High-CTI (comparative tracking index) glass fiber reinforced PBT / PC (polybutylene terephthalate / polycarbonate) material and preparation method thereof

Abstract

The invention discloses a high-CTI (comparative tracking index) glass fiber reinforced PBT / PC (polybutylene terephthalate / polycarbonate) material and a preparation method thereof. The high-CTI glass fiber reinforced PBT / PC material is prepared from the following raw materials in parts by weight: 20-60 parts of polybutylene terephthalate, 10-25 parts of polycarbonate, 15-25 parts of a filler A, 10-25 parts of a toughening agent, 5-10 parts of a light response compound, 1-5 parts of a microcapsule chemical substance and 0.5-3 parts of a bio-based polymer, the 1-5 parts of microcapsule chemical substances are phase change material microcapsules, and the phase change material microcapsules are composed of chitosan, hexadecane, heat storage salt and a stabilizer. Through microcapsule chemical substances, the high-strength anti-creeping function of the PBT / PC material is realized, the problem that the PBT / PC material is easily subjected to electric spark generation and heat release in electrical equipment and electronic products is solved, the arc resistance, the insulating property and the heat stability of the material are improved, and the electric leakage and breakdown risks of the material under a high-voltage condition are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of engineering plastics, in particular to a high CTI glass fiber reinforced PBT / PC material and a preparation method thereof. Background Art

[0002] With the rapid development of electronic appliances, automobile industry and other fields, the requirements for material performance are increasing day by day. High CTI (Comparative Tracking Index) value materials are increasingly widely used in electronic appliances such as low-voltage capacitor housings, load-break switches, and carbon brush brackets due to their excellent electrical insulation properties. At the same time, the increase in environmental awareness has led to an increasing market demand for environmentally friendly and high-performance materials. Since the material contains a large amount of glass fiber, its processing performance will be affected to a certain extent, resulting in poor fluidity and easy mold scale. In the long-term use process, the performance of the material will change due to environmental factors, and the hydrolysis resistance, weather resistance and other properties will decrease. In addition, due to factors such as raw material costs, production process complexity and equipment investment, the material preparation cost is relatively high.

[0003] Therefore, it is very necessary to propose a high CTI glass fiber reinforced PBT / PC material and a preparation method in this application to solve the problems in the background.

[0004] Patent document CN104231568B discloses a high glow-wire high CTI ultra-tough flame-retardant PBT / PC alloy material and a preparation method thereof. The above patent achieves excellent comprehensive performance of PBT / PC alloy materials, ASTM notched impact> 600J / M, flame retardancy up to UL94 V-0 level (1.6mm), glow-wire temperature GWIT> 850°C, leakage resistance CTI> 600V, which can greatly expand the application field of PBT / PC alloy materials, but the above patent cannot realize the shape memory function of the material.

[0005] Patent document CN108624006B discloses a high-flow glass fiber reinforced flame-retardant PC / PBT alloy material. The above patent realizes the preparation of high-flow glass fiber reinforced flame-retardant PC / PBT alloy material by adding glass fiber and composite flame retardant and adopting twin-screw blending process. It not only has excellent rigidity and impact toughness, but also has excellent flame retardant and heat resistance. It can reduce costs and replace PPO materials. There is no exposed glass fiber on the surface of the injection molded parts, and it can be used in different fields. The material is directly molded by injection molding, with high production efficiency. The used parts can be recycled after crushing, but the above patent cannot achieve the optical color change function.

[0006] Patent document CN103709702B discloses a PC / PBT alloy material and a preparation method thereof. The above patent realizes that the PC / PBT alloy material has good mechanical properties, low temperature resistance and impact resistance, warping resistance and processing performance. The preparation method is simple in process, the process conditions are reasonable and controllable, and it is suitable for industrial production. However, the above patent cannot realize the self-healing function of the material.

[0007] Patent document CN107227002B discloses a high glow-wire ignition temperature and high CTI glass fiber reinforced PBT / PA alloy material. The above patent realizes the use of brominated flame retardants and red phosphorus masterbatch compounded and used together with compounded synergistic flame retardants; it can achieve UL94 V0 grade flame retardant effect, and at the same time can make the glow-wire non-ignition temperature reach 875 degrees, and the comparative tracking index (CTI) can reach 425V. At the same time, due to the introduction of PA6 and appropriate compatibilizers, the toughness of the base resin is improved, expanding the application range of the material, but the above patent cannot achieve the degradability of the material.

