PC modified ABS resin material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses a PC modified ABS resin material and a preparation method thereof.The PC modified ABS resin material is prepared from, by weight, 80-110 parts of ABS resin, 30-40 parts of PC resin, 5-10 parts of ABS-g-MAH, 10-15 parts of modified carbon fibers, 1-3 parts of hyperbranched polyester modified polysiloxane, 0.5-1.5 parts of a rare earth organic complex, 0.1-0.5 part of an antioxidant, 0.1-0.5 part of an ultraviolet light absorber and 0.1-0.5 part of a lubricant. According to the invention, by adding maleic anhydride grafted ABS and hyperbranched polyester modified polysiloxane, good heat resistance and excellent processability are provided for the material, and by adding the modified carbon fiber and the rare earth organic complex, the impact resistance and weather resistance of the material are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a PC modified ABS resin material and a preparation method thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene (ABS) resin is a ternary graft copolymer composed of styrene, acrylonitrile, and butadiene. The acrylonitrile in ABS imparts excellent heat resistance, chemical resistance, and tensile strength; the butadiene imparts good toughness and impact resistance; and the styrene imparts good gloss, rigidity, and ease of processing. ABS resin's excellent room- and low-temperature toughness, good processing fluidity, exceptional chemical resistance, good colorability, high gloss, and good water resistance have led to its widespread application in electronics, instrumentation, automotive components, and building materials.

[0003] In recent years, the rapid development of the home appliance and automotive industries has placed higher demands on the performance of ABS resin. In addition to excellent processability, ABS resin is also required to exhibit high weather resistance and impact strength. Admixtures and toughening materials are typically added to enhance ABS's heat resistance and strength. However, these additions can reduce the material's melt flowability, leading to reduced melt strength and processing performance. This can easily lead to uneven wall thickness and surface defects in blow-molded products. Furthermore, admixtures and toughening materials are mostly inorganic, making them poorly compatible with the ABS resin matrix. Excessive additions can also degrade the material's overall performance. Summary of the Invention

[0004] To address the deficiencies mentioned in the above background technology, the present invention aims to provide a PC-modified ABS resin material and a preparation method thereof. By adding maleic anhydride-grafted ABS and hyperbranched polyester-modified polysiloxane, the material is provided with good heat resistance and excellent processing performance. By adding modified carbon fiber and rare earth organic complexes, the impact resistance and weather resistance of the material are improved.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A PC-modified ABS resin material comprises the following raw materials in parts by weight: 80-110 parts of ABS resin, 30-40 parts of PC resin, 5-10 parts of ABS-g-MAH, 10-15 parts of modified carbon fiber, 1-3 parts of hyperbranched polyester-modified polysiloxane, 0.5-1.5 parts of a rare earth organic complex, 0.1-0.5 parts of an antioxidant, 0.1-0.5 parts of an ultraviolet absorber, and 0.1-0.5 parts of a lubricant; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is made by coating the surface of short carbon fibers with polydopamine and then loading them with nano-titanium dioxide; the hyperbranched polyester modified polysiloxane is prepared by introducing hyperbranched polyester into the polysiloxane molecular chain through a condensation reaction, and its molecular weight is 5000-20000 g / mol; the rare earth organic complex is synthesized by a coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone, and its rare earth element content is 10~20 wt%.

[0006] Further preferably, the antioxidant is one of antioxidant 1010, antioxidant 618, and antioxidant 1076, the ultraviolet absorber is one of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and para-aminobenzoate ultraviolet absorbers, and the lubricant is one of sodium stearate, paraffin, and polyethylene wax.

[0007] Further preferably, the method for preparing the modified carbon fiber comprises the following steps: (1) The carbon fibers were dispersed in a Tris buffer solution, and then ultrasonically treated in an ice bath for 20 to 40 minutes. Dopamine hydrochloride was then added and ultrasonic treatment was continued for 5 to 15 minutes. The mixture was then vigorously stirred at room temperature for 20 to 24 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain polydopamine-coated carbon fibers. (2) Add nano-titanium dioxide to 95 Vol% ethanol, stir evenly and then ultrasonically disperse for 1-2 hours to obtain a nano-titanium dioxide dispersion, then add 3-aminopropyltrimethoxysilane to the dispersion, stir and heat to 80 °C for 3-5 hours, centrifuge, wash, filter and dry to obtain silane-modified nano-titanium dioxide; (3) The polydopamine-modified carbon fiber is added to N,N-dimethylformamide and ultrasonically treated for 20 to 40 minutes to form a uniform suspension. The silane-modified nano-titanium dioxide obtained in step (2) is then added to the above suspension and ultrasonically treated again for 20 to 40 minutes. The suspension is then heated to 100 to 110°C and stirred for reaction for 4 to 6 hours. The product is centrifuged, washed, filtered, and dried to obtain the modified carbon fiber.

