggle to simultaneously achieve good low-temperature toughness, rigidity, weather resistance, and resistance to environmental stress cracking, this invention provides a high-impact ABS composite material and its preparation method. The composite material consists of ABS resin, a reactive toughening agent (ethylene-methyl acrylate-glycidyl methacrylate copolymer), a reactive heat-resistant rigidifying agent (styrene-maleic anhydride copolymer), a reaction catalyst, an antioxidant, and a lubricant. Through melt reactive extrusion, E-MA-GMA and SMA undergo in-situ ring-opening esterification to form a crosslinked network. This composite material simultaneously achieves excellent low-temperature impact resistance, high flexural modulus, and high heat distortion temperature, while significantly improving resistance to environmental stress cracking and UV aging.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a high-impact ABS composite material and its preparation method. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS) is widely used in automotive interior and exterior trim, electronics, and cold chain logistics equipment due to its excellent overall properties. In extreme applications such as polar expeditions, cold chain storage and transportation, and automotive bumpers, the material must possess extremely high low-temperature impact resistance.

[0003] However, the existing technology has the following mutually restrictive technical problems: Ordinary ABS resin undergoes a brittle-ductile transition at low temperatures (such as -30°C), resulting in a sharp decrease in impact strength.

[0004] To improve low-temperature toughness, a common method is to physically blend the materials with a large amount of elastomers (such as MBS, POE, and high-resin powder). However, this leads to a significant decrease in the material's flexural modulus (rigidity) and heat distortion temperature, making the parts susceptible to deformation under stress.

[0005] The elastomer has limited compatibility with the ABS matrix and is prone to phase separation under long-term stress or chemical solvent erosion, resulting in extremely poor environmental stress cracking resistance (ESCR) of the material, making it very easy to crack when in contact with automotive oils or cleaning agents.

[0006] Furthermore, there is a long-neglected problem in this field: traditional modifiers used to toughen ABS (such as MBS or high-rubber powder) contain a large number of butadiene double bonds in their molecular chains. These double bonds are prone to chain breakage and cross-linking aging under outdoor ultraviolet radiation or long-term thermo-oxidative environments, leading to severe surface yellowing of ABS composites. Moreover, their mechanical properties (especially low-temperature toughness) experience a precipitous decline after aging, severely limiting their application in outdoor and long-life-sustaining scenarios.

[0007] Therefore, there is an urgent need for a new type of ABS composite material that can simultaneously address the issues of poor low-temperature impact resistance, decreased rigidity / heat resistance, and extremely poor ESCR, while also overcoming the weathering defects of traditional materials. Summary of the Invention

[0008] To address the aforementioned problems in existing technologies, this invention provides a high-impact ABS composite material and its preparation method. The core improvement of this invention lies in its departure from the traditional "physical blend elastomer" approach. Instead, it simultaneously improves the two core raw materials of the toughening system and the heat-resistant rigidity system by innovatively introducing ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA) and styrene-maleic anhydride copolymer (SMA), achieving synergistic effects under the action of a specific catalyst.

[0009] Specifically, SMA, as a high-rigidity and high-heat-resistant resin, compensates for the loss of rigidity and heat resistance caused by the addition of elastomers; while E-MA-GMA, as a flexible elastomer, provides excellent low-temperature toughness.

[0010] Specifically, during melt extrusion, under the promotion of a catalyst, the maleic anhydride groups on the SMA molecular chain undergo an in-situ ring-opening esterification reaction with the epoxy groups on the E-MA-GMA. This chemical bonding constructs a micro-crosslinked network of "rigid skeleton (SMA) - flexible nodes (E-MA-GMA)" in the ABS matrix. The presence of this micro-crosslinked network prevents chemical solvent molecules from penetrating the phase interface, significantly improving environmental stress cracking resistance (ESCR). Simultaneously, under low-temperature impact, the rigid SMA segments act as efficient stress transfer bridges, evenly distributing the impact energy to the E-MA-GMA flexible nodes, inducing crazes and shear bands to absorb energy, achieving a simultaneous, non-linear improvement in low-temperature impact resistance and rigidity.

[0011] Finally, the E-MA-GMA main chain selected in this invention is saturated, and combined with the excellent UV resistance of SMA, it eliminates the hidden dangers of photo-oxidative aging caused by traditional MBS toughening, and endows the material with excellent ultra-high weather resistance and anti-yellowing ability.

[0012] The objective of this invention can be achieved through the following technical solutions: A high-impact ABS composite material, by weight, is composed of the following raw materials: ABS resin: 65-75 parts; Reactive toughening agent: 10-15 parts; Reactive heat-resistant rigid agent: 10-15 parts; Reaction catalyst: 0.1-0.3 parts; Antioxidant: 0.2-0.6 parts; Lubricant: 0.5-1.0 parts.

[0013] Furthermore, the antioxidant is a compound of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0014] Furthermore, the reactive toughening agent comprises the following raw materials in parts by weight: Base resin: 100 parts; Graft monomers: 4-8 parts; Graft copolymer monomer: 1-2 parts; Initiator: 0.1-0.3 parts.