[0008] In summary, the above patents cannot realize the shape memory function, optical color change function, self-repair function and degradability of the material, which makes the material vulnerable to damage during use and requires frequent replacement and maintenance, increasing the use cost and waste of resources. The material preparation cost is relatively high, the fluidity is poor, and mold scale is easy to generate. In the long-term use process, the hydrolysis resistance and weather resistance decrease, and the application scope of the material is limited, which affects its market competitiveness and cannot meet the needs of some special fields, affecting the innovation and market appeal of the material. To this end, the present application proposes a high CTI glass fiber reinforced PBT / PC material and a preparation method that can realize the material's shape memory function, optical color change function, material self-repair function and material degradability. Summary of the invention

[0009] The object of the present invention is to provide a high CTI glass fiber reinforced PBT / PC material and a preparation method thereof, so as to solve the technical problems proposed in the above-mentioned background technology that the shape memory function, optical color change function, self-repair function and degradability of the material cannot be realized, resulting in the material being easily damaged during use, requiring frequent replacement and maintenance, increasing the use cost and waste of resources, the material preparation cost is relatively high, the fluidity is poor, and mold scale is easily generated. During long-term use, the hydrolysis resistance and electrical resistance decrease, the application scope of the material is limited, affecting its market competitiveness, and failing to meet the needs of some special fields, affecting the material's innovation and market attractiveness.

[0010] To achieve the above object, the present invention provides the following technical solution: a high CTI glass fiber reinforced PBT / PC material, wherein the high CTI glass fiber reinforced PBT / PC material is prepared from the following raw materials in parts by weight: 20-60 parts of polybutylene terephthalate, 10-25 parts of polycarbonate, 15-25 parts of filler A, 10-25 parts of toughening agent, 5-10 parts of light-responsive compound, 1-5 parts of microcapsule chemical substance, and 0.5-3 parts of bio-based polymer; The filler A is a shape memory polymer, which is composed of a thermoplastic polymer, a cross-linking agent and a shape memory additive; The thermoplastic polymer is a polymer of polyvinyl alcohol, the cross-linking agent is isocyanate, and the shape memory additive is carbon nanotubes.

[0011] Preferably, the 10-25 parts of toughening agent are core-shell structured rubber particles, the core-shell structured rubber particles are composed of a core monomer and a shell monomer, the core monomer is methyl methacrylate, and the shell monomer is butadiene.

[0012] Preferably, the 5-10 parts of the light-responsive compounds are quantum dots, which are nanoscale photosensitive materials, and the BET specific surface area of ​​the quantum dots is 50-200 m² / g.

[0013] Preferably, polybutylene terephthalate and polycarbonate are used as base materials, the intrinsic viscosity of polybutylene terephthalate is 1.3-2.0 dL / g, and the relative density and melting temperature of polycarbonate are 1.20-1.22 g / cm³ and 220-230°C, respectively.

[0014] Preferably, the 1-5 parts of microcapsule chemical substances are phase change material microcapsules, the phase change material microcapsules are composed of chitosan, hexadecane, heat storage salt and stabilizer, and the particle size of the microcapsules is 10-50 microns.

[0015] Preferably, the 0.5-3 parts of bio-based polymers include cellulose polymers, starch polymers, 0.2-2 parts of bio-based butylene syringate and 0.1 parts of bio-based polycaprolactam, the cellulose polymers are 0.1-0.5 parts of cellulose acetate, and the starch polymers are 0.1-0.4 parts of starch-polylactic acid copolymer.

[0016] Preferably, the high CTI glass fiber reinforced PBT / PC material further comprises the following raw materials in parts by weight: 10-30 parts of glass fiber, 8-30 parts of flame retardant, 0.2-0.5 parts of stabilizer, 0.1-0.5 parts of compatibilizer, 0.1-0.5 parts of plasticizer, 0.1-0.3 parts of lubricant, 0.1-0.5 parts of antioxidant, and masterbatch.

[0017] Preferably, the 8-30 parts of flame retardant include the following components in parts by weight: 5-20 parts of silicate flame retardant, 1-5 parts of phosphorus nitrogen flame retardant, 2-5 parts of inorganic flame retardant synergist, the plasticizer is a styrene copolymer, the stabilizer is an organic tin compound, the compatibilizer is an ethylene copolymer, the lubricant is a silicone oil compound, the antioxidant is dibutyl bis(2,4-dimethyl-p-hydroxyphenyl)succinate, and the glass fiber uses S-glass fiber and AR-glass fiber.

