High-toughness and high-hardness PC material and preparation method thereof

Abstract

The invention discloses a high-toughness and high-hardness PC (polycarbonate) material and a preparation method thereof, and belongs to the technical field of materials, double bonds on the surface of a modified corrosion inhibition microcapsule and sulfydryl in a modified flame-retardant functional ligand are subjected to sulfydryl-alkene click reaction to be co-extruded with polycarbonate, and the high-toughness and high-hardness PC material is obtained. Excellent strength, toughness, flame retardance and aging resistance are achieved; double bonds on the surface of the modified corrosion inhibition microcapsule and sulfydryl in the modified flame-retardant functional ligand are subjected to a sulfydryl-alkene click reaction, and the sulfydryl-alkene click reaction can avoid agglomeration caused by the nano-size effect of the modified flame-retardant functional ligand, so that the modified flame-retardant functional ligand can be stably grafted on the surface of the modified corrosion inhibition microcapsule; and the modified corrosion inhibition microcapsule internally contains a corrosion inhibition component benzotriazole, so that the benzotriazole can be released when the microcapsule is broken or decomposed, and the PC material is repaired.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of materials, and particularly relates to a high-toughness high-hardness PC material and a preparation method thereof. BACKGROUND

[0002] Polycarbonate (PC) resin is a thermoplastic engineering plastic with excellent comprehensive performance in general engineering plastics, and is well-known for high impact strength, excellent electrical insulation, high heat resistance, cold resistance, creep resistance, ultraviolet radiation resistance and electrical comprehensive performance, good dimensional stability, and certain inherent flame retardance, and is widely used in household appliances, automobiles, electronic appliances and the like. The PC material has low surface hardness, and is prone to scratches, finger scratches and cloth wiping in the process of use, thereby affecting the appearance. In addition, the PC material has poor toughness and low impact strength in the long-term use process, and therefore, it is important to develop a high-hardness PC material while maintaining high toughness.

[0003] A kind of flame-retardant PC / ABS alloy is disclosed in Chinese patent CN117229622B, the core of functional additive in the scheme is nano cerium oxide and nano zirconium oxide, which itself has certain anti-ultraviolet aging performance and fire resistance, by depositing aluminum hydroxide, magnesium hydroxide and zinc hydroxide on its surface, a hydroxide film layer is generated on its surface, further improving its flame retardant performance, and the introduction of 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid and 2-phenyl benzimidazole-5-sulfonic acid also effectively improves the anti-ultraviolet aging performance of the functional additive, effectively ensures the aging resistance of the provided PC / ABS alloy, and to some extent, prolongs its service life, but the 2-phenyl benzimidazole-5-sulfonic acid in the scheme is prone to migration, resulting in weakened anti-ultraviolet aging performance. SUMMARY

[0004] The purpose of the present application is to provide a high-toughness high-hardness PC material and a preparation method thereof, by modifying the double bond on the surface of the corrosion inhibition microcapsule and the mercapto group in the modified flame-retardant functional ligand to undergo mercapto-alkene click reaction and co-extrusion with polycarbonate, the mercapto-alkene click reaction can avoid the agglomeration caused by the nano-size effect of the modified flame-retardant functional ligand, so that it can be stably grafted on the surface of the modified corrosion inhibition microcapsule, the corrosion inhibition component benzotriazole is contained in the modified corrosion inhibition microcapsule, which can release benzotriazole when the microcapsule is broken or decomposed, and repair the PC material.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A preparation method of a high-toughness high-hardness PC material, comprising the following steps:

[0007] Step one: through the esterification reaction of sodium tripolyphosphate and 2,5-dihydroxyterephthalic acid, the phosphoric acid monomer is obtained, and then the phosphoric acid monomer is coordinated with zinc chloride under hydrothermal conditions to obtain the flame-retardant functional ligand.

[0008] Step two: the flame-retardant functional ligand is treated with (3-mercaptopropyl) trimethoxysilane to obtain a modified flame-retardant functional ligand.

[0009] Step three: the sodium alginate and paraffin form corrosion inhibition microcapsules and are grafted with acrylic acid to obtain modified corrosion inhibition microcapsules.

[0010] Step four: the modified flame-retardant functional ligand and the modified corrosion inhibition microcapsules undergo thiol-ene click reaction and are mixed with polycarbonate to obtain a high-toughness high-hardness PC material.

[0011] Further, the preparation steps of the phosphoric acid monomer are as follows:

[0012] Sodium tripolyphosphate, 2,5-dihydroxyterephthalic acid and tetrahydrofuran are added to a reaction kettle, stirred at 20-25℃ and 500-600r / min for 20-30min, anhydrous magnesium sulfate is added to the reaction system as a dehydrating agent and concentrated sulfuric acid with a mass fraction of 98%, and the stirring is continued for 24-26h, the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times respectively, and vacuum dried at 60-70℃ for 1-2h to obtain the phosphoric acid monomer.