[0015] Furthermore, the reactive toughening agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, mix the grafted monomer, grafted copolymer monomer and initiator for 10-30 minutes to obtain a mixture, then spray the mixture evenly on the surface of the base resin, stir and mix at room temperature for 5-10 minutes, let stand for 2 hours to obtain the swollen material; Reactive extrusion: The swollen material is added to a co-rotating twin-screw extruder for melt grafting. After the extruded material is cooled with water, pelletized, and dried, a reactive toughening agent is obtained.

[0016] Furthermore, the reactive heat-resistant rigid agent comprises the following raw materials in parts by weight: Base resin: 100 parts; Graft monomers: 2-5 parts; Initiator: 0.1-0.2 parts; Lubricant: 0.5 parts.

[0017] Furthermore, the reactive heat-resistant rigid agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, mix the base resin and lubricant for 2-5 minutes, then add the powdered graft monomer and initiator, and continue mixing for 3-5 minutes. After completion, the premix is ​​obtained. Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt grafting. After the extruded material is cooled with water and pelletized, a reactive heat-resistant rigid agent is obtained.

[0018] Furthermore, the temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 190℃, Zone 2 210℃, Zones 3 to 6 230-245℃, Zones 7 to 8 230℃, and the die head 225℃. The screw speed is set to 300-350 rpm.

[0019] Furthermore, the preparation method of the high-impact ABS composite material includes the following steps: Premix: Weigh each raw material according to the weight parts, mix ABS resin, reactive toughening agent and reactive heat-resistant rigid agent at 300-500 rpm for 3-5 minutes, then add reaction catalyst, antioxidant and lubricant, and continue mixing for 5-10 minutes to obtain premix; Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt blending and in-situ reactive extrusion. After extrusion, the extrudate is obtained. Granulation: After the extrudate is cooled in a water tank and dried by an air knife, it is granulated by a pelletizer to obtain high-impact ABS composite material.

[0020] Furthermore, the temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 160-170℃, Zones 2 to 4 190-210℃, Zones 5 to 8 230-245℃, Zones 9 to 10 215-225℃, and the die head temperature 220-230℃.

[0021] The beneficial effects of this invention are: This invention addresses the technical problems in existing technologies, such as the decreased impact resistance of ordinary ABS resin at low temperatures, and the mutually restrictive effects of traditional physical blending toughening methods leading to deterioration in material rigidity, heat resistance, insufficient environmental stress cracking resistance (ESCR), and poor weather resistance. It proposes a novel high-impact ABS composite material based on reactive extrusion to construct a micro-crosslinked network. By innovatively introducing ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA) and styrene-maleic anhydride copolymer (SMA), and with the synergistic effect of a specific catalyst, this invention achieves a significant improvement in the overall performance of the material, specifically in the following aspects: (1) It effectively overcomes the traditional technical contradiction of "mutual constraint between toughness and rigidity / heat resistance", and achieves synergistic improvement of mechanical properties: In traditional polymer modification, adding elastomers to improve low-temperature toughness often comes at the cost of sacrificing the material's flexural modulus (rigidity) and heat distortion temperature. This invention achieves a better balance between these two aspects through the rational blending and chemical crosslinking of rigid and flexible components.

[0022] Based on the test results in Table 1, the high-impact ABS composite materials prepared in Examples 7-9 achieved notched impact strengths of 48.5-55.2 kJ / m² at room temperature (23°C). 2 It maintained a power output of 28.6-35.8 kJ / m² even at a low temperature of -30℃. 2 It exhibits excellent impact resistance; at the same time, its flexural modulus remains at a high level of 2450-2650 MPa, and its heat distortion temperature (HDT) reaches 96.5-100.5℃.

[0023] In contrast, in Comparative Example 4, the reactive toughening agent was removed (only the rigidifying agent SMA was retained), and the notched impact strength of the material at -30°C plummeted to 5.2 kJ / m. 2 It exhibited obvious low-temperature brittleness; while in Comparative Example 5, the reactive heat-resistant rigid agent was removed (only the toughening agent E-MA-GMA was retained), although its low-temperature impact strength reached 30.5 kJ / m. 2 However, the flexural modulus dropped significantly to 1750 MPa, and the heat distortion temperature decreased to 78.5℃. The material is prone to softening and deformation when heated or stressed.

[0024] Principle Analysis: Embodiments 7-9 of this invention combine SMA with E-MA-GMA. When subjected to low-temperature impact, SMA, as a high-rigidity and high-heat-resistant resin, compensates for the loss of rigidity and heat resistance caused by the addition of the elastomer. Simultaneously, the rigid segments of SMA act as efficient stress transfer bridges, uniformly distributing external impact energy to the flexible E-MA-GMA node, thereby inducing crazing and shear banding to absorb a large amount of impact energy. This "rigid-flexible" structural design enables the material to achieve a nonlinear synergistic improvement in low-temperature impact resistance while maintaining high rigidity and high heat resistance.

[0025] (2) A micro-crosslinked network was successfully constructed, which significantly improved the environmental stress cracking resistance (ESCR) of the material: In traditional physical blending modification, the compatibility between the elastomer and the ABS matrix is ​​limited, and phase separation easily occurs under long-term stress or chemical solvent erosion, resulting in poor ESCR performance of the material. This invention significantly enhances the bonding force at the phase interface through in-situ chemical reaction.