[0018] Preferably, the preparation method comprises the following steps: (1) Raw material preparation: prepare polybutylene terephthalate resin, polycarbonate resin, glass fiber, flame retardant, stabilizer, compatibilizer, plasticizer, lubricant, antioxidant, and masterbatch; (2) Drying: Dry the glass fiber in a drying oven to remove moisture and impurities and ensure that the material is dry; (3) Mixing ratio: Put polybutylene terephthalate resin, polycarbonate resin, glass fiber and the additives in (1) into a mixer according to the ratio and mix and stir to ensure that all raw materials are fully mixed; (4) Extrusion: The mixed raw materials are put into the extruder and extruded under high temperature and high pressure; (5) Cooling and solidification: The extruded material is cooled to form a uniform billet; (6) Cutting and granulation: cutting the cooled and solidified blank into granular particles; (7) Injection molding: Place the granular high CTI glass fiber reinforced PBT / PC material into an injection molding machine for injection molding to form the required parts; (8) Heat treatment: Heat treatment of injection molded parts to improve the strength and stability of the material; (9) Surface treatment: Surface treatment is performed on the prepared high CTI glass fiber reinforced PBT / PC material to improve the appearance quality and durability.

[0019] Preferably, the preparation method further comprises the following steps: (10) Preparation of shape memory polymers preparing polyvinyl alcohol, a cross-linking agent, and a shape memory additive; The polymer monomer is mixed with a cross-linking agent and a shape memory additive, and a polymerization reaction is carried out at 50-90° C. to form a polymer network with a cross-linked structure; Performing a hydrolysis reaction to convert the vinyl ether into hydroxyl groups to form polyvinyl alcohol; The polyvinyl alcohol solution after polymerization is filtered to remove the residual initiator and stabilizer, and then washed with water to remove the impurities remaining in the polymer; The washed polyvinyl alcohol solution is dried to remove excess water to obtain a polyvinyl alcohol solid polymer; Processing solid polyvinyl alcohol into the desired shape through a series of operations such as extrusion, injection molding and film blowing; The shape memory polymer is cured by ultraviolet radiation so that the shape memory polymer maintains a desired shape; (11) Preparation of core-shell rubber particles Synthesis of Methyl Methacrylate Core: preparing methyl methacrylate monomer as a core material; Introducing methyl methacrylate monomer into toluene organic solvent, adding ammonium persulfate and stabilizer, controlling reaction conditions to carry out polymerization reaction, and forming methyl methacrylate core particles; Synthetic Butadiene Shell: preparing butadiene monomer as a shell material; The methyl methacrylate core particles are suspended in a toluene organic solvent, butadiene monomer, an initiator and a polymerization accelerator are added to carry out a polymerization reaction; Surface modification and post-processing: A cross-linking agent is introduced on the surface of the formed core-shell structure rubber particles to achieve cross-linking of the rubber particles; The prepared core-shell structure rubber particles are cleaned and dried to remove residual solvent and impurities, thereby obtaining pure methyl methacrylate / butadiene core-shell structure rubber particles; (12) Preparation of microencapsulated chemical substances Dissolving chitosan in a dilute organic acid to form a solution of the wall material; Fully mixing hexadecane and heat storage salt with the wall material solution, so that the hexadecane and heat storage salt are evenly wrapped in the chitosan solution; The phase change material and the wall material mixture are formed into a stable emulsion under the action of fatty acid sorbitan; Ultrasonic waves emulsify the mixture to form a precursor for microcapsules; The chitosan in the emulsified mixture gradually cools and solidifies naturally to form a microcapsule structure; The formed microcapsules are subjected to consolidation treatment to enhance the stability of the microcapsules, and then the microcapsules are separated by centrifugation to obtain chitosan-based hexadecane / thermal storage salt composite microcapsules; The obtained microcapsules are dried to remove residual water; The dried microcapsules are vacuum packed to ensure the stability and storage performance of the microcapsules; (13) Preparation of bio-based polymers Cellulose is extracted from bamboo and cellulose acetate is obtained by esterifying the cellulose with acetate; Starch is extracted from cassava, polylactic acid is synthesized by polymerization of lactic acid, and starch and polylactic acid are copolymerized to prepare starch-polylactic acid copolymer; Extract syringic acid from cloves and prepare butylene syringate through esterification reaction; Glucose and lactam monomers are polymerized to synthesize bio-based polycaprolactam.

