PC / ABS composition and preparation method thereof

Abstract

The invention discloses a PC (polycarbonate) / ABS (acrylonitrile butadiene styrene) composition and a preparation method thereof. The PC / ABS composition is prepared from the following raw materials: PC resin, ABS resin, a phosphorus-containing acrylate flexibilizer, an SMA-g-SiO2 compatilizer, functionalized POSS (polyhedral oligomeric silsesquioxane), modified basic copper phosphate, modified tin oxide and a hindered phenol antioxidant. The PC / ABS composition has excellent mechanical property, flame retardant property, low dielectric property and laser forming property, and can be widely applied to the field of communication requiring laser forming property.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and particularly relates to a PC / ABS composition and a preparation method thereof. Background Art

[0002] Laser direct structuring (LDS) functional materials are a kind of functional modified plastics containing metal compounds or complexes. Through laser activation and electroless plating processes, metal conductive circuits can be constructed on the surface of plastic injection parts to form three-dimensional circuit carriers, namely the so-called three-dimensional molded interconnect device (3D-MID). The manufacturing process includes: (1) functional material formulation design and preparation; (2) injection molding; (3) laser activation; (4) selective metallization; (5) spraying and assembly. At present, LDS functional materials have been widely used in 4G communication mobile phone antennas, intelligent sensing / response fields, medical devices, smart furniture, drones, etc., realizing the functionalization, intelligence, lightweight and miniaturization of intelligent terminal structural components.

[0003] With the rapid development of 5G communication technology, its characteristics of low latency, high reliability and low power consumption during transmission will surely promote the concepts of Internet of Everything, autonomous driving, smart city, etc. to become a reality, and will be further more widely applied to high-end fields such as industry, medical treatment, security, aerospace, etc. 5G communication technology also puts forward higher performance requirements for LDS functional materials, such as low dielectric, low loss, high flame retardancy, heat conduction and dissipation, higher rigidity and fluidity, better environmental resistance, and adaptation to more new technologies and new processes, etc.

[0004] At present, some research has been done on PC compositions with laser direct structuring in the prior art. For example: Chinese Patent CN106883577A discloses a modified LDS laser direct structuring PC composite material and its preparation method. The material is composed of the following raw materials in parts by weight: 550 - 750 parts of PC powder, 150 - 350 parts of siloxane, 100 - 250 parts of filler, 10 - 40 parts of passivator, 40 - 110 parts of metal compound, 3 - 30 parts of stabilizer, 3 - 30 parts of antioxidant, 3 - 30 parts of lubricant, 10 - 60 parts of chain extender, and 3 - 20 parts of color powder. Chinese Patent CN 112920589A discloses a flame-retardant PC composition based on LDS technology and having heat conduction function, including the following components in parts by weight: 20 - 80 parts of polycarbonate, 10 - 50 parts of organopolysiloxane-polycarbonate block copolymer, 1 - 15 parts of LDS laser engraving additive, 5 - 40 parts of heat conduction additive, 0.01 - 15 parts of flame retardant, 0.1 - 0.5 parts of heat stabilizer, 0.1 - 0.5 parts of anti-UV agent, and 0 - 5 parts of other components. Chinese Patent CN 106751389A discloses a light-colored engineering plastic for LDS technology and its preparation method. The plastic includes the following components in parts by weight: 20 - 80 parts of PC, 10 - 40 parts of ABS, 0.05 - 30 parts of LDS additive, and 0.05 - 10 parts of antioxidant. Chinese Patent CN 103756278A discloses an engineering plastic applicable to LDS molding process, its preparation method and application. The weight percentage components of the engineering plastic include: 45.0 - 80.0% of PC resin, 7.8 - 15.0% of ABS resin, 5.0 - 40.0% of laser activator treated with coupling agent, 2.5 - 5.5% of compatibilizer, 4.0 - 7.0% of toughening agent, 0.5% - 1.0% of lubricant, 0.1 - 1.0% of antioxidant, and 0.1 - 1.0% of heat stabilizer. It can be seen from the above patents that in the current prior art, the laser direct structuring function is mainly achieved through metal oxides. However, the above patents do not involve adjusting the dielectric properties of PC compositions. Summary of the Invention

[0005] Based on this, one object of the present invention is to provide a PC / ABS composition, which has excellent mechanical properties, flame retardant properties, low dielectric properties and laser forming properties, and can be widely applied to the communication field requiring laser forming properties.

[0006] The specific technical solutions for achieving the above invention objects are as follows.

[0007] A PC / ABS composition, which is prepared from the following raw materials in parts by weight:

[0008] 80 - 90 parts of PC resin,

[0009] 10 to 20 parts of ABS resin,

[0010] The total weight parts of the PC resin and the ABS resin is 100 parts,

[0011]

[0012] The SMA-g-SiO2 compatibilizer is styrene-maleic anhydride copolymer grafted silica; the functionalized POSS is functionalized polyhedral oligomeric silsesquioxane.

[0013] In some embodiments, the PC / ABS composition is prepared from the following raw materials in parts by weight:

[0014] 82 to 88 parts of PC resin,

[0015] 12 to 18 parts of ABS resin,

[0016] The total weight parts of the PC resin and the ABS resin is 100 parts,

[0017]

[0018] In some embodiments, the PC / ABS composition is prepared from the following raw materials in parts by weight:

[0019] 84 to 86 parts of PC resin,

[0020] 14 to 16 parts of ABS resin,

[0021] The total weight parts of the PC resin and the ABS resin is 100 parts,

[0022]

[0023] In some embodiments, the number-average relative molecular mass of the PC resin is 20,000 to 30,000; the butadiene content of the ABS resin is 14% to 18%.

[0024] In some embodiments, the end groups of the functionalized POSS contain epoxy groups; the modified basic copper phosphate is obtained by organically modifying basic copper phosphate with γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the modified tin oxide is obtained by organically modifying tin oxide with γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the hindered phenolic antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0025] In some of these embodiments, the preparation method of the phosphorus-containing acrylate toughening agent comprises the following steps:

[0026] (1) Mix 85 g to 95 g of octamethylcyclotetrasiloxane, 6 g to 10 g of γ-methacryloxypropyltrimethoxysilane, 1.5 g to 2.5 g of dodecylbenzenesulfonic acid, and 150 mL to 200 mL of deionized water in a flask, and perform pre-emulsification for 0.3 h to 0.7 h at a stirring speed of 300 rpm to 500 rpm. Then add 0.8 g to 1.2 g of dodecylbenzenesulfonic acid and 400 mL to 600 mL of deionized water, heat in a constant-temperature water bath to 75°C to 95°C, and maintain the rotation speed at 150 rpm to 250 rpm. After reacting for 2 h to 4 h, cool down to obtain a polysiloxane core emulsion. Adjust the pH value of the above polysiloxane core emulsion to 7.8 to 8.2 with a 2 wt% to 4 wt% sodium hydroxide solution. After adjustment, add 1.5 g to 2.5 g of potassium persulfate dropwise to the polysiloxane core emulsion.