[0026] Based on the data in Table 1, the ESCR cracking times of Examples 7-9 were as long as 320-420 minutes, demonstrating excellent resistance to solvent cracking. In contrast, Comparative Example 1, after removing the reaction catalyst, showed a significantly reduced ESCR cracking time to 45 minutes, and its low-temperature impact strength also decreased to 15.2 kJ / m. 2 In addition, Comparative Example 3 used conventional SAN resin instead of SMA. Due to the lack of reactive groups in SAN, its ESCR cracking time was only 40 minutes, and its heat distortion temperature dropped to 86.5°C.

[0027] Principle Analysis: In Examples 7-9, during melt extrusion, under the promotion of the reaction catalyst (2-methylimidazole), the maleic anhydride groups on the SMA molecular chain and the epoxy groups on E-MA-GMA underwent an in-situ ring-opening esterification reaction. This chemical bonding successfully constructed a micro-crosslinked network of "rigid skeleton (SMA) - flexible nodes (E-MA-GMA)" in the ABS matrix. In Comparative Example 1, due to the lack of a catalyst, the two only remained at the physical blending level and could not form effective chemical crosslinks; in Comparative Example 3, because SAN lacked maleic anhydride groups, it also could not participate in the crosslinking reaction. The presence of the micro-crosslinked network in this invention effectively enhances the density and stability of the phase interface, making it difficult for chemical solvent molecules such as isopropanol / toluene to penetrate into the phase interface, thereby significantly extending the cracking time of the material under the combined action of stress and solvents.

[0028] (3) Significantly improved the material's weather resistance and anti-yellowing ability, extending the material's service life in complex environments: Traditional modifiers used to toughen ABS (such as MBS) contain a large number of butadiene double bonds in their molecular chains. These double bonds are prone to chain breakage and cross-linking aging under ultraviolet radiation or thermo-oxidative environments, leading to yellowing of the material surface and degradation of mechanical properties. This invention effectively avoids this problem by optimizing the toughening agent system.

[0029] Based on the weathering test results in Table 1, after 500 hours of accelerated UV aging testing, Examples 7-9 showed a yellowing index difference (ΔYI) of only 2.0-2.5, and a notched impact retention rate of 88.5%-94.5% at -30°C after aging. In contrast, Comparative Example 2 used a traditional MBS toughening agent instead of the E-MA-GMA of this invention, resulting in a sharp increase in the yellowing index difference to 28.5 after aging, exhibiting severe surface yellowing. More significantly, its impact retention rate at -30°C after aging was only 18.5%, indicating a severe degradation in mechanical properties. Furthermore, because MBS lacks epoxy groups, it cannot crosslink with SMA, and the ESCR cracking time of Comparative Example 2 was only 30 minutes.

[0030] Principle Analysis: The E-MA-GMA elastomer selected in Examples 7-9 of this invention has a saturated main chain chemical structure, eliminating the photo-oxidative aging sensitivity caused by double bonds in traditional MBS at the molecular level. Combined with the excellent UV resistance inherent in SMA, the composite material of this invention is less prone to macromolecular chain degradation or disordered cross-linking under long-term UV irradiation and thermo-oxidative environments. Therefore, this material not only maintains a good appearance and color (low yellowing) but also retains excellent low-temperature toughness after aging, significantly broadening its application prospects in outdoor, polar scientific expeditions, or long-life-requirement scenarios. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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. Furthermore, unless otherwise specified, the raw materials, reagents, or devices used in the following embodiments can be obtained from conventional commercial channels or by existing known methods. Example 1

[0032] Preparation of reactive toughening agents: First, the reactive toughening agent comprises the following raw materials in parts by weight: Base resin (EMA): 100 parts (commercially available ethylene-methyl acrylate copolymer, wherein the methyl acrylate (MA) content is 20%-24% by mass, the melt flow rate (MFI) is 2.0-3.0 g / 10min, ExxonMobil Optema TC120); Graft monomer (GMA): 4 parts (glycidyl methacrylate, commercially available industrial grade, purity ≥99.0%); Graft copolymer monomer (St): 1 part (styrene, commercially available industrial grade, purity ≥99.5%); Initiator (DCP): 0.1 parts (dicumyl peroxide, commercially available industrial grade).

[0033] Then, the reactive toughening agent is prepared by the following steps: Premixing: Weigh each raw material according to the weight parts, put the base resin (EMA) into a high-speed mixer, mix the graft monomer (GMA), graft copolymer monomer (St) and initiator (DCP) for 10 minutes to obtain a mixture, then spray the mixture evenly on the surface of the base resin (EMA), stir (200 rpm) at room temperature for 5 minutes, let it stand for 2 hours to allow the liquid monomer and initiator to fully swell and penetrate into the interior of the EMA particles to obtain swollen material; Reactive extrusion: The swollen material is added to a co-rotating twin-screw extruder for melt grafting reaction. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 40:1, the screw speed is 250 rpm, and the temperature settings of each section of the co-rotating twin-screw extruder are as follows: Zone 1 140℃, Zone 2 160℃, Zones 3 to 6 (reaction zone) 175-185℃, Zones 7 to 8 170℃, and the die head 165℃. Deviation and granulation: The vacuum devolatilization device (vacuum degree ≤ -0.08MPa) is turned on in the seventh zone of the co-rotating twin-screw extruder to remove unreacted GMA and styrene monomer. After water cooling, pelleting and drying, the extruded material is obtained as a reactive toughening agent. According to the titration test, the GMA grafting rate of the reactive toughening agent is about 3.5%. Example 2