[0020] Compared with the prior art, the present invention has the following beneficial effects: The present invention realizes the high-strength anti-leakage function of PBT / PC materials through microcapsule chemical substances, solves the problem that PBT / PC materials are easily susceptible to electric spark generation and heat release in electrical equipment and electronic products, improves the arc resistance, insulation performance and thermal stability of the materials, reduces the risk of leakage breakdown of the materials under high voltage conditions and the deformation and aging speed under high temperature environments, ensures the normal operation and safe use of equipment and products, and prolongs the service life of high CTI glass fiber reinforced PBT / PC materials; 2. The present invention uses core-shell structured rubber particles to achieve self-repairing ability of PBT / PC materials, solving the problem of surface breakage, cracks and damage during use of the materials, thereby extending the service life of the materials, improving the stability and durability of the materials, and opening up new possibilities for the application of the materials; 3. The present invention uses shape memory polymer to make PBT / PC material have shape memory function, solves the problem of limited application scope of PBT / PC material, and can restore the original shape of PBT / PC material after heating, which is suitable for medical devices, smart materials and other fields; 4. The present invention realizes the degradable function of PBT / PC materials through bio-based polymers, solves the problems of environmental impact and resource waste in the process of production, use and disposal, can reduce dependence on traditional petroleum-based raw materials, reduce the environmental impact of materials, reduce resource consumption, and promote circular economy and green manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the preparation process of the shape memory polymer of the present invention; Figure 2 This is a schematic diagram of the preparation process of the core-shell structure rubber particles of the present invention; Figure 3 It is a schematic diagram of the preparation process of the microcapsule chemical substance of the present invention; Figure 4 This is a schematic diagram of the preparation process of the bio-based polymer of the present invention; Figure 5 This is a schematic diagram of the preparation process of the high CTI glass fiber reinforced PBT / PC material of the present invention; DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention. Example 1

[0023] See also Figure 1 , Figure 2 , Figure 3 and Figure 4 , a method for preparing a high CTI glass fiber reinforced PBT / PC material: preparing a shape memory polymer, core-shell structured rubber particles, microencapsulated chemicals and bio-based polymers; Further, firstly, polyvinyl alcohol, a cross-linking agent, and a shape memory additive are prepared, a polymer monomer is mixed with the cross-linking agent and the shape memory additive, a polymerization reaction is carried out at 50-90° C. to form a polymer network with a cross-linked structure, a hydrolysis reaction is carried out to convert vinyl ether into hydroxyl groups to form polyvinyl alcohol, the polyvinyl alcohol solution after the polymerization is filtered to remove residual initiator and stabilizer, and then washed with water to remove impurities remaining in the polymer, the washed polyvinyl alcohol solution is dried to remove excess water to obtain a polyvinyl alcohol solid polymer, a cross-linking reaction is initiated by ultraviolet radiation to form chemical bonds between polymer chains to fix the shape of the material, the cross-linked material is heated to 108° C. to soften and change shape, and then cooled to room temperature to fix the new shape, and the material is restored to its original shape by external stimulation to verify its shape memory performance; Then, a methyl methacrylate core is synthesized: a methyl methacrylate monomer is prepared as a core material, the methyl methacrylate monomer is introduced into a toluene organic solvent, and ammonium persulfate and a stabilizer are added, and the reaction conditions are controlled to perform a polymerization reaction to form methyl methacrylate core particles; Synthesizing butadiene shell: preparing butadiene monomer as the shell material, suspending methyl methacrylate core particles in toluene organic solvent, adding butadiene monomer, initiator and polymerization accelerator, and carrying out polymerization reaction; Surface modification and post-treatment: introducing a crosslinking agent on the surface of the core-shell rubber particles to achieve crosslinking of the rubber particles, washing and drying the prepared core-shell rubber particles to remove residual solvents and impurities, and obtaining pure methyl methacrylate / butadiene core-shell rubber particles, dissolving chitosan in dilute organic acid to form a wall material solution, fully mixing hexadecane and thermal storage salt with the wall material solution to uniformly wrap them in the chitosan solution, forming a stable emulsion of the phase change material and the wall material mixture under the action of fatty acid sorbitan, emulsifying the mixture by ultrasound to form a precursor of microcapsules, and the chitosan in the emulsified mixture is gradually cooled and solidified naturally to form a microcapsule structure, and the formed microcapsules are consolidated to enhance the stability of the microcapsules, and then the microcapsules are separated by centrifugation to obtain chitosan-based hexadecane / thermal storage salt composite microcapsules, and the obtained microcapsules are dried to remove residual moisture, and the dried microcapsules are vacuum packaged to ensure the stability and storage performance of the microcapsules; Finally, cellulose is extracted from bamboo, and cellulose acetate is obtained by acetic acid esterification of cellulose. Starch is extracted from cassava, and polylactic acid is synthesized by polymerization of lactic acid. Starch and polylactic acid are copolymerized to prepare starch-polylactic acid copolymer. Syringic acid is extracted from cloves and prepared by esterification to prepare butylene syringate. Glucose and lactam monomers are polymerized to synthesize bio-based polycaprolactam. Example 2