[0013] Further, the amount ratio of sodium tripolyphosphate, 2,5-dihydroxyterephthalic acid, tetrahydrofuran, anhydrous magnesium sulfate and concentrated sulfuric acid is 180-190g:120-140g:2-3L:12-13g:2-3mL.

[0014] Further, the preparation steps of the flame-retardant functional ligand are as follows:

[0015] The phosphoric acid monomer, N,N-dimethylformamide and an ice acetic acid solution with a concentration of 1mol / L are added to a polytetrafluoroethylene reaction kettle, stirred at 20-25℃ and 500-600r / min for 20-30min, ultrasonically dispersed for 40-60min, then zinc chloride is added, ultrasonically dispersed for 45-60min, and reacted at 125-130℃ for 24-26h, then naturally cooled to room temperature, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times respectively, and vacuum dried at 60-70℃ for 1-2h to obtain the flame-retardant functional ligand.

[0016] Further, the amount ratio of the phosphoric acid monomer, N,N-dimethylformamide, the ice acetic acid solution and zinc chloride is 170-180g:3-4L:27-30mL:40-50g.

[0017] Further, the specific preparation steps of the modified flame-retardant functional ligand are as follows:

[0018] (3-mercaptopropyl) trimethoxysilane, flame-retardant functional precursor, anhydrous ethanol and deionized water are added to the reaction kettle, stirred at 50-70℃ and 500-600r / min for 2-3h, filtered, the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times, vacuum dried at 60-70℃ for 1-2h, and the modified flame-retardant functional ligand is obtained.

[0019] Further, the amount ratio of (3-mercaptopropyl) trimethoxysilane, flame-retardant functional precursor, anhydrous ethanol and deionized water is 50-60g:160-170g:200-250mL:500-600mL.

[0020] Further, the specific preparation steps of the modified flame-retardant functional ligand are as follows:

[0021] Sodium alginate and deionized water are added to the reaction kettle, stirred at 20-25℃ and 1000-1200r / min for 10-15min, then a benzotriazole solution with a mass fraction of 40-50% is added, and stirring is continued for 30-40min to obtain a mixed solution; the mixed solution is added dropwise into a calcium chloride solution with a mass fraction of 5-7%, stirring is continued for 3-4h, filtration is performed, the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times, and vacuum drying is performed at 60-70℃ for 1-2h to obtain the corrosion inhibition microcapsule.

[0022] Further, the amount ratio of sodium alginate, deionized water and benzotriazole solution is 120-130g:1-2L:80-90mL.

[0023] Further, the amount ratio of the mixed solution and the calcium chloride solution is 200-300mL:300-400mL.

[0024] Further, the specific preparation steps of the modified corrosion inhibition microcapsule are as follows:

[0025] Corrosion inhibition microcapsule, acrylic acid and deionized water are added to the reaction kettle, stirred at 20-25℃ and 500-600r / min for 20-30min, then concentrated sulfuric acid with a mass fraction of 98% is added, heated to 50-60℃, and stirring is continued for 1-2h, filtration is performed, the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times, and vacuum drying is performed at 60-70℃ for 1-2h to obtain the modified corrosion inhibition microcapsule.

[0026] Further, the amount ratio of corrosion inhibition microcapsule, acrylic acid, deionized water and concentrated sulfuric acid is 80-90g:100-120mL:1-2L:8-10mL.

[0027] Further, the specific preparation steps of the high-toughness high-hardness PC material are as follows:

[0028] The modified flame-retardant functional ligand, the modified corrosion-inhibiting microcapsule, 2,2-dimethylol propionic acid and tetrahydrofuran are added into a reaction kettle, stirred at 20-25 DEG C and 500-600 r / min for 20-30 min, then the obtained solution is poured on a polytetrafluoroethylene mold, irradiated at 20-25 DEG C, ultraviolet light 365-370 nm and light intensity 50-60 mW / cm 2 The conditions, and light-cured for 25-30 min, then the thiol-ene click reaction is induced by ultraviolet light, and then polycarbonate is added and transferred into a twin-screw extruder, extruded at 200-220 DEG C, cooled, and granulated to obtain a high-toughness high-hardness PC material.

[0029] Further, the usage ratio of the modified flame-retardant functional ligand, the modified corrosion-inhibiting microcapsule, 2,2-dimethylol propionic acid, tetrahydrofuran and polycarbonate is 130-140 g: 50-60 g: 12-15 g: 4-5 L: 4-5 kg.