[0034] Preparation of reactive toughening agents: First, the reactive toughening agent comprises the following raw materials in parts by weight: Base resin (EMA): 100 parts (commercially available ethylene-methyl acrylate copolymer, wherein the methyl acrylate (MA) content is 20%-24% by mass, the melt flow rate (MFI) is 2.0-3.0 g / 10min, ExxonMobil Optema TC120); Graft monomer (GMA): 6 parts (glycidyl methacrylate, commercially available industrial grade, purity ≥99.0%); Graft copolymer monomer (St): 1.2 parts (styrene, commercially available industrial grade, purity ≥99.5%); Initiator (DCP): 0.2 parts (dicumyl peroxide, commercially available industrial grade).

[0035] Then, the reactive toughening agent is prepared by the following steps: Premixing: Weigh each raw material according to the weight parts, put the base resin (EMA) into a high-speed mixer, mix the graft monomer (GMA), graft copolymer monomer (St) and initiator (DCP) for 30 minutes to obtain a mixture, then spray the mixture evenly on the surface of the base resin (EMA), stir (200 rpm) at room temperature for 10 minutes, let it stand for 2 hours to allow the liquid monomer and initiator to fully swell and penetrate into the interior of the EMA particles to obtain swollen material; Reactive extrusion: The swollen material is added to a co-rotating twin-screw extruder for melt grafting reaction. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 40:1, the screw speed is 300 rpm, and the temperature settings of each section of the co-rotating twin-screw extruder are as follows: Zone 1 140℃, Zone 2 160℃, Zones 3 to 6 (reaction zone) 175-185℃, Zones 7 to 8 170℃, and the die head 165℃. Deviation and granulation: The vacuum devolatilization device (vacuum degree ≤ -0.08MPa) is turned on in the seventh zone of the co-rotating twin-screw extruder to remove unreacted GMA and styrene monomer. After water cooling, pelleting and drying, the extruded material is obtained as a reactive toughening agent. According to the titration test, the GMA grafting rate of the reactive toughening agent is about 4.5%. Example 3

[0036] Preparation of reactive toughening agents: First, the reactive toughening agent comprises the following raw materials in parts by weight: Base resin (EMA): 100 parts (commercially available ethylene-methyl acrylate copolymer, wherein the methyl acrylate (MA) content is 20%-24% by mass, the melt flow rate (MFI) is 2.0-3.0 g / 10min, ExxonMobil Optema TC120); Graft monomer (GMA): 8 parts (glycidyl methacrylate, commercially available industrial grade, purity ≥99.0%); Graft copolymer monomer (St): 2 parts (styrene, commercially available industrial grade, purity ≥99.5%); Initiator (DCP): 0.3 parts (dicumyl peroxide, commercially available industrial grade).

[0037] Then, the reactive toughening agent is prepared by the following steps: Premixing: Weigh each raw material according to the weight parts, put the base resin (EMA) into a high-speed mixer, mix the graft monomer (GMA), graft copolymer monomer (St) and initiator (DCP) for 30 minutes to obtain a mixture, then spray the mixture evenly on the surface of the base resin (EMA), stir (200 rpm) at room temperature for 10 minutes, let it stand for 2 hours to allow the liquid monomer and initiator to fully swell and penetrate into the interior of the EMA particles to obtain swollen material; Reactive extrusion: The swollen material is added to a co-rotating twin-screw extruder for melt grafting reaction. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 40:1, the screw speed is 300 rpm, and the temperature settings of each section of the co-rotating twin-screw extruder are as follows: Zone 1 140℃, Zone 2 160℃, Zones 3 to 6 (reaction zone) 175-185℃, Zones 7 to 8 170℃, and the die head 165℃. Deviation and Granulation: In the seventh zone of the co-rotating twin-screw extruder, the vacuum devolatilization device (vacuum degree ≤ -0.08 MPa) is activated to remove unreacted GMA and styrene monomers. After water cooling, pelletizing, and drying, the extruded material yields the reactive toughening agent. Titration testing shows that the GMA grafting rate of the reactive toughening agent is approximately 5.0%. Example 4

[0038] Preparation of reactive heat-resistant rigid agents: First, the reactive heat-resistant rigid agent comprises the following raw materials in parts by weight: Base resin (α-MS-SAN): 100 parts (commercially available α-methylstyrene-acrylonitrile copolymer, wherein the α-methylstyrene content is ≥70% by mass, the Vicat softening point is ≥105℃, Kumho Sunrise SAN 200); Graft monomer (MAH): 2 parts (maleic anhydride, commercially available industrial grade, purity ≥99.0%); Initiator (DCP): 0.1 parts (dicumyl peroxide, commercially available industrial grade); Lubricant (white oil): 0.5 parts (commercially available industrial-grade liquid paraffin).