[0027] (2) Mix 75 to 85 g of diethyl methylphosphonate acrylate, 130 g to 170 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted acrylate monomer, 1.5 g to 2.5 g of sodium dodecyl sulfate, and 300 mL to 500 mL of deionized water in a flask, and perform pre-emulsification for 0.3 h to 0.7 h at a stirring speed of 300 rpm to 500 rpm. Then, dropwise add the mixture to the polysiloxane core emulsion obtained in step (1) above, the temperature of which has been raised to 75°C to 85°C, at a certain speed. After the dropping is completed, add 1 g to 1.4 g of potassium persulfate as a supplement. After reacting for 2 hours to 4 hours, cool down, discharge, demulsify, filter, wash with deionized water multiple times, and dry to finally obtain a phosphorus-containing acrylate toughening agent.

[0028] In some of these embodiments, the preparation method of the SMA-g-SiO2 compatibilizer comprises the following steps:

[0029] Add 100 g of SiO2 containing amino groups to 500 mL to 700 mL of N,N-dimethylformamide, and perform ultrasonic treatment for 10 min to 20 min to obtain a uniform dispersion. At the same time, dissolve 40 g to 60 g of styrene-maleic anhydride copolymer in 200 mL to 400 mL of N,N-dimethylformamide. Pour the N,N-dimethylformamide dispersion of SiO2 containing amino groups into a flask, stir at a rotation speed of 300 rpm to 500 rpm, and slowly dropwise add the N,N-dimethylformamide solution of the styrene-maleic anhydride copolymer at 85°C to 95°C, and keep the reaction conditions unchanged for condensation reflux for 10 h to 14 h. Centrifuge the reacted solution, wash with absolute ethanol, and then dry at 55°C to 65°C for 10 h to 14 h to obtain the SMA-g-SiO2 compatibilizer.

[0030] Another object of the present invention is to provide a method for preparing the above PC / ABS composition.

[0031] The specific technical solutions for achieving the above invention objects are as follows.

[0032] A method for preparing a PC / ABS composition, comprising the following steps:

[0033] (1) After drying the PC resin at a temperature of 104°C to 114°C for 2.2 hours to 4.2 hours, it is cooled; the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant are added to a blender for mixing;

[0034] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide are added to another high-speed blender for mixing;

[0035] (3) The mixture well-mixed in step (1) is added to a parallel twin-screw extruder through a feeder, and the mixture well-mixed in step (2) is added laterally (for example, the third zone) of the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 210°C to 230°C, the temperature of the second zone is 210°C to 230°C, the temperature of the third zone is 215°C to 235°C, the temperature of the fourth zone is 215°C to 235°C, the temperature of the fifth zone is 220°C to 240°C, the temperature of the sixth zone is 220°C to 240°C, the temperature of the seventh zone is 220°C to 240°C, the temperature of the eighth zone is 220°C to 240°C, the die head temperature is 215°C to 235°C, and the screw speed is 400 rpm to 800 rpm.

[0036] In some embodiments, the method for preparing the PC / ABS composition comprises the following steps:

[0037] (1) After drying the PC resin at a temperature of 107°C to 111°C for 2.6 hours to 3.8 hours, it is cooled; the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant are added to a blender for mixing;

[0038] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide are added to another high-speed blender for mixing;

[0039] (3) Add the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (for example, in the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletization. The process parameters include: the temperature of the first zone is 215°C - 225°C, the temperature of the second zone is 215°C - 225°C, the temperature of the third zone is 220°C - 230°C, the temperature of the fourth zone is 220°C - 230°C, the temperature of the fifth zone is 225°C - 235°C, the temperature of the sixth zone is 225°C - 235°C, the temperature of the seventh zone is 225°C - 235°C, the temperature of the eighth zone is 225°C - 235°C, the die head temperature is 220°C - 230°C, and the screw speed is 500 rpm - 700 rpm.

[0040] In some of the embodiments, the screw shape of the parallel twin-screw extruder is single-threaded; the ratio of the screw length L to the diameter D, L / D, is 35 - 55; and there are more than 1 (including 1) kneading block zones and more than 1 (including 1) reverse-thread zones on the screw.

[0041] In some of the embodiments, the ratio of the screw length L to the diameter D, L / D, is 40 - 50; and there are 2 kneading block zones and 1 reverse-thread zone on the screw.

[0042] In some of the embodiments, in step (1) and / or step (2), the mixer is a high-speed mixer with a rotation speed of 500 revolutions per minute - 1500 revolutions per minute.

[0043] The functions of the raw materials of the PC / ABS composition of the present invention are as follows:

[0044] The present invention improves the flame retardancy of a PC / ABS composition by compounding and using a phosphorus-containing acrylate toughening agent, an SMA-g-SiO2 compatibilizer, and functionalized POSS. Among them, (1) the phosphorus-containing acrylate toughening agent is an ACR-type flame retardant toughening agent with both flame retardancy and toughening functions. Utilizing the synergistic flame retardancy of P-Si and the toughening structural characteristics of ACR, a siloxane is selected as the core layer, a phosphorus-containing acrylate monomer is used as the shell layer, and a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) is used as the crosslinking agent. By inhibiting the generation and growth of microcracks, the impact performance of the material is improved. At the same time, the phosphorus-containing acrylate toughening agent can play a role in flame retardancy of PC / ABS in the gas phase and the condensed phase; (2) the SMA-g-SiO2 compatibilizer grafts a styrene-maleic anhydride copolymer (SMA) onto the surface of nano-SiO2 to prepare a nano-SiO2 with amphiphilic properties. The styrene structural unit of the SMA-g-SiO2 compatibilizer has good compatibility with the polycarbonate resin and the ABS resin, and the maleic anhydride group can react with the terminal hydroxyl group of the polycarbonate resin to improve the interfacial adhesion and compatibility between the polycarbonate resin and the ABS resin. At the same time, the SMA-g-SiO2 compatibilizer can form a continuous silicon-containing carbon layer at the interface to inhibit the decomposition of the more flammable ABS, playing a role in synergistic flame retardancy; (3) functionalized polyhedral oligomeric silsesquioxane (POSS), as a typical silicone-based flame retardant, its compounded flame retardant system can effectively flame retard the PC / ABS composition. The end groups of the functionalized POSS contain epoxy groups, and these epoxy groups can react with the terminal hydroxyl groups of the PC resin, thereby improving the dispersibility and compatibility of the functionalized POSS in the PC resin material, and ultimately enhancing the flame retardancy of the PC / ABS composition. The functionalized POSS has low dielectric properties. Under the condition that the test frequency is 5 GHz, its dielectric constant is only 2.1 - 2.4. This characteristic mainly stems from the unique cage-like three-dimensional structure of POSS. The center of this structure is an inorganic inner core composed of alternating silicon-oxygen (Si-O) connections, and the silicon atoms at the eight vertices are respectively connected with organic substituents (R groups). This cage-like structure allows for a large space inside the molecule, resulting in the inability of molecules to be closely packed, thereby reducing the degree of molecular polarization. When an electric field acts, the molecules are difficult to be polarized, and the dielectric constant decreases accordingly. The Si-O bond has a relatively high bond energy of 445.2 kJ / mol. In contrast, the bond energy of the C-C bond is 350.7 kJ / mol, and the bond energy of the C-O bond is 359.1 kJ / mol. The Si-O bond is more difficult to be broken. Therefore, in an electric field, the vibration and rotation of the Si-O bond are less affected, and the response to the electric field is weakened, which further reduces the dielectric constant.