[0030] The beneficial effects of the application are as follows:

[0031] 1. The high-toughness high-hardness PC material prepared by the application is obtained by the thiol-ene click reaction between the double bond on the surface of the modified corrosion-inhibiting microcapsule and the thiol group in the modified flame-retardant functional ligand and the co-extrusion of polycarbonate, and has excellent strength, toughness, flame retardancy and aging resistance.

[0032] 2. The phosphoric acid group monomer is obtained by esterification of sodium tripolyphosphate and 2,5-dihydroxyterephthalate, and the flame-retardant functional ligand is formed by hydrothermal coordination of the phosphoric acid group monomer and zinc chloride, and the molecular structure contains phosphoric acid groups and zinc ions, and when burning, the phosphoric acid is decomposed into poly-metaphosphoric acid, catalyzing the dehydration of PC molecular chains to form a dense carbon layer, and the zinc ions act as Lewis acid catalysts to accelerate the rearrangement reaction of PC to generate phenolic hydroxyl groups and further crosslink into carbon to block the diffusion of heat and oxygen; the rigid structure formed by the coordination of the phosphoric acid group monomer and zinc chloride can significantly improve the rigidity of PC segments through the benzene ring and phosphoric acid ester groups in the molecule; the three-dimensional network formed by the hydrolysis of (3-mercapto propyl) trimethoxysilane is bonded to the flame-retardant ligand, and the click reaction of thiol and acrylic double bond occurs during ultraviolet curing to form covalent crosslinking, which can significantly increase the toughness of the PC material.

[0033] 3. The application is by modifying the surface of the corrosion inhibitor microcapsule double bond and the thiol group in the modified flame-retardant functional ligand occur thiol-alkene click reaction, thiol-alkene click reaction can avoid the agglomeration caused by the nano size effect of the modified flame-retardant functional ligand, so that it can be stably grafted on the surface of the modified corrosion inhibitor microcapsule, the modified corrosion inhibitor microcapsule contains corrosion inhibitor component benzotriazole, which can release benzotriazole when the microcapsule breaks or decomposes, and repair the PC material.

[0034] 4. The application is by modifying the surface of the corrosion inhibitor microcapsule double bond and the thiol group in the modified flame-retardant functional ligand occur thiol-alkene click reaction, thiol-alkene click reaction can avoid the agglomeration caused by the nano size effect of the modified flame-retardant functional ligand, so that it can be stably grafted on the surface of the modified corrosion inhibitor microcapsule, the modified corrosion inhibitor microcapsule contains corrosion inhibitor component benzotriazole, which can release benzotriazole when the microcapsule breaks or decomposes, and repair the PC material. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the application.

[0036] Embodiment 1: A preparation method of a high-toughness high-hardness PC material, comprising the following steps:

[0037] S1: 180g of sodium tripolyphosphate, 120g of 2,5-dihydroxyterephthalic acid and 2L of tetrahydrofuran are added to a reaction kettle, stirred at 20℃ and 500r / min for 20min, 12g of anhydrous magnesium sulfate is added to the reaction system as a dehydrating agent and 2mL of concentrated sulfuric acid with a mass fraction of 98%, and continues to stir for 24h, and then the filter cake is washed with deionized water and anhydrous ethanol for 2 times respectively, and vacuum dried at 60℃ for 1h to obtain a phosphoric acid monomer.

[0038] S2: 170g of the phosphoric acid monomer, 3L of N,N-dimethylformamide and 27mL of a 1mol / L glacial acetic acid solution are added to a polytetrafluoroethylene reaction kettle, stirred at 20℃ and 500r / min for 20min, ultrasonically dispersed for 40min, then 40g of zinc chloride is added, ultrasonically dispersed for 45min, and reacted at 125℃ for 24h, and then naturally cooled to room temperature, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2 times respectively, and vacuum dried at 60℃ for 1h to obtain a flame-retardant functional ligand.

[0039] S3: 50 g (3-mercapto propyl) trimethoxysilane, 160 g flame-retardant functional precursor, 200 mL anhydrous ethanol and 500 mL deionized water were added into a reaction kettle, stirred at 50℃ and 500 r / min for 2 h, filtered, the filter cake was washed with deionized water and anhydrous ethanol for 2 times respectively, vacuum dried at 60℃ for 1 h, to obtain a modified flame-retardant functional ligand.

[0040] S4: 120 g sodium alginate and 1 L deionized water were added into a reaction kettle, stirred at 20℃ and 1000 r / min for 10 min, then 80 mL of 40% benzotriazole solution was added, and stirred for 30 min to obtain a mixed solution; 200 mL of the mixed solution was added dropwise into 300 mL of 5% calcium chloride solution, and stirred for 3 h, filtered, the filter cake was washed with deionized water and anhydrous ethanol for 2 times respectively, vacuum dried at 60℃ for 1 h, to obtain corrosion inhibition microcapsules.