[0008] Further preferably, in step (1), the mass ratio of dopamine hydrochloride to carbon fiber is 1:5-8.

[0009] Further preferably, in step (3), the mass ratio of the polydopamine-modified carbon fiber to the silane-modified nano-titanium dioxide is 3-5:1.

[0010] Further preferably, the preparation of the hyperbranched polyester-modified polysiloxane comprises the following steps: A. Add methyl acrylate and diethanolamine to methanol, heat to 40°C under a nitrogen atmosphere, and keep warm for 2-4 hours to obtain the monomer N,N-dihydroxyethyl-3-aminopropionic acid methyl ester. Then, mix 1,1,1-trimethylolpropane and N,N-dihydroxyethyl-3-aminopropionic acid methyl ester, add p-toluenesulfonic acid, heat to 120°C, react for 2-4 hours, and evaporate to remove methanol to obtain a branched polyester; B. The branched polyester is further polymerized with N,N-dihydroxyethyl-3-aminopropionic acid methyl ester monomer to obtain a hyperbranched polyester, and then the hyperbranched polyester and phthalic anhydride are added to triethylamine and refluxed for 3 to 5 hours to obtain a carboxyl-terminated hyperbranched polyester; C. Add carboxyl modified hyperbranched polyester and N,N-dimethylformamide into the reactor. After the carboxyl modified hyperbranched polyester is completely dissolved, slowly add thionyl chloride dropwise, raise the temperature to 60°C and reflux for 2-4 hours, then cool to 0°C and remove the unreacted thionyl chloride by vacuum pump, then add hydroxy silicone oil dropwise, stir and react at room temperature for 12-14 hours to obtain hyperbranched polyester modified polysiloxane.

[0011] Further preferably, in step A, the molar ratio of methyl acrylate to diethanolamine is 1:1, and the molar ratio of 1,1,1-trimethylolpropane to methyl N,N-dihydroxyethyl-3-aminopropionate is 1:3-4.

[0012] Further preferably, in step B, the molar ratio of the hyperbranched polyester to the phthalic anhydride is 1:1 to 1.2.

[0013] Further preferably, the preparation method of the rare earth organic complex comprises the following steps: Dissolve 2,4-dihydroxybenzophenone powder in anhydrous ethanol. Heat the lanthanum nitrate solution until it becomes viscous and then dissolve it in an appropriate amount of anhydrous ethanol. Slowly add the anhydrous ethanol solution containing lanthanum nitrate dropwise to the 2,4-dihydroxybenzophenone solution, stir for 20-40 minutes, adjust the pH to 6 with sodium hydroxide solution, and continue stirring for 2-4 hours to generate a yellow precipitate. Let the precipitate stand at room temperature for 10-12 hours, filter and wash it, and then place it in a vacuum drying oven at 60°C to a constant mass.

[0014] A method for preparing a PC-modified ABS resin material comprises the following steps: S1. Add ABS resin, PC resin, ABS-g-MAH, antioxidant, UV absorber and lubricant into a high mixing pot and mix thoroughly for 10-20 minutes; S2. Add modified carbon fiber, hyperbranched polyester modified polysiloxane, and rare earth organic complex in sequence and stir at high speed until uniformly dispersed. Then add the mixture into a twin-screw extruder for melt blending at a temperature of 180-220°C and a rotation speed of 200 rpm, and extrude and granulate to obtain PC modified ABS resin material.