[0045] The present invention improves the laser direct moldability of a PC / ABS composition by using a combination of modified basic copper phosphate and modified tin oxide. The epoxy groups of the basic copper phosphate and tin oxide organically modified with γ-(2,3-epoxypropoxy)propyltrimethoxysilane can react with the terminal hydroxyl groups of the polycarbonate resin, thereby improving the compatibility and dispersibility between the basic copper phosphate and tin oxide and the polycarbonate resin substrate, and also improving the laser direct moldability. Among them, (1) the basic copper phosphate has a specific crystal structure and electron cloud distribution, enabling it to absorb laser energy of a specific wavelength. At the same time, after the basic copper phosphate induces changes in the polymer matrix under laser irradiation, its own chemical properties will also change to a certain extent, and it can act as a catalyst to promote the subsequent electroless metal plating process. In the electroless plating solution, metal ions (such as copper ions, nickel ions, etc.) will undergo reduction reactions around the active sites generated by the basic copper phosphate. The basic copper phosphate can lower the activation energy of metal ion reduction, making it easier for metal ions to gain electrons and be reduced to metal atoms. (2) Tin oxide itself has a certain electron conduction ability. Before metallization, it can improve the electrical properties of the material. During the metal deposition process, tin oxide can form good contact with the deposited metal, helping electrons to be transmitted between the metal and the substrate, improving the electroless plating effect, and thus improving the laser direct moldability.

[0046] 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is an efficient antioxidant. Its molecule contains multiple phenolic hydroxyl groups, and the hydrogen atoms on the phenolic hydroxyl groups are relatively active and can react with the free radicals generated in the material. Specifically, the phenolic hydroxyl hydrogen atoms in the antioxidant molecule will combine with ROO· to convert it into a relatively stable hydroperoxide (ROOH), which will not further initiate a free radical chain reaction, thereby interrupting the transmission of the oxidation chain reaction and effectively inhibiting the oxidative degradation of the polycarbonate resin.

[0047] Compared with the prior art, the PC / ABS composition and its preparation method provided by the present invention have the following

[0048] Beneficial effects:

[0049] 1. The present invention improves the flame retardancy of the PC / ABS composition by compounding and using a phosphorus-containing acrylate toughening agent, an SMA-g-SiO2 compatibilizer, and a functionalized POSS, and improves the laser direct moldability of the PC / ABS composition by compounding and using a modified basic copper phosphate and a modified tin oxide. At the same time, the low dielectric property of the PC / ABS composition is achieved through the functionalized POSS, and the compatibility and toughness of the PC / ABS composition are improved by the phosphorus-containing acrylate toughening agent and the SMA-g-SiO2 compatibilizer. Moreover, the maleic anhydride groups of the SMA-g-SiO2 compatibilizer can react with the epoxy groups of the functionalized POSS, the modified basic copper phosphate, and the modified tin oxide, reacting with the terminal hydroxyl groups of the PC resin, improving the compatibility and interfacial adhesion between the PC resin and the ABS resin, as well as improving the dispersibility and compatibility of the modified basic copper phosphate and the modified tin oxide in the PC resin material, thereby improving the mechanical properties, flame retardancy, low dielectric property, and laser molding property of the PC / ABS composition. A hindered phenolic antioxidant 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is used to improve the thermal stability and antioxidant property of the PC / ABS composition during the processing and use processes.

[0050] 2. The preparation method of the PC / ABS composition of the present invention has a simple process, is easy to control, has low requirements for equipment, and the equipment used is all general polymer processing equipment, with low investment, which is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 is the process flow chart of the preparation of the PC / ABS composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0052] For the convenience of understanding the present invention, the present invention will be described more comprehensively below in conjunction with the drawings. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosed content of the present invention more thorough and comprehensive.

[0053] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not used to limit the present invention. The term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items.

[0054] The reaction mechanism of the PC / ABS composition of the present invention is as follows (please refer to the process flow chart of the preparation in Figure 1 ):

[0055]

[0056] Reaction mechanism

[0057] Among them, R1 is a PC resin; R2 is a functionalized POSS, or a modified basic copper phosphate, or a modified tin oxide; R3 is an SMA-g-SiO2 compatibilizer.

[0058] It can be seen from the above reaction formula that the maleic anhydride group of the SMA-g-SiO2 compatibilizer and the epoxy groups of the functionalized POSS, the modified basic copper phosphate and the modified tin oxide can react with the terminal hydroxyl groups of the PC resin, improving the compatibility and interfacial adhesion between the PC resin and the ABS resin, as well as improving the dispersibility and compatibility of the modified basic copper phosphate and the modified tin oxide in the PC resin material, thereby preparing a PC / ABS composition with excellent mechanical properties, flame retardant properties, low dielectric properties and laser forming properties.

[0059] The raw materials used in the examples and comparative examples of the present invention are as follows:

[0060] PC resin, with a number average relative molecular mass of 25,000, purchased from Covestro AG, Germany.

[0061] ABS resin, with a butadiene content of 16%, purchased from Tianjin Dagu Chemical Industry Co., Ltd.

[0062] Octamethylcyclotetrasiloxane, purchased from Zhongshan Dixin Chemical Co., Ltd.

[0063] γ-Methacryloxypropyltrimethoxysilane, purchased from Hubei Jusheng Technology Co., Ltd.

[0064] Dodecylbenzenesulfonic acid, purchased from Guangzhou Yuanda New Materials Co., Ltd.

[0065] Sodium hydroxide, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0066] Diethyl methylphosphonate acrylate, purchased from Zhengzhou Alpha Chemical Co., Ltd.

[0067] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted acrylate monomer, purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0068] Sodium dodecyl sulfate, purchased from Hunan Yunbang Biotechnology Co., Ltd.