[0024] See also Figure 5 A high CTI glass fiber reinforced PBT / PC material includes the following raw materials in parts by weight: 50 parts of high CTI glass fiber reinforced PBT / PC blend (60 parts of polybutylene terephthalate, 25 parts of polycarbonate, 20 parts of glass fiber), 10 parts of flame retardant, 0.3 parts of stabilizer, 0.2 parts of compatibilizer, 0.15 parts of plasticizer, 0.11 parts of lubricant, 0.3 parts of antioxidant, 1 part of masterbatch, 15 parts of polyvinyl alcohol, 22 parts of methyl methacrylate / butadiene core-shell structured rubber particles, 5 parts of quantum dots, 2.5 parts of chitosan-based hexadecane / thermal storage salt composite microcapsules, 3 parts of bio-based polymers, a total of 109.56 parts of raw materials; Furthermore, the high CTI glass fiber reinforced PBT / PC blend is first added to a high-speed mixer and stirred at high speed for 2 hours, preheated at 100-150°C to make it evenly heated and melted, and then the pre-dissolved polyvinyl alcohol is slowly added, and stirring and mixing are continued to ensure that the polyvinyl alcohol is evenly dispersed in the blend, and then methyl methacrylate / butadiene core-shell structure rubber particles are added, and stirring and mixing are continued to improve the impact strength and toughness of the material, and chitosan-based hexadecane / thermal storage salt composite microcapsules are added to ensure that the microcapsules are evenly dispersed in the material to improve the thermal stability of the material. Qualitative and flame retardant properties, add bio-based polymers, mix evenly, then put the pretreated composite material into a twin-screw extruder, and extrude the material into shape through the high-speed rotation of the twin screw and the heating effect of the heating system. The temperature is controlled at 220-250°C, the extrusion time is 1-2h, and the extruded material is sent to the injection molding machine. The mold temperature is controlled at 180-220°C, the injection time is 20-30s, and the cooling time is 30-60s. Finally, the molded product is subjected to a series of surface treatment processes such as deburring, polishing, and size measurement, which takes about 30 minutes. Example 3

[0025] See also Figure 5 A high CTI glass fiber reinforced PBT / PC material includes the following raw materials in parts by weight: 50 parts of high CTI glass fiber reinforced PBT / PC blend, 10 parts of flame retardant, 0.3 parts of stabilizer, 0.2 parts of compatibilizer, 0.15 parts of plasticizer, 0.11 parts of lubricant, 0.3 parts of antioxidant, 1 part of masterbatch, 10 parts of polyvinyl alcohol, 27 parts of methyl methacrylate / butadiene core-shell structured rubber particles, 5 parts of quantum dots, 2.5 parts of chitosan-based hexadecane / thermal storage salt composite microcapsules, 3 parts of bio-based polymers, a total of 109.56 parts of raw materials; Furthermore, the high CTI glass fiber reinforced PBT / PC blend is first added to a high-speed mixer and stirred at high speed for 2 hours, preheated at 100-150°C to make it evenly heated and melted, and then the pre-dissolved polyvinyl alcohol is slowly added, and stirring and mixing are continued to ensure that the polyvinyl alcohol is evenly dispersed in the blend, and then methyl methacrylate / butadiene core-shell structure rubber particles are added, and stirring and mixing are continued to improve the impact strength and toughness of the material, and chitosan-based hexadecane / thermal storage salt composite microcapsules are added to ensure that the microcapsules are evenly dispersed in the material to improve the thermal stability of the material. Qualitative and flame retardant properties, add bio-based polymers, mix evenly, then put the pretreated composite material into a twin-screw extruder, and extrude the material into shape through the high-speed rotation of the twin screw and the heating effect of the heating system. The temperature is controlled at 220-250°C, the extrusion time is 1-2h, and the extruded material is sent to the injection molding machine. The mold temperature is controlled at 180-220°C, the injection time is 20-30s, and the cooling time is 30-60s. Finally, the molded product is subjected to a series of surface treatment processes such as deburring, polishing, and size measurement, which takes about 30 minutes. Example 4

[0026] See also Figure 5 A high CTI glass fiber reinforced PBT / PC material includes the following raw materials in parts by weight: 50 parts of high CTI glass fiber reinforced PBT / PC blend, 10 parts of flame retardant, 0.3 parts of stabilizer, 0.2 parts of compatibilizer, 0.15 parts of plasticizer, 0.11 parts of lubricant, 0.3 parts of antioxidant, 1 part of masterbatch, 15 parts of polyvinyl alcohol, 23.5 parts of methyl methacrylate / butadiene core-shell structured rubber particles, 5 parts of quantum dots, 1 part of chitosan-based hexadecane / thermal storage salt composite microcapsules, 3 parts of bio-based polymers, a total of 109.56 parts of raw materials; Furthermore, the high CTI glass fiber reinforced PBT / PC blend is first added to a high-speed mixer and stirred at high speed for 2 hours, preheated at 100-150°C to make it evenly heated and melted, and then the pre-dissolved polyvinyl alcohol is slowly added, and stirring and mixing are continued to ensure that the polyvinyl alcohol is evenly dispersed in the blend, and then methyl methacrylate / butadiene core-shell structure rubber particles are added, and stirring and mixing are continued to improve the impact strength and toughness of the material, and chitosan-based hexadecane / thermal storage salt composite microcapsules are added to ensure that the microcapsules are evenly dispersed in the material to improve the thermal stability of the material. Qualitative and flame retardant properties, add bio-based polymers, mix evenly, then put the pretreated composite material into a twin-screw extruder, and extrude the material into shape through the high-speed rotation of the twin screw and the heating effect of the heating system. The temperature is controlled at 220-250°C, the extrusion time is 1-2h, and the extruded material is sent to the injection molding machine. The mold temperature is controlled at 180-220°C, the injection time is 20-30s, and the cooling time is 30-60s. Finally, the molded product is subjected to a series of surface treatment processes such as deburring, polishing, and size measurement, which takes about 30 minutes. Example 5