[0015] Beneficial effects of the present invention: The PC-modified ABS resin material of the present invention is compounded by compounding PC resin with ABS resin, and adding a compatibilizer, maleic anhydride grafted ABS, and hyperbranched polyester modified polysiloxane, to provide the material with good heat resistance and excellent processing performance. The PC-modified ABS resin material of the present invention is also added with modified carbon fibers and rare earth organic complexes, thereby improving the material's impact resistance and weather resistance. The modified carbon fibers are prepared by coating the surface of chopped carbon fibers with polydopamine and then loading them with nano-titanium dioxide. The polydopamine coating greatly increases the interfacial compatibility between the ABS matrix and the carbon fibers, making them more evenly dispersed in the resin matrix and preventing carbon fiber agglomeration. At the same time, the nano-titanium dioxide attached to the surface also increases the surface roughness of the carbon fibers and the interfacial adhesion between the fibers and the matrix. Compared with the unmodified carbon fiber composite material, the mechanical properties of the modified carbon fiber composite material show an increasing trend. At the same time, the synergistic effect of nano-titanium dioxide grafted onto the surface of carbon fibers and ultraviolet absorbers can significantly enhance the UV protection effect. Nano-titanium dioxide mainly protects against UVB, while ultraviolet absorbers are more effective against UVA. The combination of the two can provide more comprehensive UV protection. At the same time, nano-titanium dioxide can reduce the photodegradation of ultraviolet absorbers and extend their service life. The rare earth organic complex is synthesized by the coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone. It has the effects of both heat stabilizer and light stabilizer, which can improve the thermal stability of the material. 2,4-dihydroxybenzophenone, as a UV absorber, can reduce the amount of added UV absorber. It also has a synergistic effect with the nano-titanium dioxide in the modified carbon fiber. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0017] Example 1 A modified carbon fiber, the preparation method of which comprises the following steps: (1) 5.5 g of carbon fiber was dispersed in 200 mL of 10 mM Tris buffer solution, and then ultrasonically treated in an ice bath for 30 min. Then, 1 g of dopamine hydrochloride was added to the above solution and ultrasonicated for 10 min. The mixture was then vigorously stirred at room temperature for 24 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain polydopamine-coated carbon fiber: (2) Add nano-titanium dioxide to 95 Vol% ethanol, stir evenly and disperse by ultrasonic for 2 hours to obtain nano-titanium dioxide dispersion, then add 3-aminopropyltrimethoxysilane to the dispersion, stir and heat to 80 °C for 4 hours, centrifuge, wash, filter and dry to obtain silane-modified nano-titanium dioxide; (3) The polydopamine-modified carbon fiber is added to N,N-dimethylformamide and ultrasonically treated for 30 minutes to form a uniform suspension. The silane-modified nano-titanium dioxide obtained in step S2 is then added to the above suspension and ultrasonically treated again for 30 minutes. The suspension is then heated to 105°C and stirred for reaction for 5 hours. The product is centrifuged, washed, filtered, and dried to obtain the modified carbon fiber.

[0018] Example 2 A hyperbranched polyester modified polysiloxane is prepared by introducing a hyperbranched polyester into a polysiloxane molecular chain through a polycondensation reaction. The preparation thereof comprises the following steps: A. Methyl acrylate and diethanolamine were added to methanol in a molar ratio of 1:1, and the temperature was raised to 40°C under a nitrogen atmosphere. The mixture was kept warm for 3 hours to obtain a monomer, N,N-dihydroxyethyl-3-aminopropionic acid methyl ester. 1,1,1-trimethylolpropane and N,N-dihydroxyethyl-3-aminopropionic acid methyl ester were then mixed in a molar ratio of 1:3. p-Toluenesulfonic acid was added, the temperature was raised to 120°C, the reaction was carried out for 3 hours, and the methanol was evaporated to obtain a branched polyester. B. The branched polyester is further polymerized with N,N-dihydroxyethyl-3-aminopropionic acid methyl ester monomer to obtain a hyperbranched polyester, and then the hyperbranched polyester and phthalic anhydride are added to triethylamine in a molar ratio of 1:1, and refluxed for 4 hours to obtain a carboxyl-terminated hyperbranched polyester; C. Add carboxyl modified hyperbranched polyester and N,N-dimethylformamide into the reactor. After the carboxyl modified hyperbranched polyester is completely dissolved, slowly add thionyl chloride dropwise, raise the temperature to 60°C and reflux for 2-4 hours, then cool to 0°C and remove the unreacted thionyl chloride by vacuum pump, then add hydroxy silicone oil dropwise, stir and react at room temperature for 12-14 hours to obtain hyperbranched polyester modified polysiloxane.