[0039] Then, the reactive heat-resistant rigid agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, add the base resin (α-MS-SAN) and lubricant (white oil) to a high speed mixer and mix for 2 minutes to wet the resin surface. Then add the powdered graft monomer (MAH) and initiator (DCP) and continue to mix at high speed (400 rpm) for 3 minutes to make the graft monomer and initiator evenly adhere to the resin surface. After completion, the premix is ​​obtained. Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt grafting. Due to the high heat resistance of α-MS-SAN, the temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 190℃, Zone 2 210℃, Zones 3 to 6 (reaction zone) 230-245℃, Zones 7 to 8 230℃, Die head 225℃, and the screw speed is set to 300 rpm. Deviation and granulation: Similarly, high vacuum devolatilization (vacuum degree ≤ -0.09MPa) is started in the rear section of the co-rotating twin-screw extruder to forcefully remove unreacted free maleic anhydride (to avoid generating an irritating odor during subsequent use). After extrusion into strands, water cooling, and pelletizing, the reactive heat-resistant rigid agent is obtained. According to infrared spectroscopy and titration analysis, the MAH grafting rate of the reactive heat-resistant rigid agent is about 1.5%. Example 5

[0040] Preparation of reactive heat-resistant rigid agents: First, the reactive heat-resistant rigid agent comprises the following raw materials in parts by weight: Base resin (α-MS-SAN): 100 parts (commercially available α-methylstyrene-acrylonitrile copolymer, wherein the α-methylstyrene content is ≥70% by mass, the Vicat softening point is ≥105℃, Kumho Sunrise SAN 200); Graft monomer (MAH): 4 parts (maleic anhydride, commercially available industrial grade, purity ≥99.0%); Initiator (DCP): 0.2 parts (dicumyl peroxide, commercially available industrial grade); Lubricant (white oil): 0.5 parts (commercially available industrial-grade liquid paraffin).

[0041] Then, the reactive heat-resistant rigid agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, add the base resin (α-MS-SAN) and lubricant (white oil) into a high-speed mixer and mix for 5 minutes to wet the resin surface. Then add the powdered graft monomer (MAH) and initiator (DCP) and continue to mix at high speed (400 rpm) for 5 minutes to make the graft monomer and initiator evenly adhere to the resin surface. After completion, the premix is ​​obtained. Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt grafting. Due to the high heat resistance of α-MS-SAN, the temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 190℃, Zone 2 210℃, Zones 3 to 6 (reaction zone) 230-245℃, Zones 7 to 8 230℃, Die head 225℃, and the screw speed is set to 350 rpm. Deviation and granulation: Similarly, high vacuum devolatilization (vacuum degree ≤ -0.09MPa) is started in the rear section of the co-rotating twin-screw extruder to forcefully remove unreacted free maleic anhydride (to avoid generating an irritating odor during subsequent use). After extrusion into strands, water cooling, and pelletizing, the reactive heat-resistant rigid agent is obtained. According to infrared spectroscopy and titration analysis, the MAH grafting rate of the reactive heat-resistant rigid agent is about 2.8%. Example 6

[0042] Preparation of reactive heat-resistant rigid agents: First, the reactive heat-resistant rigid agent comprises the following raw materials in parts by weight: Base resin (α-MS-SAN): 100 parts (commercially available α-methylstyrene-acrylonitrile copolymer, wherein the α-methylstyrene content is ≥70% by mass, the Vicat softening point is ≥105℃, Kumho Sunrise SAN 200); Graft monomer (MAH): 5 parts (maleic anhydride, commercially available industrial grade, purity ≥99.0%); Initiator (DCP): 0.2 parts (dicumyl peroxide, commercially available industrial grade); Lubricant (white oil): 0.5 parts (commercially available industrial-grade liquid paraffin).

[0043] Then, the reactive heat-resistant rigid agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, add the base resin (α-MS-SAN) and lubricant (white oil) into a high-speed mixer and mix for 5 minutes to wet the resin surface. Then add the powdered graft monomer (MAH) and initiator (DCP) and continue to mix at high speed (400 rpm) for 5 minutes to make the graft monomer and initiator evenly adhere to the resin surface. After completion, the premix is ​​obtained. Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt grafting. Due to the high heat resistance of α-MS-SAN, the temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 190℃, Zone 2 210℃, Zones 3 to 6 (reaction zone) 230-245℃, Zones 7 to 8 230℃, Die head 225℃, and the screw speed is set to 350 rpm. Deviation and granulation: Similarly, high vacuum devolatilization (vacuum degree ≤ -0.09MPa) is started in the rear section of the co-rotating twin-screw extruder to forcefully remove unreacted free maleic anhydride (to avoid generating an irritating odor during subsequent use). After extrusion into strands, water cooling, and pelletizing, the reactive heat-resistant rigid agent is obtained. According to infrared spectroscopy and titration analysis, the MAH grafting rate of the reactive heat-resistant rigid agent is about 3.0%. Example 7

[0044] Preparation of high-impact ABS composite materials: First, the high-impact ABS composite material, by weight, is composed of the following raw materials: ABS resin: 65 parts (Chi Mei PA-757 from Taiwan, China, melt flow rate 1.8 g / 10 min); The reactive toughening agent prepared in Example 1: 10 parts; The reactive heat-resistant rigid agent prepared in Example 4: 10 parts; Reaction catalyst: 0.1 parts (2-methylimidazole, purity ≥99%, commercially available industrial grade); Antioxidant: 0.2 parts (antioxidant 1010 and antioxidant 168 are mixed in a 1:1 mass ratio); Lubricant: 0.5 parts (EBS, ethylene bis-stearamide, commercially available industrial grade).