[0027] See also Figure 5 A high CTI glass fiber reinforced PBT / PC material includes the following raw materials in parts by weight: 50 parts of high CTI glass fiber reinforced PBT / PC blend, 10 parts of flame retardant, 0.3 parts of stabilizer, 0.2 parts of compatibilizer, 0.15 parts of plasticizer, 0.11 parts of lubricant, 0.3 parts of antioxidant, 1 part of masterbatch, 15 parts of polyvinyl alcohol, 22 parts of methyl methacrylate / butadiene core-shell structured rubber particles, 5 parts of quantum dots, 4.5 parts of chitosan-based hexadecane / thermal storage salt composite microcapsules, 1 part of bio-based polymer, a total of 109.56 parts of raw materials; Furthermore, the high CTI glass fiber reinforced PBT / PC blend is first added to a high-speed mixer and stirred at high speed for 2 hours, preheated at 100-150°C to make it evenly heated and melted, and then the pre-dissolved polyvinyl alcohol is slowly added, and stirring and mixing are continued to ensure that the polyvinyl alcohol is evenly dispersed in the blend, and then methyl methacrylate / butadiene core-shell structure rubber particles are added, and stirring and mixing are continued to improve the impact strength and toughness of the material, and chitosan-based hexadecane / thermal storage salt composite microcapsules are added to ensure that the microcapsules are evenly dispersed in the material to improve the thermal stability of the material. Qualitative and flame retardant properties, add bio-based polymers, mix evenly, then put the pretreated composite material into a twin-screw extruder, and extrude the material into shape through the high-speed rotation of the twin screw and the heating effect of the heating system. The temperature is controlled at 220-250°C, the extrusion time is 1-2h, and the extruded material is sent to the injection molding machine. The mold temperature is controlled at 180-220°C, the injection time is 20-30s, and the cooling time is 30-60s. Finally, the molded product is subjected to a series of surface treatment processes such as deburring, polishing, and size measurement, which takes about 30 minutes. Example 6

[0028] See also Figure 5 , a comparison group 1 is set, a high CTI glass fiber reinforced PBT / PC material includes the following raw materials in parts by weight: 50 parts of high CTI glass fiber reinforced PBT / PC blend, 10 parts of flame retardant, 0.3 parts of stabilizer, 0.2 parts of compatibilizer, 0.15 parts of plasticizer, 0.11 parts of lubricant, 0.3 parts of antioxidant, a total of 61.06 parts of raw materials; Furthermore, the glass fiber is first dried in a drying oven to remove moisture and impurities to ensure that the material is dry, polybutylene terephthalate resin, polycarbonate resin, glass fiber and flame retardant, stabilizer, compatibilizer, plasticizer, lubricant, antioxidant are put into a mixer according to the ratio for mixing and stirring to ensure that various raw materials are fully mixed and uniform, the mixed raw materials are put into an extruder for extrusion, and extrusion molding is performed under high temperature and high pressure, the extruded material is cooled to form a uniform billet, the cooled and solidified billet is cut into granular particles, the granular high CTI glass fiber reinforced PBT / PC material is put into an injection molding machine for injection molding to form the required parts, the injection molded parts are heat treated to improve the strength and stability of the material, and the prepared high CTI glass fiber reinforced PBT / PC material is surface treated to improve the appearance quality and durability. Example 7

[0029] Please refer to Table 1, a high CTI glass fiber reinforced PBT / PC material and preparation method, and performance tests were performed on Examples 2-6; Tensile strength test: According to ISO 527, using a universal materials testing machine, dumbbell-type specimens, type 1A specimens with nominal width and thickness of 10 mm and 4 mm respectively, and a gauge length of usually 75 mm; Thermal expansion coefficient test: According to ISO 11359 standard, GCTKP-700b composite material thermal expansion coefficient tester of Zhongke Micro-Nano is equipped with high-precision, low-temperature drift micro-displacement sensor, which can accurately measure the dimensional changes of materials at different temperatures; UL94 grade test: According to UL 94 standard, use a combustion test machine to record the time from ignition to extinguishing of the material; Dielectric strength test: According to IEC 60243-1 standard, use a high voltage breakdown tester to measure and record the breakdown voltage of the sample; Degradability test: According to GB / T 20197 standard, an infrared spectrometer is used to analyze the chemical composition of the degradation products to further understand the degradation mechanism of the material. The unit % is used to indicate the remaining mass percentage of the material.