[0019] Example 3 A rare earth organic complex is synthesized by a coordination reaction of a rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone, and the preparation method thereof comprises the following steps: Dissolve 0.05 mol of 2,4-dihydroxybenzophenone powder in anhydrous ethanol. Heat 10 mL of 1.2 mol / L lanthanum nitrate solution until viscous and then dissolve it in an appropriate amount of anhydrous ethanol. Slowly add the anhydrous ethanol solution containing lanthanum nitrate dropwise to the 2,4-dihydroxybenzophenone solution. Stir for 30 minutes, then adjust the pH to 6 with sodium hydroxide solution. Continue stirring for 3 hours to generate a yellow precipitate. Let the precipitate stand at room temperature for 12 hours, filter under reduced pressure, wash with anhydrous ethanol solution and deionized water 3 to 4 times, and then dry in a vacuum drying oven at 60°C to constant mass.

[0020] Example 4 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 80 parts of ABS resin, 40 parts of PC resin, 5 parts of ABS-g-MAH, 15 parts of modified carbon fiber, 1 part of hyperbranched polyester-modified polysiloxane, 1.5 parts of rare earth organic complex, 0.1 part of antioxidant 618, 0.5 part of benzophenone ultraviolet absorber, and 0.1 part of sodium stearate; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is obtained by coating the surface of the chopped carbon fiber with polydopamine and then loading nano-titanium dioxide in Example 1; the hyperbranched polyester-modified polysiloxane is obtained by introducing the hyperbranched polyester into the polysiloxane molecular chain through a condensation reaction in Example 2; the rare earth organic complex is synthesized by coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone in Example 3.

[0021] The preparation method of the above-mentioned PC modified ABS resin material comprises the following steps: S1. Add ABS resin, PC resin, ABS-g-MAH, antioxidant, UV absorber and lubricant into a high-mix pot and mix thoroughly for 15 minutes; S2. Add modified carbon fiber, hyperbranched polyester modified polysiloxane, and rare earth organic complex in sequence and stir at high speed until uniformly dispersed. Then add the mixture into a twin-screw extruder for melt blending at a temperature of 180-220°C and a rotation speed of 200 rpm, and extrude and granulate to obtain PC modified ABS resin material.

[0022] Example 5 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 110 parts of ABS resin, 30 parts of PC resin, 10 parts of ABS-g-MAH, 10 parts of modified carbon fiber, 3 parts of hyperbranched polyester-modified polysiloxane, 0.5 parts of rare earth organic complex, 0.5 parts of antioxidant 1076, 0.1 parts of para-aminobenzoic acid ester ultraviolet absorber, and 0.5 parts of paraffin; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is obtained by coating the surface of the chopped carbon fiber with polydopamine and then loading nano-titanium dioxide in Example 1; the hyperbranched polyester-modified polysiloxane is obtained by introducing the hyperbranched polyester into the polysiloxane molecular chain through a condensation reaction in Example 2; the rare earth organic complex is synthesized by coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone in Example 3.

[0023] The preparation method of the above PC modified ABS resin material is the same as that in Example 4.

[0024] Example 6 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 95 parts of ABS resin, 35 parts of PC resin, 8 parts of ABS-g-MAH, 12 parts of modified carbon fiber, 2 parts of hyperbranched polyester-modified polysiloxane, 1 part of rare earth organic complex, 0.2 parts of antioxidant 1010, 0.3 parts of benzotriazole ultraviolet absorber, and 0.3 parts of polyethylene wax; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is obtained by coating the surface of the chopped carbon fiber with polydopamine and then loading nano-titanium dioxide in Example 1; the hyperbranched polyester-modified polysiloxane is obtained by introducing the hyperbranched polyester into the polysiloxane molecular chain through a condensation reaction in Example 2; the rare earth organic complex is synthesized by coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone in Example 3.

[0025] The preparation method of the above PC modified ABS resin material is the same as that in Example 4.