[0069] Potassium persulfate, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0070] SiO2, with terminal groups containing amino groups, purchased from Hubei Huifu Nanomaterials Co., Ltd.

[0071] N,N-dimethylformamide, purchased from Changzhou Wanyi Run Chemical Co., Ltd.

[0072] Styrene-maleic anhydride copolymer, purchased from Nantong Zhonghe Chemical New Materials Co., Ltd.

[0073] Absolute ethanol, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0074] Functionalized POSS with epoxy groups at the end groups, selected from Hybrid Plastics Company, USA.

[0075] Modified basic copper phosphate, purchased from Hubei Xin Hongli Chemical Co., Ltd.

[0076] Modified tin oxide, purchased from Nanjing Kailinston Chemical Technology Co., Ltd.

[0077] 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, purchased from Hubei Shishun Biotech Co., Ltd.

[0078] The preparation method of the phosphorus-containing acrylate toughening agent used in the following examples and comparative examples includes the following steps:

[0079] (1) Mix 90 g of octamethylcyclotetrasiloxane, 8 g of γ-methacryloxypropyltrimethoxysilane, 2 g of dodecylbenzenesulfonic acid and 175 mL of deionized water in a flask, perform pre-emulsification for 0.5 h at a stirring speed of 400 rpm, then add 1.0 g of dodecylbenzenesulfonic acid and 500 mL of deionized water, heat in a constant temperature water bath to 85 °C, and maintain the rotation speed at 200 rpm. After reacting for 3 h, cool down to obtain a polysiloxane core emulsion. Adjust the pH value of the above polysiloxane core emulsion to 8.0 with 3 wt% sodium hydroxide solution. After adjustment, add 2.0 g of potassium persulfate dropwise to the polysiloxane core emulsion.

[0080] (2) Mix 80 g of diethyl methylphosphonate acrylate, 150 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted acrylate monomer, 2.0 g of sodium dodecyl sulfate and 400 mL of deionized water in a flask, perform pre-emulsification for 0.5 h at a stirring speed of 400 rpm, and then add dropwise to the polysiloxane core emulsion obtained in step (1) with a temperature raised to 80 °C at a speed of 2 drops per second. After dropwise addition, add 1.2 g of potassium persulfate additionally, react for 3 hours, then cool down, discharge, demulsify, filter, wash with deionized water for multiple times and dry to finally obtain the phosphorus-containing acrylate toughening agent.

[0081] The preparation method of the SMA-g-SiO2 compatibilizer used in the following examples and comparative examples includes the following steps:

[0082] 100 g of amino group-containing SiO2 was added to 600 mL of N,N-dimethylformamide, and ultrasonic treatment was carried out for 15 min to obtain a uniform dispersion. At the same time, 50 g of styrene-maleic anhydride copolymer was dissolved in 300 mL of N,N-dimethylformamide. The N,N-dimethylformamide dispersion of amino group-containing SiO2 was poured into a flask, stirred at a speed of 400 rpm, and the N,N-dimethylformamide solution of styrene-maleic anhydride copolymer was slowly added dropwise at 90 °C, and the reaction conditions were kept unchanged for reflux condensation for 12 h. The reaction solution was separated by centrifugation, washed with absolute ethanol, and dried at 60 °C for 12 h to obtain the SMA-g-SiO2 compatibilizer.

[0083] The present invention will be described in detail below with reference to the accompanying drawings and specific examples.

[0084] Example 1 PC / ABS composition and its preparation method

[0085] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0086]

[0087] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0088] Please refer to Figure 1 , the preparation method of the PC / ABS composition of this example includes the following steps:

[0089] (1) After drying the PC resin at a temperature of 104 °C for 4.2 hours, it was cooled; the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant were added to a mixer for mixing;

[0090] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide were added to another high-speed mixer for mixing;

[0091] (3) The mixture obtained in step (1) was added to a parallel twin-screw extruder through a feeder, and the mixture obtained in step (2) was added laterally (the third zone) to the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletization. The process parameters include: the temperature of the first zone is 210 °C, the temperature of the second zone is 210 °C, the temperature of the third zone is 215 °C, the temperature of the fourth zone is 215 °C, the temperature of the fifth zone is 220 °C, the temperature of the sixth zone is 220 °C, the temperature of the seventh zone is 220 °C, the temperature of the eighth zone is 220 °C, the die head temperature is 215 °C, and the screw speed is 400 rpm.

[0092] The screw of the parallel twin-screw extruder has a single-thread thread shape; the ratio of the screw length L to the diameter D, L / D, is 35; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 400 revolutions per minute.

[0093] Example 2 PC / ABS Composition and Its Preparation Method

[0094] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0095]

[0096] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0097] The preparation method of the PC / ABS composition of this example includes the following steps:

[0098] (1) After drying PC resin at a temperature of 114 °C for 2.2 hours, it is cooled; the cooled PC resin, ABS resin, phosphorus-containing acrylate toughener, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant are added to a mixer for mixing.

[0099] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide are added to another high-speed mixer for mixing.

[0100] (3) The mixture well-mixed in step (1) is added to a parallel twin-screw extruder through a feeder, and the mixture well-mixed in step (2) is added laterally (the third zone) to the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 230 °C, the temperature of the second zone is 230 °C, the temperature of the third zone is 235 °C, the temperature of the fourth zone is 235 °C, the temperature of the fifth zone is 240 °C, the temperature of the sixth zone is 240 °C, the temperature of the seventh zone is 240 °C, the temperature of the eighth zone is 240 °C, the die head temperature is 235 °C, and the screw rotation speed is 800 rpm.

[0101] The screw of the parallel twin-screw extruder has a single-thread thread shape; the ratio of the screw length L to the diameter D, L / D, is 55; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1500 revolutions per minute.

[0102] Example 3 PC / ABS Composition and Its Preparation Method

[0103] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0104]

[0105] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0106] The preparation method of the PC / ABS composition of this example includes the following steps:

[0107] (1) Place the PC resin at a temperature of 107 °C and dry it for 3.8 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant to a blender for mixing;

[0108] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide to another high-speed blender for mixing;

[0109] (3) Add the mixture well-mixed in step (1) to a parallel twin-screw extruder through a feeder, and add the mixture well-mixed in step (2) laterally (in the third zone) of the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 215 °C, the temperature of the second zone is 215 °C, the temperature of the third zone is 220 °C, the temperature of the fourth zone is 220 °C, the temperature of the fifth zone is 225 °C, the temperature of the sixth zone is 225 °C, the temperature of the seventh zone is 225 °C, the temperature of the eighth zone is 225 °C, the die head temperature is 220 °C, and the screw speed is 500 rpm.

[0110] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 40; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the blender is a high-speed blender with a rotation speed of 500 revolutions per minute.