[0045] Then, the preparation method of high-impact ABS composite material includes the following steps: Premix: Weigh each raw material according to the weight parts, put ABS resin, reactive toughening agent prepared in Example 1 and reactive heat-resistant rigid agent prepared in Example 4 into a high-speed mixer, mix at 300 rpm for 3 minutes, then add reaction catalyst, antioxidant and lubricant, and continue mixing for 5 minutes to obtain a uniform premix; Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt blending and in-situ reactive extrusion. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 40:1, and the screw speed is set to 350 rpm. To match the reaction rate of the acid anhydride and epoxy, the temperature of each section of the co-rotating twin-screw extruder is set as follows: Zone 1 160℃, Zones 2 to 4 190-210℃, Zones 5 to 8 (core reaction section) 230-245℃, Zones 9 to 10 215-225℃, and the die head temperature is 220℃. After extrusion, the extrudate is obtained. Granulation: After the extrudate is cooled in a water tank and dried by an air knife, it is granulated by a pelletizer to obtain high-impact ABS composite material. Example 8

[0046] Preparation of high-impact ABS composite materials: First, the high-impact ABS composite material, by weight, is composed of the following raw materials: ABS resin: 72 parts (Chi Mei PA-757 from Taiwan, China, melt flow rate 1.8 g / 10 min); The reactive toughening agent prepared in Example 2: 14 parts; The reactive heat-resistant rigid agent prepared in Example 5: 14 parts; Reaction catalyst: 0.3 parts (2-methylimidazole, purity ≥99%, commercially available industrial grade); Antioxidant: 0.6 parts (antioxidant 1010 and antioxidant 168 are mixed in a 1:1 mass ratio); Lubricant: 1.0 part (EBS, ethylene bis-stearamide, commercially available industrial grade).

[0047] Then, the preparation method of high-impact ABS composite material includes the following steps: Premix: Weigh each raw material according to the weight parts, put ABS resin, reactive toughening agent prepared in Example 2 and reactive heat-resistant rigid agent prepared in Example 5 into a high-speed mixer, mix at 500 rpm for 5 minutes, then add reaction catalyst, antioxidant and lubricant, and continue mixing for 10 minutes to obtain a uniform premix; Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt blending and in-situ reactive extrusion. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 48:1, and the screw speed is set to 450 rpm. To match the reaction rate of the acid anhydride and epoxy, the temperature of each section of the co-rotating twin-screw extruder is set as follows: Zone 1 165℃, Zones 2 to 4 190-210℃, Zones 5 to 8 (core reaction section) 230-245℃, Zones 9 to 10 215-225℃, and the die head temperature is 230℃. After extrusion, the extrudate is obtained. Granulation: After the extrudate is cooled in a water tank and dried by an air knife, it is granulated by a pelletizer to obtain high-impact ABS composite material. Example 9

[0048] Preparation of high-impact ABS composite materials: First, the high-impact ABS composite material, by weight, is composed of the following raw materials: ABS resin: 75 parts (Chi Mei PA-757 from Taiwan, China, melt flow rate 1.8 g / 10 min); The reactive toughening agent prepared in Example 3: 15 parts; The reactive heat-resistant rigid agent prepared in Example 6: 15 parts; Reaction catalyst: 0.3 parts (2-methylimidazole, purity ≥99%, commercially available industrial grade); Antioxidant: 0.6 parts (antioxidant 1010 and antioxidant 168 are mixed in a 1:1 mass ratio); Lubricant: 1.0 part (EBS, ethylene bis-stearamide, commercially available industrial grade).

[0049] Then, the preparation method of high-impact ABS composite material includes the following steps: Premix: Weigh each raw material according to the weight parts, put ABS resin, reactive toughening agent prepared in Example 3 and reactive heat-resistant rigid agent prepared in Example 6 into a high-speed mixer, mix at 500 rpm for 5 minutes, then add reaction catalyst, antioxidant and lubricant, and continue mixing for 10 minutes to obtain a uniform premix; Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt blending and in-situ reactive extrusion. The length-to-diameter ratio (L / D) of the co-rotating twin-screw extruder is 48:1, and the screw speed is set to 450 rpm. To match the reaction rate of the acid anhydride and epoxy, the temperature of each section of the co-rotating twin-screw extruder is set as follows: Zone 1 170℃, Zones 2 to 4 190-210℃, Zones 5 to 8 (core reaction section) 230-245℃, Zones 9 to 10 215-225℃, and the die head temperature is 230℃. After extrusion, the extrudate is obtained. Granulation: After the extrudate is cooled in a water tank and dried by an air knife, it is granulated by a pelletizer to obtain high-impact ABS composite material.