[0026] Comparative Example 1 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 95 parts of ABS resin, 35 parts of PC resin, 8 parts of ABS-g-MAH, 12 parts of carbon fiber, 2 parts of hyperbranched polyester-modified polysiloxane, 1 part of rare earth organic complex, 0.2 parts of antioxidant 1010, 0.3 parts of benzotriazole ultraviolet absorber, and 0.3 parts of polyethylene wax; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the hyperbranched polyester-modified polysiloxane is obtained by introducing a hyperbranched polyester into a polysiloxane molecular chain through a condensation reaction in Example 2; the rare earth organic complex is synthesized by a coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone in Example 3.

[0027] The preparation method of the above PC modified ABS resin material is the same as that in Example 4.

[0028] Comparative Example 2 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 95 parts of ABS resin, 35 parts of PC resin, 8 parts of ABS-g-MAH, 12 parts of modified carbon fiber, 1 part of rare earth organic complex, 0.2 parts of antioxidant 1010, 0.3 parts of benzotriazole ultraviolet absorber, and 0.3 parts of polyethylene wax; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is obtained by coating the surface of the chopped carbon fiber in Example 1 with polydopamine and then loading it with nano-titanium dioxide; the rare earth organic complex is synthesized by coordination reaction of the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone in Example 3.

[0029] The preparation method of the above PC modified ABS resin material is the same as that in Example 4.

[0030] Comparative Example 3 A PC-modified ABS resin material comprises the following raw materials in parts by weight: 95 parts of ABS resin, 35 parts of PC resin, 8 parts of ABS-g-MAH, 12 parts of modified carbon fiber, 2 parts of hyperbranched polyester-modified polysiloxane, 0.2 parts of antioxidant 1010, 0.3 parts of benzotriazole ultraviolet absorber, and 0.3 parts of polyethylene wax; ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; the modified carbon fiber is obtained by coating the surface of the chopped carbon fiber in Example 1 with polydopamine and then loading nano-titanium dioxide; the hyperbranched polyester-modified polysiloxane is obtained by introducing the hyperbranched polyester into the polysiloxane molecular chain through a condensation reaction in Example 2.

[0031] The preparation method of the above PC modified ABS resin material is the same as that in Example 4.

[0032] Performance testing 1. Mechanical properties test The PC-modified ABS resin pellets from Examples 4-6 and Comparative Examples 1-3 were injection molded to produce corresponding test specimens. Mechanical properties were tested using a universal testing machine. According to GB / T 528-2009, the molded specimens were cut into 25 mm × 4 mm dumbbell-shaped tensile bars at a tensile rate of 20 mm / min. The test results are shown in Table 1 below.

[0033] Table 1 Mechanical properties test results of PC modified ABS resin materials

[0034] From the data in Table 1, it can be seen that no modified carbon fiber is added in Comparative Document 1, but an equal amount of carbon fiber is directly added. It can be seen that the tensile strength and impact strength of the ABS resin composition in Comparative Example 1 are both reduced. It can be seen that the present invention can further improve the mechanical properties of the material by loading nano-titanium dioxide after coating the carbon fiber surface with polydopamine. The reason is that after polydopamine coating, the interfacial compatibility between the ABS matrix and the carbon fiber is greatly increased, making it more evenly dispersed in the resin matrix, preventing carbon fiber agglomeration. At the same time, the nano-titanium dioxide attached to the surface also increases the surface roughness of the carbon fiber and the interfacial adhesion between the fiber and the matrix. Compared with the unmodified carbon fiber composite material, the mechanical properties of the modified carbon fiber composite material have shown an increasing trend.

[0035] 2. Light stability test The PC-modified ABS resin material pellets prepared in Examples 4 to 6 and Comparative Examples 1 to 3 were injection molded to produce corresponding test specimens. The tensile strength retention after 1000 hours of QUV aging was tested according to GB / T 1040.2-2006, and the surface gloss was tested according to GB / T 8807-1988. The data obtained are shown in Table 2 below.