[0030] Furthermore, the test results are shown in Table 1.

[0031]

[0032] Analyzing Table 1, Example 2 is the best example with the best comprehensive performance.

[0033] Working principle: a. Add high CTI glass fiber reinforced PBT / PC blend into a mixer and stir at high speed for 2 hours, preheat at 100-150℃ to make it evenly heated and melted; b. Slowly add pre-dissolved polyvinyl alcohol and continue to stir and mix to ensure that polyvinyl alcohol is evenly dispersed in the blend; c. Add methyl methacrylate / butadiene core-shell structure rubber particles and continue to stir and mix to improve the impact strength and toughness of the material; d. Add chitosan-based hexadecane / thermal storage salt composite microcapsules to ensure that the microcapsules are evenly dispersed in the material to improve the thermal stability and flame retardant properties of the material; e. Finally, add bio-based polymer and mix evenly; put the prepared composite material into a twin-screw extruder at 220-250℃, extrude it according to demand, and prepare it into a product with the required shape and size; cool and solidify the prepared product, remove internal stress and perform a series of post-processing processes on the surface to ensure product quality and performance; perform performance testing on the prepared high CTI glass fiber reinforced PBT / PC material to ensure that the product meets relevant standards and requirements.

[0034] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A high CTI glass fiber reinforced PBT / PC material, Features: The high CTI glass fiber reinforced PBT / PC material is prepared from the following raw materials in parts by weight: 20-60 parts of polybutylene terephthalate, 10-25 parts of polycarbonate, 15-25 parts of filler A, 10-25 parts of toughening agent, 5-10 parts of light-responsive compound, 1-5 parts of microcapsule chemical substances, and 0.5-3 parts of bio-based polymer; The 1-5 parts of microcapsule chemical substances are phase change material microcapsules, which are composed of chitosan, hexadecane, heat storage salt and stabilizer, and the particle size of the microcapsules is 10-50 microns.

2. A high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The 10-25 parts of toughening agent are core-shell structure rubber particles, which are composed of core monomers and shell monomers. The core monomer is methyl methacrylate and the shell monomer is butadiene.

3. A high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The 5-10 parts of the light-responsive compounds are quantum dots, which are nano-scale photosensitive materials, and the BET specific surface area of ​​the quantum dots is 50-200 m2 / g.

4. A high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The polybutylene terephthalate and polycarbonate are used as base materials, the intrinsic viscosity of polybutylene terephthalate is 1.3-2.0 dL / g, and the relative density and melting temperature of polycarbonate are 1.20-1.22 g / cm³ and 220-230°C, respectively.

5. The high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The filler A is a shape memory polymer, which is composed of a thermoplastic polymer, a cross-linking agent and a shape memory additive; The thermoplastic polymer is a polymer of polyvinyl alcohol, the cross-linking agent is isocyanate, and the shape memory additive is carbon nanotubes.

6. A high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The 0.5-3 parts of bio-based polymers include cellulose polymers, starch polymers, 0.2-2 parts of bio-based butylene syringate and 0.1 parts of bio-based polycaprolactam, the cellulose polymers are 0.1-0.5 parts of cellulose acetate, and the starch polymers are 0.1-0.4 parts of starch-polylactic acid copolymer.

7. The high CTI glass fiber reinforced PBT / PC material according to claim 1, Features: The high CTI glass fiber reinforced PBT / PC material also includes the following raw materials in parts by weight: 10-30 parts of glass fiber, 8-30 parts of flame retardant, 0.2-0.5 parts of stabilizer, 0.1-0.5 parts of compatibilizer, 0.1-0.5 parts of plasticizer, 0.1-0.3 parts of lubricant, 0.1-0.5 parts of antioxidant, and masterbatch.

8. A high CTI glass fiber reinforced PBT / PC material according to claim 7, Features The 8-30 parts of flame retardant include the following components in parts by weight: 5-20 parts of silicate flame retardant, 1-5 parts of phosphorus nitrogen flame retardant, 2-5 parts of inorganic flame retardant synergist, the plasticizer is a styrene copolymer, the stabilizer is an organic tin compound, the compatibilizer is an ethylene copolymer, the lubricant is a silicone oil compound, the antioxidant is dibutyl bis(2,4-dimethyl-p-hydroxyphenyl)succinate, and the glass fiber uses S-glass fiber and AR-glass fiber.