[0050] Comparative Example 1 Comparative Example 1 served as the control group for Example 8. The raw material reaction catalyst in Example 8 was removed, while the remaining raw materials, raw material amounts, and preparation steps remained consistent with those in Example 8, ultimately yielding a high-impact ABS composite material.

[0051] Comparative Example 2 Comparative Example 2 served as the control group for Example 8. The reactive toughening agent prepared in Example 2 was replaced with a traditional MBS toughening agent (domestic CM701) in Example 8. The remaining raw materials, raw material amounts, and preparation steps remained consistent with those in Example 8, and a high-impact ABS composite material was finally obtained.

[0052] Comparative Example 3 Comparative Example 3 served as the control group for Example 8. The reactive heat-resistant rigid agent prepared in Example 5 was replaced with conventional SAN resin (Kumho Sunny SAN 200) in Example 8. The remaining raw materials, raw material amounts, and preparation steps remained consistent with those in Example 8, and a high-impact ABS composite material was finally obtained.

[0053] Comparative Example 4 Comparative Example 4 served as the control group for Example 8. The reactive toughening agent prepared in Example 2 was removed from the raw materials in Example 8, and the amount of ABS resin was increased from 72 parts to 86 parts (to make up the weight parts). The remaining raw materials, raw material amounts, and preparation steps remained consistent with those in Example 8, and a high-impact ABS composite material was finally obtained.

[0054] Comparative Example 5 Comparative Example 5 served as the control group for Example 8. The reactive heat-resistant rigid agent prepared in Example 5 was removed from the raw materials in Example 8, and the amount of ABS resin was increased from 72 parts to 86 parts (to make up the weight parts). The remaining raw materials, raw material amounts, and preparation steps remained consistent with those in Example 8, and a high-impact ABS composite material was finally obtained.

[0055] Test Example 1 The high-impact ABS composite materials prepared in Examples 7-9 and Comparative Examples 1-5 were subjected to performance tests. The test process is as follows, and the test results are shown in Table 1. After drying the above-mentioned high-impact ABS composite material at 80°C for 4 hours, it was injection molded into standard test specimens (injection temperature 230°C, mold temperature 60°C).

[0056] (1) Notched impact strength of cantilever beam: Performed according to ISO 180 standard. Tested at room temperature (23℃) and low temperature (-30℃, tested rapidly after 4 hours of constant temperature), unit kJ / m 2 .

[0057] (2) Flexural modulus and heat distortion temperature (HDT): Flexural modulus shall be performed in accordance with ISO 178 (2 mm / min, MPa); HDT shall be performed in accordance with ISO 75 (1.8 MPa load, °C).

[0058] (3) Environmental stress cracking resistance (ESCR): The critical strain fixture method was used. The specimen was fixed on a semi-elliptical fixture with a fixed bending strain of 1.5%, and an isopropanol / toluene (volume ratio 1:1) mixed solvent was applied at the point of maximum stress. The time (min) from application to the appearance of the first visible microcrack was recorded.

[0059] (4) Weathering resistance test (addressing hidden issues): Following ISO 4892-3 standards, the samples were subjected to a 500-hour aging test using a QUV accelerated ultraviolet light aging tester (UVA-340 lamp, light / condensation cycle). The difference in yellow index before and after aging (ΔYI, tested according to ASTM E313; the smaller the value, the better the resistance to yellowing), and the retention rate (%) of the notched impact strength at -30℃ after aging were measured.

[0060] Table 1 Test Results project Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 <![CDATA[Notched impact strength (23 °C, kJ / m 2 )]]> 48.5 52.6 55.2 35.4 46.2 38.5 14.5 58.6 <![CDATA[Notched impact strength (-30 °C, kJ / m 2 )]]> 28.6 32.4 35.8 15.2 22.5 18.6 5.2 30.5 Flexural modulus (MPa) 2450 2580 2650 2350 2400 2150 2850 1750 Heat distortion temperature (HDT) (°C) 96.5 98.2 100.5 94.5 95.0 86.5 104.0 78.5 ESCR cracking time (min) 320 385 420 45 30 40 25 55 Yellowing index difference after aging (ΔYI) 2.5 2.2 2.0 2.8 28.5 2.6 1.8 2.4 -30℃ impact retention rate after aging (%) 88.5 92.4 94.5 85.0 18.5 86.5 95.0 89.0 Analysis of the data in Table 1: (1) The present invention has excellent comprehensive performance (Examples 7-9): The high-impact ABS composite materials prepared in Examples 7-9 maintain extremely high notched impact strength at both room temperature and -30℃ (low-temperature impact strength up to 35.8 kJ / m). 2Meanwhile, the flexural modulus (≥2450 MPa) and heat distortion temperature (≥96.5℃) did not show a significant decrease, resolving the contradiction of "mutual constraint between toughness and rigidity / heat resistance" in traditional toughening modification. In addition, its ESCR cracking time is over 300 minutes, the difference in yellowing index after aging is extremely small (≤2.5), and the low-temperature impact retention rate is over 88%, demonstrating excellent solvent resistance and weather resistance.