[0111] Example 4 PC / ABS Composition and Its Preparation Method

[0112] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0113]

[0114] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0115] The preparation method of the PC / ABS composition of this embodiment includes the following steps:

[0116] (1) Place the PC resin at a temperature of 111 °C and dry it for 2.6 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a blender for mixing;

[0117] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide into another high-speed blender for mixing;

[0118] (3) Add the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 225 °C, the temperature of the second zone is 225 °C, the temperature of the third zone is 230 °C, the temperature of the fourth zone is 230 °C, the temperature of the fifth zone is 235 °C, the temperature of the sixth zone is 235 °C, the temperature of the seventh zone is 235 °C, the temperature of the eighth zone is 235 °C, the die head temperature is 230 °C, and the screw speed is 700 rpm.

[0119] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D is 50; there are 2 meshing block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the blender is a high-speed blender with a rotation speed of 1500 revolutions per minute.

[0120] Example 5 PC / ABS Composition and Its Preparation Method

[0121] The PC / ABS composition of this embodiment is prepared from the following raw materials in parts by weight:

[0122]

[0123] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0124] The preparation method of the PC / ABS composition of this embodiment includes the following steps:

[0125] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a blender for mixing;

[0126] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide to another high-speed mixer for mixing;

[0127] (3) Add the mixture prepared in step (1) to a co-rotating twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (in the third zone) of the co-rotating twin-screw extruder (with a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die temperature is 225 °C, and the screw speed is 600 rpm.

[0128] The screw of the co-rotating twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0129] Example 6 PC / ABS Composition and Its Preparation Method

[0130] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0131]

[0132] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0133] The preparation method of the PC / ABS composition of this example includes the following steps:

[0134] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughener, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant to a mixer for mixing;

[0135] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide to another high-speed mixer for mixing;

[0136] (3) Feed the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and granulation. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0137] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0138] Example 7 PC / ABS Composition and Its Preparation Method

[0139] The PC / ABS composition of this example is prepared from the following raw materials in parts by weight:

[0140]

[0141] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0142] The preparation method of the PC / ABS composition of this example includes the following steps:

[0143] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughener, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a mixer for mixing;

[0144] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide into another high-speed mixer for mixing;

[0145] (3) Feed the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and granulation. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0146] The screw of the parallel twin-screw extruder has a single-thread thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0147] Comparative Example 1

[0148] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0149]

[0150] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0151] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0152] (1) After drying the PC resin at a temperature of 109 °C for 3.2 hours, it is cooled; the cooled PC resin, ABS resin, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant are added to a mixer for mixing;

[0153] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide are added to another high-speed mixer for mixing;

[0154] (3) The mixture prepared in step (1) is added to a parallel twin-screw extruder through a feeder, and the mixture prepared in step (2) is added laterally (the third zone) to the parallel twin-screw extruder (a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw rotation speed is 600 rpm.

[0155] The screw of the parallel twin-screw extruder has a single-thread thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0156] Comparative Example 2

[0157] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0158]

[0159]

[0160] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0161] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0162] (1) After drying the PC resin at a temperature of 109 °C for 3.2 hours, it is cooled; the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, and hindered phenol antioxidant are added to a blender for mixing;

[0163] (2) The functionalized POSS, modified basic copper phosphate, and modified tin oxide are added to another high-speed blender for mixing;

[0164] (3) The mixture well-mixed in step (1) is added to a parallel twin-screw extruder through a feeder, and the mixture well-mixed in step (2) is added laterally (the third zone) to the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0165] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the blender is a high-speed blender with a rotation speed of 1000 revolutions per minute.

[0166] Comparative Example 3

[0167] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0168]

[0169]

[0170] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0171] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0172] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a blender for mixing;

[0173] (2) Add the modified basic copper phosphate and modified tin oxide into another high-speed blender for mixing;

[0174] (3) Add the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (in the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletization. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die temperature is 225 °C, and the screw speed is 600 rpm.

[0175] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the blender is a high-speed blender with a rotation speed of 1000 revolutions per minute.

[0176] Comparative Example 4

[0177] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0178]

[0179]

[0180] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0181] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0182] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a blender for mixing;

[0183] (2) Add the functionalized POSS and modified tin oxide to another high-speed mixer for mixing;

[0184] (3) Add the mixture prepared in step (1) to a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0185] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0186] Comparative Example 5

[0187] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0188]

[0189]

[0190] The hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0191] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0192] (1) After drying the PC resin at a temperature of 109 °C for 3.2 hours, cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant to a mixer for mixing;

[0193] (2) Add the functionalized POSS and modified basic copper phosphate to another high-speed mixer for mixing;

[0194] (3) Feed the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0195] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0196] Comparative Example 6

[0197] The PC / ABS composition of this comparative example is prepared from the following raw materials in parts by weight:

[0198]

[0199] The preparation method of the PC / ABS composition of this comparative example includes the following steps:

[0200] (1) Place the PC resin at a temperature of 109 °C and dry it for 3.2 hours, then cool it; add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, and SMA-g-SiO2 compatibilizer to a mixer for mixing;

[0201] (2) Add the functionalized POSS, modified basic copper phosphate, and modified tin oxide to another high-speed mixer for mixing;

[0202] (3) Feed the mixture prepared in step (1) into a parallel twin-screw extruder through a feeder, and add the mixture prepared in step (2) laterally (the third zone) of the parallel twin-screw extruder (with a total of eight zones) for melt extrusion and pelletizing. The process parameters include: the temperature of the first zone is 220 °C, the temperature of the second zone is 220 °C, the temperature of the third zone is 225 °C, the temperature of the fourth zone is 225 °C, the temperature of the fifth zone is 230 °C, the temperature of the sixth zone is 230 °C, the temperature of the seventh zone is 230 °C, the temperature of the eighth zone is 230 °C, the die head temperature is 225 °C, and the screw speed is 600 rpm.

[0203] The screw of the parallel twin-screw extruder has a single-thread shape; the ratio of the screw length L to the diameter D, L / D, is 45; there are 2 kneading block zones and 1 reverse-thread zone on the screw; in steps (1) and (2), the mixer is a high-speed mixer with a rotation speed of 1000 revolutions per minute.

[0204] The following is a list of the raw material compositions of Examples 1-7 and Comparative Examples 1-6.