[0036] Table 2 Light stability test results of PC modified ABS resin material

[0037] As can be seen from the data in Table 2, the PC modified ABS resin material in Comparative Example 1 has a greater decrease in tensile strength and yellowing resistance after UV accelerated aging than other groups, while the modified carbon fiber of the present invention is not added in Comparative Example 1, indicating that the modified carbon fiber of the present invention can improve the mechanical properties of the material while also improving the light stability of the material. The reason is that the synergistic effect of the nano-titanium dioxide grafted on the surface of the carbon fiber and the ultraviolet absorber can significantly enhance the ultraviolet protection effect. Nano-titanium dioxide mainly protects UVB, while the ultraviolet absorber is more effective for UVA. The combination of the two can provide more comprehensive ultraviolet protection. At the same time, nano-titanium dioxide can reduce the photodegradation of the ultraviolet absorber and extend its service life. The light stability of the PC modified ABS resin material in Comparative Example 3 also decreases. The reason is that the organic ligand 2,4-dihydroxybenzophenone of the rare earth organic complex of the present invention is itself a ultraviolet absorber. It and the added ultraviolet absorber can reduce the amount of the added ultraviolet absorber and improve the light stability of the material. It also has a synergistic effect with the nano-titanium dioxide in the modified carbon fiber.

[0038] 3. Thermal stability test The aging-resistant reinforced PP daily plastic products prepared in Examples 3 to 5 and Comparative Examples 1 to 2 were aged at 100°C for 24 h, 48 h, and 72 h, respectively, and then their tensile strength was tested. The tensile strength test was carried out in accordance with GB / T 528-2009. The molded specimens were cut into 25 mm × 4 mm dumbbell-shaped tensile strips. The tensile rate was 20 mm / min, and the tensile strength retention rate was calculated by comparing the results with the initial tensile strength. The data are shown in Table 3.

[0039] Table 3 Thermal stability test results of PC modified ABS resin materials

[0040] The data in Table 3 show that the PC-modified ABS resin material in Comparative Example 3 exhibits a greater decrease in tensile strength after thermal aging than the other groups, indicating that the material without the rare earth organic complex exhibits poorer thermal stability than the other groups. The rare earth organic complex of the present invention is synthesized by a coordination reaction with the rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone, thereby enhancing its thermal stability.

[0041] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0042] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A PC modified ABS resin material, characterized in that: The invention comprises the following raw materials in parts by weight: 80-110 parts of ABS resin, 30-40 parts of PC resin, 5-10 parts of ABS-g-MAH, 10-15 parts of modified carbon fiber, 1-3 parts of hyperbranched polyester modified polysiloxane, 0.5-1.5 parts of rare earth organic complex, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of ultraviolet absorber, and 0.1-0.5 parts of lubricant; The ABS-g-MAH is maleic anhydride grafted ABS, which is obtained by drying and mixing ABS, maleic anhydride and DCP, and then adding them into a twin-screw extruder for melt extrusion; The modified carbon fiber is prepared by coating the surface of chopped carbon fiber with polydopamine and then loading nano-titanium dioxide; The hyperbranched polyester modified polysiloxane is prepared by introducing a hyperbranched polyester into a polysiloxane molecular chain through a polycondensation reaction, and has a molecular weight of 5000-20000 g / mol; The rare earth organic complex is synthesized by using a rare earth element lanthanum organic ligand 2,4-dihydroxybenzophenone through coordination reaction, and the rare earth element content thereof is 10-20 wt%.

2. The PC modified ABS resin material according to claim 1, characterized in that The antioxidant is one of antioxidant 1010, antioxidant 618, and antioxidant 1076; the ultraviolet absorber is one of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and para-aminobenzoate ultraviolet absorbers; and the lubricant is one of sodium stearate, paraffin, and polyethylene wax.

3. The PC modified ABS resin material according to claim 1, characterized in that: The preparation method of the modified carbon fiber comprises the following steps: (1) The carbon fibers were dispersed in a Tris buffer solution, and then ultrasonically treated in an ice bath for 20 to 40 minutes. Dopamine hydrochloride was then added and ultrasonic treatment was continued for 5 to 15 minutes. The mixture was then vigorously stirred at room temperature for 20 to 24 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain polydopamine-coated carbon fibers. (2) Add nano-titanium dioxide to 95 Vol% ethanol, stir evenly and then ultrasonically disperse for 1-2 hours to obtain a nano-titanium dioxide dispersion, then add 3-aminopropyltrimethoxysilane to the dispersion, stir and heat to 80 °C for 3-5 hours, centrifuge, wash, filter and dry to obtain silane-modified nano-titanium dioxide; (3) The polydopamine-modified carbon fiber is added to N,N-dimethylformamide and ultrasonically treated for 20 to 40 minutes to form a uniform suspension. The silane-modified nano-titanium dioxide obtained in step (2) is then added to the above suspension and ultrasonically treated again for 20 to 40 minutes. The suspension is then heated to 100 to 110°C and stirred for reaction for 4 to 6 hours. The product is centrifuged, washed, filtered, and dried to obtain the modified carbon fiber.