9. A method for preparing a high CTI glass fiber reinforced PBT / PC material, applicable to a high CTI glass fiber reinforced PBT / PC material as described in any one of 1 to 8, Features: The preparation method comprises the following steps: (1) Raw material preparation: prepare polybutylene terephthalate resin, polycarbonate resin, glass fiber, flame retardant, stabilizer, compatibilizer, plasticizer, lubricant, antioxidant, and masterbatch; (2) Drying: Dry the glass fiber in a drying oven to remove moisture and impurities and ensure that the material is dry; (3) Mixing ratio: Put polybutylene terephthalate resin, polycarbonate resin, glass fiber and the additives in (1) into a mixer in a ratio of 1:3:2 and mix and stir to ensure that all raw materials are fully mixed; (4) Extrusion: The mixed raw materials are put into the extruder and extruded under high temperature and high pressure; (5) Cooling and solidification: The extruded material is cooled to form a uniform billet; (6) Cutting and granulation: cutting the cooled and solidified blank into granular particles; (7) Injection molding: Place the granular high CTI glass fiber reinforced PBT / PC material into an injection molding machine for injection molding to form the required parts; (8) Heat treatment: Heat treatment of injection molded parts to improve the strength and stability of the material; (9) Surface treatment: Surface treatment is performed on the prepared high CTI glass fiber reinforced PBT / PC material to improve the appearance quality and durability.

10. The method for preparing a high CTI glass fiber reinforced PBT / PC material according to claim 9, Features: The preparation method further comprises the following steps: (10) Preparation of shape memory polymers preparing polyvinyl alcohol, a cross-linking agent, and a shape memory additive; The polymer monomer is mixed with a cross-linking agent and a shape memory additive, and a polymerization reaction is carried out at 50-90° C. to form a polymer network with a cross-linked structure; Performing a hydrolysis reaction to convert the vinyl ether into hydroxyl groups to form polyvinyl alcohol; The polyvinyl alcohol solution after polymerization is filtered to remove the residual initiator and stabilizer, and then washed with water to remove the impurities remaining in the polymer; The washed polyvinyl alcohol solution is dried to remove excess water to obtain a polyvinyl alcohol solid polymer; Processing solid polyvinyl alcohol into the desired shape through a series of operations such as extrusion, injection molding and film blowing; The shape memory polymer is cured by ultraviolet radiation so that the shape memory polymer maintains a desired shape; (11) Preparation of core-shell rubber particles Synthesis of Methyl Methacrylate Core: preparing methyl methacrylate monomer as a core material; Introducing methyl methacrylate monomer into toluene organic solvent, adding ammonium persulfate and stabilizer, controlling reaction conditions to carry out polymerization reaction, and forming methyl methacrylate core particles; Synthetic Butadiene Shell: preparing butadiene monomer as a shell material; The methyl methacrylate core particles are suspended in a toluene organic solvent, butadiene monomer, an initiator and a polymerization accelerator are added to carry out a polymerization reaction; Surface modification and post-processing: A cross-linking agent is introduced on the surface of the formed core-shell structure rubber particles to achieve cross-linking of the rubber particles; The prepared core-shell structure rubber particles are cleaned and dried to remove residual solvent and impurities, thereby obtaining pure methyl methacrylate / butadiene core-shell structure rubber particles; (12) Preparation of microencapsulated chemical substances Dissolving chitosan in a dilute organic acid to form a solution of the wall material; Fully mixing hexadecane and heat storage salt with the wall material solution, so that the hexadecane and heat storage salt are evenly wrapped in the chitosan solution; The phase change material and the wall material mixture are formed into a stable emulsion under the action of fatty acid sorbitan; Ultrasonic waves emulsify the mixture to form a precursor for microcapsules; The chitosan in the emulsified mixture gradually cools and solidifies naturally to form a microcapsule structure; The formed microcapsules are subjected to consolidation treatment to enhance the stability of the microcapsules, and then the microcapsules are separated by centrifugation to obtain chitosan-based hexadecane / thermal storage salt composite microcapsules; The obtained microcapsules are dried to remove residual water; The dried microcapsules are vacuum packed to ensure the stability and storage performance of the microcapsules; (13) Preparation of bio-based polymers Cellulose is extracted from bamboo and cellulose acetate is obtained by esterifying the cellulose with acetate; Starch is extracted from cassava, polylactic acid is synthesized by polymerization of lactic acid, and starch and polylactic acid are copolymerized to prepare starch-polylactic acid copolymer; Extract syringic acid from cloves and prepare butylene syringate through esterification reaction; Glucose and lactam monomers are polymerized to synthesize bio-based polycaprolactam.

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