[0205] Table 1 List of the raw material compositions of Examples 1-7 and Comparative Examples 1-6

[0206]

[0207]

[0208] Examples 1 to 7 are to prepare PC / ABS compositions by adjusting the addition amounts of PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, functionalized POSS, modified basic copper phosphate, modified tin oxide, and hindered phenol antioxidant. Comparative Example 1 is to prepare a PC / ABS composition without adding a phosphorus-containing acrylate toughening agent. Comparative Example 2 is to prepare a PC / ABS composition without adding an SMA-g-SiO2 compatibilizer. Comparative Example 3 is to prepare a PC / ABS composition without adding functionalized POSS. Comparative Example 4 is to prepare a PC / ABS composition without adding modified basic copper phosphate. Comparative Example 5 is to prepare a PC / ABS composition without adding modified tin oxide. Comparative Example 6 is to prepare a PC / ABS composition without adding a hindered phenol antioxidant.

[0209] The PC / ABS compositions prepared in the above examples and comparative examples were subjected to the following performance tests:

[0210] Tensile strength: Tested according to the standard of GB / T 1040-2006, and the tensile rate is 50 mm / min.

[0211] Notched impact strength: Tested according to the standard of GB / T 1843-2008.

[0212] Flame retardant performance: Tested according to the standard of GB / T 2406.2-2009. The limiting oxygen index of the specimen was measured using an oxygen index meter, and the sample size was 150 mm × 6.5 mm × 3 mm.

[0213] Dielectric constant: Tested according to the standard of GB / T 5597-1999, and the test frequency is 5 GHz.

[0214] Laser direct forming: Adopt the adhesion test of metal coating on the surface of plastic parts (or called hundred-grid test), test according to ASTMD3359 standard, as follows: at room temperature 23±2℃, relative humidity 50±5%, use a sharp blade (blade angle is 15°~30°) to draw 10×10 1mm×1mm small grids on the surface of the test sample, and each line is deep to the bottom layer of the coating; brush the test area clean; use 3M 600 tape to firmly stick to the small grid to be tested, and use an eraser to wipe the tape vigorously to increase the contact area and strength between the tape and the tested area; grab one end of the tape with your hand, and quickly tear off the transparent tape at a 60° angle in the vertical direction, and perform the same test twice at the same position. Result determination: Adhesion is qualified when it is ≥4B; 5B-the edge of the line is smooth, and there is no paint falling off at the edge and intersection of the line; 4B-small pieces of paint fall off at the intersection of the line, and the total falling area is less than 5%; 3B-small pieces of paint fall off at the edge and intersection of the line, and the total falling area is between 5% and 15%; 2B-large pieces of paint fall off at the edge and intersection of the line, and the total falling area is between 15% and 35%; 1B-large pieces of paint fall off at the edge and intersection of the line, and the total falling area is between 35% and 65%; 0B-large pieces of paint fall off at the edge and intersection of the line, and the total falling area is greater than 65%.

[0215] The performance test results are shown in Table 2.

[0216] Table 2 Properties of PC / ABS compositions of Examples 1-7 and Comparative Examples 1-6

[0217]

[0218] From Table 2 we can see that:

[0219] As the amount of PC resin added decreases and the amount of ABS resin and phosphorus-containing acrylate toughening agent added increases, the tensile strength of the PC / ABS composition gradually decreases and the impact strength gradually increases. This is because the tensile strength of the ABS resin and phosphorus-containing acrylate toughening agent substrates is lower than that of the PC resin, and the phosphorus-containing acrylate toughening agent plays a role in toughening the PC / ABS composition.

[0220] With the increase in the addition amounts of the phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and functionalized POSS, the flame retardancy of the PC / ABS composition gradually improves. The reasons are as follows: (1) The phosphorus-containing acrylate toughening agent is an ACR-type flame retardant toughening agent with both flame retardant and toughening functions. Utilizing the synergistic flame retardant effect of P-Si and the toughening structural characteristics of ACR, it selects siloxane as the core layer, phosphorus-containing acrylate monomer as the shell layer, and silane coupling agent (γ-methacryloxypropyltrimethoxysilane) as the cross-linking agent. By inhibiting the generation and growth of microcracks, it improves the impact performance of the material. At the same time, the phosphorus-containing acrylate toughening agent can play a role in flame retarding PC / ABS in the gas phase and condensed phase; (2) The SMA-g-SiO2 compatibilizer grafts styrene-maleic anhydride copolymer (SMA) onto the surface of nano-SiO2 to prepare a nano-SiO2 with amphiphilic properties. The styrene structural unit of the SMA-g-SiO2 compatibilizer has good compatibility with polycarbonate resin and ABS resin, and the maleic anhydride group can react with the terminal hydroxyl group of polycarbonate resin to improve the interfacial adhesion and compatibility between polycarbonate resin and ABS resin. At the same time, the SMA-g-SiO2 compatibilizer can form a continuous silicon-containing carbon layer at the interface to inhibit the decomposition of more flammable ABS and play a synergistic flame retardant role; (3) Functionalized polyhedral oligomeric silsesquioxane (POSS), as a typical organosilicon-based flame retardant, its compound flame retardant system can effectively flame retard the PC / ABS composition. The terminal groups of functionalized POSS contain epoxy groups, and these epoxy groups can react with the terminal hydroxyl groups of PC resin, thereby enhancing the dispersibility and compatibility of functionalized POSS in PC resin materials and ultimately enhancing the flame retardancy of the PC / ABS composition.

[0221] With the increase in the addition amount of functionalized POSS, the dielectric constant of the PC / ABS composition gradually decreases. This is because functionalized POSS has low dielectric characteristics. Under the condition of a test frequency of 5 GHz, its dielectric constant is only 2.1 - 2.4. This characteristic mainly stems from the unique cage-like three-dimensional structure of POSS. The center of this structure is an inorganic inner core composed of alternating silicon-oxygen (Si-O) connections, and the silicon atoms at the eight vertices are respectively connected with organic substituents (R groups). This cage-like structure results in a large space inside the molecule, making it impossible for the molecules to be closely packed, thereby reducing the degree of molecular polarization. When an electric field acts, the molecules are difficult to be polarized, and the dielectric constant decreases accordingly. The Si-O bond has a relatively high bond energy of 445.2 kJ / mol. In contrast, the bond energy of the C-C bond is 350.7 kJ / mol, and the bond energy of the C-O bond is 359.1 kJ / mol. The Si-O bond is more difficult to be broken. Therefore, in an electric field, the vibration and rotation of the Si-O bond are less affected, and the response to the electric field weakens, which further reduces the dielectric constant.

[0222] With the increase in the addition amounts of modified basic copper phosphate and modified tin oxide, the laser forming properties of the PC / ABS composition are both 5B. The reasons are as follows: (1) Basic copper phosphate has a specific crystal structure and electron cloud distribution, enabling it to absorb laser energy of a specific wavelength. At the same time, after the basic copper phosphate induces changes in the polymer matrix under laser irradiation, its own chemical properties will also change to a certain extent. It can act as a catalyst to promote the subsequent electroless plating process. In the electroless plating solution, metal ions (such as copper ions, nickel ions, etc.) will undergo reduction reactions around the active sites generated by basic copper phosphate. Basic copper phosphate can lower the activation energy of metal ion reduction, making it easier for metal ions to gain electrons and be reduced to metal atoms. (2) Tin oxide itself has certain electron conduction ability. Before metallization, it can improve the electrical properties of the material. During the metal deposition process, tin oxide can form good contact with the deposited metal, which helps the transmission of electrons between the metal and the matrix, improves the electroless plating effect, and thus enhances the laser direct formability.