4. The PC modified ABS resin material according to claim 3, characterized in that: In the step (1), the mass ratio of dopamine hydrochloride to carbon fiber is 1:5-8.

5. The PC modified ABS resin material according to claim 3, characterized in that: In step (3), the mass ratio of the polydopamine-modified carbon fiber to the silane-modified nano-titanium dioxide is 3-5:

1.

6. The PC modified ABS resin material according to claim 1, characterized in that: The preparation of the hyperbranched polyester modified polysiloxane comprises the following steps: A. Add methyl acrylate and diethanolamine to methanol, heat to 40°C under a nitrogen atmosphere, and keep warm for 2-4 hours to obtain the monomer N,N-dihydroxyethyl-3-aminopropionic acid methyl ester. Then, mix 1,1,1-trimethylolpropane and N,N-dihydroxyethyl-3-aminopropionic acid methyl ester, add p-toluenesulfonic acid, heat to 120°C, react for 2-4 hours, and evaporate to remove methanol to obtain a branched polyester; B. The branched polyester is further polymerized with N,N-dihydroxyethyl-3-aminopropionic acid methyl ester monomer to obtain a hyperbranched polyester, and then the hyperbranched polyester and phthalic anhydride are added to triethylamine and refluxed for 3 to 5 hours to obtain a carboxyl-terminated hyperbranched polyester; C. Add carboxyl modified hyperbranched polyester and N,N-dimethylformamide into the reactor. After the carboxyl modified hyperbranched polyester is completely dissolved, slowly add thionyl chloride dropwise, raise the temperature to 60°C and reflux for 2-4 hours, then cool to 0°C and remove the unreacted thionyl chloride by vacuum pump, then add hydroxy silicone oil dropwise, stir and react at room temperature for 12-14 hours to obtain hyperbranched polyester modified polysiloxane.

7. The PC modified ABS resin material according to claim 6, characterized in that: In the step A, the molar ratio of methyl acrylate to diethanolamine is 1:1, and the molar ratio of 1,1,1-trimethylolpropane to methyl N,N-dihydroxyethyl-3-aminopropionate is 1:3-4.

8. The PC modified ABS resin material according to claim 6, characterized in that: In the step B, the molar ratio of the hyperbranched polyester to the phthalic anhydride is 1:1 to 1.

2.

9. The PC modified ABS resin material according to claim 1, characterized in that: The preparation method of the rare earth organic complex comprises the following steps: Dissolve 2,4-dihydroxybenzophenone powder in anhydrous ethanol. Heat the lanthanum nitrate solution until it becomes viscous and then dissolve it in an appropriate amount of anhydrous ethanol. Slowly add the anhydrous ethanol solution containing lanthanum nitrate dropwise to the 2,4-dihydroxybenzophenone solution, stir for 20-40 minutes, adjust the pH to 6 with sodium hydroxide solution, and continue stirring for 2-4 hours to generate a yellow precipitate. Let the precipitate stand at room temperature for 10-12 hours, filter and wash it, and then place it in a vacuum drying oven at 60°C to a constant mass.

10. The method for preparing the PC modified ABS resin material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Add ABS resin, PC resin, ABS-g-MAH, antioxidant, UV absorber and lubricant into a high mixing pot and mix thoroughly for 10-20 minutes; S2. Add modified carbon fiber, hyperbranched polyester modified polysiloxane, and rare earth organic complex in sequence and stir at high speed until uniformly dispersed. Then add the mixture into a twin-screw extruder for melt blending at a temperature of 180-220°C and a rotation speed of 200 rpm, and extrude and granulate to obtain PC modified ABS resin material.

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