[0061] (2) The key role of the micro-crosslinking network (comparative Example 8 and Comparative Example 1): Comparative Example 1 removed the reaction catalyst, resulting in SMA and E-MA-GMA being only physically blended, unable to undergo in-situ ring-opening esterification. Test results showed that its low-temperature impact strength (15.2 kJ / m²) was... 2 The ESCR cracking time (45 min) showed a sharp decrease compared to Example 8. This fully demonstrates that the catalyst-induced "rigid framework-flexible node" chemical cross-linking network in this invention is the core key to achieving efficient stress transfer (high impact resistance) and blocking solvent penetration (high ESCR).

[0062] (3) Dual verification of weather resistance and reaction sites (comparative example 8 and comparative examples 2 and 3): Comparative example 2 uses traditional MBS instead of E-MA-GMA. Since MBS contains a large number of double bonds and no epoxy groups, it cannot crosslink with SMA, resulting in extremely poor ESCR (30 min). More fatally, it undergoes severe degradation after UV aging, with the yellowing index difference soaring to 28.5 and the low temperature impact retention rate remaining at only 18.5%, thus losing its outdoor use value.

[0063] Comparative Example 3 uses traditional SAN instead of SMA. Due to the lack of maleic anhydride groups, it cannot participate in crosslinking and its own heat resistance is insufficient, resulting in a significant drop in the heat distortion temperature of the material to 86.5°C. All mechanical properties are inferior to those of Example 8.

[0064] (4) Synergistic effect of rigid and flexible components (comparative Example 8 and Comparative Examples 4 and 5): Comparative Example 4 only added a rigid agent, and the material exhibited extreme brittleness (low-temperature impact strength of only 5.2 kJ / m). 2 Comparative Example 5, which only added a toughening agent, exhibited good impact performance, but its flexural modulus (1750 MPa) and heat distortion temperature (78.5℃) were severely degraded, resulting in severe softening deformation. Example 8 of this invention combines both and triggers a chemical reaction, achieving a nonlinear synergistic effect of "1+1>2," resulting in unexpected technical benefits.

[0065] It should be noted that, in this document, terms such as “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0066] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high-impact ABS composite material, characterized in that, By weight, it consists of the following raw materials: ABS resin: 65-75 parts; Reactive toughening agent: 10-15 parts; Reactive heat-resistant rigid agent: 10-15 parts; Reaction catalyst: 0.1-0.3 parts; Antioxidant: 0.2-0.6 parts; Lubricant: 0.5-1.0 parts.

2. The high-impact ABS composite material according to claim 1, characterized in that, The antioxidant is a compound of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:

1.

3. The high-impact ABS composite material according to claim 1, characterized in that, The reactive toughening agent comprises the following raw materials in parts by weight: Base resin: 100 parts; Graft monomers: 4-8 parts; Graft copolymer monomer: 1-2 parts; Initiator: 0.1-0.3 parts.

4. The high-impact ABS composite material according to claim 3, characterized in that, The reactive toughening agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, mix the grafted monomer, grafted copolymer monomer and initiator for 10-30 minutes to obtain a mixture, then spray the mixture evenly on the surface of the base resin, stir and mix at room temperature for 5-10 minutes, let stand for 2 hours to obtain the swollen material; Reactive extrusion: The swollen material is added to a co-rotating twin-screw extruder for melt grafting. After the extruded material is cooled with water, pelletized, and dried, a reactive toughening agent is obtained.

5. The high-impact ABS composite material according to claim 1, characterized in that, The reactive heat-resistant rigid agent comprises the following raw materials in parts by weight: Base resin: 100 parts; Graft monomers: 2-5 parts; Initiator: 0.1-0.2 parts; Lubricant: 0.5 parts.

6. The high-impact ABS composite material according to claim 5, characterized in that, The reactive heat-resistant rigid agent is prepared by the following steps: Premix: Weigh each raw material according to the weight parts, mix the base resin and lubricant for 2-5 minutes, then add the powdered graft monomer and initiator, and continue mixing for 3-5 minutes. After completion, the premix is ​​obtained. Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt grafting. After the extruded material is cooled with water and pelletized, a reactive heat-resistant rigid agent is obtained.

7. A high-impact ABS composite material according to claim 6, characterized in that, The temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 190℃, Zone 2 210℃, Zones 3 to 6 230-245℃, Zones 7 to 8 230℃, and the die head 225℃. The screw speed is set to 300-350 rpm.

8. A method for preparing a high-impact ABS composite material according to any one of claims 1-7, characterized in that, Includes the following steps: Premix: Weigh each raw material according to the weight parts, mix ABS resin, reactive toughening agent and reactive heat-resistant rigid agent at 300-500 rpm for 3-5 minutes, then add reaction catalyst, antioxidant and lubricant, and continue mixing for 5-10 minutes to obtain premix; Reactive extrusion: The premixed material is added to a co-rotating twin-screw extruder for melt blending and in-situ reactive extrusion. After extrusion, the extrudate is obtained. Granulation: After the extrudate is cooled in a water tank and dried by an air knife, it is granulated by a pelletizer to obtain high-impact ABS composite material.

9. The method for preparing a high-impact ABS composite material according to claim 8, characterized in that, The temperature settings for each section of the co-rotating twin-screw extruder are as follows: Zone 1 160-170℃, Zones 2 to 4 190-210℃, Zones 5 to 8 230-245℃, Zones 9 to 10 215-225℃, and Die head temperature 220-230℃.