[0223] In summary, by adjusting the addition amounts of PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, functionalized POSS, modified basic copper phosphate, modified tin oxide, and hindered phenol antioxidant, and with the synergistic cooperation of various additives, the PC / ABS composition of the present invention with excellent mechanical properties, flame retardant properties, low dielectric properties, and laser forming properties can be obtained.

[0224] Compared with Example 7, Comparative Example 1 is a PC / ABS composition prepared without adding a phosphorus-containing acrylate toughening agent. Since the phosphorus-containing acrylate toughening agent is an ACR-type flame retardant toughening agent with both flame retardant and toughening functions, it utilizes the synergistic flame retardant effect of P-Si and the toughening structural characteristics of ACR. Selecting siloxane as the core layer, phosphorus-containing acrylate monomer as the shell layer, and silane coupling agent (γ-methacryloxypropyltrimethoxysilane) as the cross-linking agent, it can improve the impact performance of the material by inhibiting the generation and growth of microcracks. At the same time, the phosphorus-containing acrylate toughening agent can play a role in flame retarding PC / ABS in the gas phase and condensed phase. Therefore, the notched impact strength and flame retardant properties of Comparative Example 1 are lower than those of Example 7.

[0225] Compared with Example 7, Comparative Example 2 is a PC / ABS composition prepared without adding the SMA-g-SiO2 compatibilizer. Since the SMA-g-SiO2 compatibilizer grafts styrene-maleic anhydride copolymer (SMA) onto the surface of nano-SiO2 to prepare a nano-SiO2 with amphiphilic properties, the styrene structural unit of the SMA-g-SiO2 compatibilizer has good compatibility with polycarbonate resin and ABS resin, and the maleic anhydride group can react with the terminal hydroxyl groups of the polycarbonate resin to improve the interfacial adhesion and compatibility between the polycarbonate resin and the ABS resin. At the same time, the SMA-g-SiO2 compatibilizer can form a continuous silicon-containing carbon layer at the interface to inhibit the decomposition of the more flammable ABS, playing a synergistic flame-retardant role. Therefore, the tensile strength, notched impact strength, and flame-retardant performance of Comparative Example 2 are lower than those of Example 7.

[0226] Compared with Example 7, Comparative Example 3 is a PC / ABS composition prepared without adding functionalized POSS. Since functionalized polyhedral oligomeric silsesquioxane (POSS), as a typical silicone-based flame retardant, its compounded flame retardant system can effectively flame-retard the PC / ABS composition. The terminal groups of functionalized POSS contain epoxy groups, and these epoxy groups can react with the terminal hydroxyl groups of the PC resin, thereby improving the dispersibility and compatibility of functionalized POSS in the PC resin material and ultimately enhancing the flame-retardant performance of the PC / ABS composition. Functionalized POSS has low dielectric properties. Under the condition that the test frequency is 5 GHz, its dielectric constant is only 2.1 - 2.4. This property mainly stems from the unique cage-like three-dimensional structure of POSS. The center of this structure is an inorganic core composed of alternating silicon-oxygen (Si-O) connections, and the silicon atoms at the eight vertices are respectively connected with organic substituents (R groups). This cage-like structure allows for a large space inside the molecule, resulting in the inability of molecules to pack tightly, thereby reducing the degree of molecular polarization. When an electric field acts, the molecules are difficult to be polarized, and the dielectric constant decreases accordingly. The Si-O bond has a relatively high bond energy of 445.2 kJ / mol. In contrast, the bond energy of the C-C bond is 350.7 kJ / mol, and the bond energy of the C-O bond is 359.1 kJ / mol. The Si-O bond is more difficult to be broken. Therefore, in an electric field, the vibration and rotation of the Si-O bond are less affected, and the response to the electric field is weakened, which further reduces the dielectric constant. Therefore, the flame-retardant performance of Comparative Example 3 is lower than that of Example 7, while the dielectric constant of Comparative Example 3 is higher than that of Example 7.

[0227] Compared with Example 7, Comparative Example 4 is a PC / ABS composition prepared without adding modified basic copper phosphate. Since basic copper phosphate has a specific crystal structure and electron cloud distribution, it can absorb laser energy of a specific wavelength. At the same time, after the basic copper phosphate induces changes in the polymer matrix through laser irradiation, its own chemical properties will also change to a certain extent. It can act as a catalyst to promote the subsequent electroless metal plating process. In the electroless plating solution, metal ions (such as copper ions, nickel ions, etc.) will undergo reduction reactions around the active sites generated by basic copper phosphate. Basic copper phosphate can lower the activation energy of metal ion reduction, making it easier for metal ions to gain electrons and be reduced to metal atoms. Therefore, Comparative Example 4 does not have laser forming performance.

[0228] Compared with Example 7, Comparative Example 5 is a PC / ABS composition prepared without adding modified tin oxide. Since tin oxide itself has a certain electron conduction ability, it can improve the electrical properties of the material before metallization. During the metal deposition process, tin oxide can form good contact with the deposited metal, which helps the transmission of electrons between the metal and the matrix and improves the electroless plating effect, thereby improving the laser direct formability. Therefore, the laser forming performance of Comparative Example 5 is lower than that of Example 7.

[0229] Compared with Example 7, Comparative Example 6 is a PC / ABS composition prepared without adding hindered phenol antioxidants. Since 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is an efficient antioxidant, its molecule contains multiple phenolic hydroxyl groups, and the hydrogen atoms on the phenolic hydroxyl groups are relatively active and can react with the free radicals generated in the material. Specifically, the phenolic hydroxyl hydrogen atoms in the antioxidant molecule will combine with ROO· to convert it into a relatively stable hydroperoxide (ROOH), which will not further initiate a free radical chain reaction, thus interrupting the transmission of the oxidation chain reaction and effectively inhibiting the oxidative degradation of the polycarbonate resin. Therefore, the tensile strength and notched impact strength of Comparative Example 6 are lower than those of Example 7.

[0230] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0231] The above-described embodiments merely represent several implementation manners of the present invention. The description thereof is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A PC / ABS composition, characterized in that: It is prepared from the following raw materials in parts by weight: 80-90 parts of PC resin, ABS resin 10-20 parts, The total weight of the PC resin and the ABS resin is 100 parts. The SMA-g-SiO2 compatibilizer is styrene-maleic anhydride copolymer grafted with silica; and the functionalized POSS is functionalized polyhedral cage-type oligomeric silsesquioxane.

2. The PC / ABS composition according to claim 1, characterized in that: It is prepared from the following raw materials in parts by weight: 82-88 parts of PC resin, ABS resin 12-18 parts, The total weight of the PC resin and the ABS resin is 100 parts.

3. The PC / ABS composition according to claim 1 or 2, characterized in that: The number average relative molecular weight of the PC resin is 20,000 to 30,000; and / or the butadiene content of the ABS resin is 14% to 18%.

4. The PC / ABS composition according to claim 1 or 2, characterized in that: The end group of the functionalized POSS contains an epoxy group; and / or the modified basic copper phosphate is obtained by organically modifying basic copper phosphate with γ-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or the modified tin oxide is obtained by organically modifying tin oxide with γ-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or the hindered phenol antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

5. The PC / ABS composition according to claim 1 or 2, characterized in that: The preparation method of the phosphorus-containing acrylate toughening agent comprises the following steps: (1) 85 g to 95 g of octamethylcyclotetrasiloxane, 6 g to 10 g of γ-methacryloxypropyltrimethoxysilane, 1.5 g to 2.5 g of dodecylbenzenesulfonic acid and 150 mL to 200 mL of deionized water are mixed, and pre-emulsified at a stirring speed of 300 rpm to 500 rpm for 0.3 h to 0.7 h, and then 0.8 g to 1.2 g of dodecylbenzenesulfonic acid and 400 mL to 600 mL of deionized water are added, and heated to 75° C. to 95° C. in a constant temperature water bath, and the rotation speed is maintained at 150 rpm to 250 rpm. After reacting for 2 h to 4 h, the temperature is lowered to obtain a polysiloxane core emulsion; the pH value of the polysiloxane core emulsion is adjusted to 7.8 to 8.2 using a 2 wt % to 4 wt % sodium hydroxide solution, and after the adjustment is completed, 1.5 g to 2.5 g of potassium persulfate is added dropwise to the polysiloxane core emulsion; (2) 75 g to 85 g of diethyl methylphosphonate acrylate, 130 g to 170 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted acrylate monomer, 1.5 g to 2.5 g of sodium dodecyl sulfate and 300 mL to 500 mL of deionized water are mixed, pre-emulsified at a stirring speed of 300 rpm to 500 rpm for 0.3 to 0.7 h, and then dropwise added to the polysiloxane core emulsion of the above step (1) heated to 75° C. to 85° C. After the dropwise addition is completed, 1 g to 1.4 g of potassium persulfate is added, and the mixture is reacted for 2 h to 4 h, then cooled, discharged, demulsified, and filtered to obtain the product.

6. The PC / ABS composition according to claim 1 or 2, characterized in that: The preparation method of the SMA-g-SiO2 compatibilizer comprises the following steps: Add 100g of SiO2 containing amino groups into 500mL~700mL of N,N-dimethylformamide, and perform ultrasonic treatment for 10min~20min to obtain a uniform dispersion; dissolve 40g~60g of styrene-maleic anhydride copolymer in 200mL~400mL of N,N-dimethylformamide to obtain an N,N-dimethylformamide solution of styrene-maleic anhydride copolymer; stir the dispersion at a speed of 300rpm~500rpm, and slowly add the N,N-dimethylformamide solution of styrene-maleic anhydride copolymer dropwise at 85℃~95℃, keep the reaction conditions unchanged, condense and reflux for 10h~14h; separate the reacted solution by centrifugation, wash with anhydrous ethanol, and dry at 55℃~65℃ for 10h~14h to obtain SMA-g-SiO2 compatibilizer.

7. A method for preparing a PC / ABS composition according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) drying the PC resin at a temperature of 104° C. to 114° C. for 2.2 to 4.2 hours, and then cooling; Add the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer and hindered phenol antioxidant into a mixer for mixing; (2) adding the functionalized POSS, modified basic copper phosphate, and modified tin oxide into another high-speed mixer and mixing them; (3) adding the mixed material prepared in step (1) into a parallel twin-screw extruder via a feeder, and adding the mixed material prepared in step (2) into the side of the parallel twin-screw extruder for melt extrusion and granulation, wherein the process parameters include: a temperature of zone 1 of 210° C. to 230° C., a temperature of zone 2 of 210° C. to 230° C., a temperature of zone 3 of 215° C. to 235° C., a temperature of zone 4 of 215° C. to 235° C., a temperature of zone 5 of 220° C. to 240° C., a temperature of zone 6 of 220° C. to 240° C., a temperature of zone 7 of 220° C. to 240° C., a temperature of zone 8 of 220° C. to 240° C., a die head temperature of 215° C. to 235° C., and a screw speed of 400 rpm to 800 rpm.

8. The preparation method according to claim 7, characterized in that: The following steps are involved: (1) drying the PC resin at a temperature of 107° C. to 111° C. for 2.6 to 3.8 hours, and then cooling the PC resin; adding the cooled PC resin, ABS resin, phosphorus-containing acrylate toughening agent, SMA-g-SiO2 compatibilizer, and hindered phenol antioxidant into a mixer for mixing; (2) adding the functionalized POSS, modified basic copper phosphate, and modified tin oxide into another high-speed mixer and mixing them; (3) adding the mixed material prepared in step (1) into a parallel twin-screw extruder via a feeder, and adding the mixed material prepared in step (2) into the side of the parallel twin-screw extruder for melt extrusion and granulation, wherein the process parameters include: a temperature of zone 1 of 215° C. to 225° C., a temperature of zone 2 of 215° C. to 225° C., a temperature of zone 3 of 220° C. to 230° C., a temperature of zone 4 of 220° C. to 230° C., a temperature of zone 5 of 225° C. to 235° C., a temperature of zone 6 of 225° C. to 235° C., a temperature of zone 7 of 225° C. to 235° C., a temperature of zone 8 of 225° C. to 235° C., a die head temperature of 220° C. to 230° C., and a screw speed of 500 rpm to 700 rpm.

9. The preparation method according to claim 7 or 8, characterized in that: The screw shape of the parallel twin-screw extruder is a single-threaded screw; and / or the ratio L / D of the screw length L and the diameter D of the parallel twin-screw extruder is 35 to 55; and / or the screw of the parallel twin-screw extruder is provided with more than one meshing block area and more than one reverse thread area; in step (1) and / or step (2), the mixer is a high-speed mixer with a rotation speed of 500 rpm-1500 rpm.

10. The preparation method according to claim 9, characterized in that: The ratio L / D of the screw length L to the diameter D of the parallel twin-screw extruder is 40-50; and / or, the screw of the parallel twin-screw extruder is provided with two meshing block areas and one reverse thread area.

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