[0041] S5: 80 g of corrosion inhibition microcapsules, 100 mL of acrylic acid and 1 L of deionized water were added into a reaction kettle, stirred at 20℃ and 500 r / min for 20 min, then 8 mL of 98% concentrated sulfuric acid was added, heated to 50℃, and stirred for 1 h, filtered, the filter cake was washed with deionized water and anhydrous ethanol for 2 times respectively, vacuum dried at 60℃ for 1 h, to obtain modified corrosion inhibition microcapsules.

[0042] S6: 130 g of modified flame-retardant functional ligand, 50 g of modified corrosion inhibition microcapsules, 12 g of 2,2-dimethylol propionic acid and 4 L of tetrahydrofuran were added into a reaction kettle, stirred at 20℃ and 500 r / min for 20 min, then the obtained solution was poured into a polytetrafluoroethylene mold, irradiated at 20℃, ultraviolet light 365 nm and light intensity 50 mW / cm 2 , and the light curing time was 25 min, then 4 kg of polycarbonate was added, transferred into a twin-screw extruder, extruded at 200℃, cooled, and granulated to obtain a high-toughness high-hardness PC material.

[0043] Example 2: A preparation method of a high-toughness high-hardness PC material, comprising the following steps:

[0044] S1: 185 g of sodium tripolyphosphate, 130 g of 2,5-dihydroxyterephthalic acid and 2.5 L of tetrahydrofuran were added into a reaction kettle, stirred at 22.5℃ and 550 r / min for 25 min, 12.5 g of anhydrous magnesium sulfate was added into the reaction system as a dehydrating agent and 2.5 mL of 98% concentrated sulfuric acid, and stirred for 25 h, filtered, the filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, vacuum dried at 65℃ for 1.5 h, to obtain a phosphonic acid monomer.

[0045] S2: 175 g of phosphonic monomer, 3.5 L of N,N-dimethylformamide and 28.5 mL of 1 mol / L glacial acetic acid solution were added into a polytetrafluoroethylene reactor, stirred at 22.5 °C and 550 r / min for 25 min, ultrasonically dispersed for 50 min, then 45 g of zinc chloride was added, ultrasonically dispersed for 52.5 min, and reacted at 127.5 °C for 25 h, and then naturally cooled to room temperature. The filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and vacuum dried at 65 °C for 1.5 h to obtain the flame-retardant functional ligand.

[0046] S3: 55 g of (3-mercaptopropyl)trimethoxysilane, 165 g of flame-retardant functional precursor, 225 mL of anhydrous ethanol and 550 mL of deionized water were added into a reactor, stirred at 60 °C and 550 r / min for 2.5 h, and then filtered. The filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and vacuum dried at 65 °C for 1.5 h to obtain the modified flame-retardant functional ligand.

[0047] S4: 125 g of sodium alginate and 1.5 L of deionized water were added into a reactor, stirred at 22.5 °C and 1100 r / min for 12.5 min, then 85 mL of 45% benzotriazole solution was added, and stirred for 35 min to obtain a mixed solution. 250 mL of the mixed solution was added dropwise into 350 mL of 6% calcium chloride solution, and stirred for 3.5 h. The filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and vacuum dried at 65 °C for 1.5 h to obtain the corrosion inhibition microcapsule.

[0048] S5: 85 g of the corrosion inhibition microcapsule, 110 mL of acrylic acid and 1.5 L of deionized water were added into a reactor, stirred at 22.5 °C and 550 r / min for 25 min, then 9 mL of 98% concentrated sulfuric acid was added, heated to 55 °C, and then stirred for 1.5 h. The filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and vacuum dried at 65 °C for 1.5 h to obtain the modified corrosion inhibition microcapsule.

[0049] S6: 135 g of the modified flame-retardant functional ligand, 55 g of the modified corrosion inhibition microcapsule, 13.5 g of 2,2-dimethylol propionic acid and 4.5 L of tetrahydrofuran were added into a reactor, stirred at 22.5 °C and 550 r / min for 25 min, then the obtained solution was poured into a polytetrafluoroethylene mold, and irradiated at 22.5 °C, 367.5 nm ultraviolet light and 55 mW / cm 2 of light intensity for 27.5 min. The thiol-ene click reaction was induced by ultraviolet light, then 4.5 kg of polycarbonate was added, transferred into a twin-screw extruder, extruded at 210 °C, cooled, and granulated to obtain a high-toughness high-hardness PC material.

[0050] Embodiment 3: A method for preparing a high-toughness high-hardness PC material, comprising the following steps:

[0051] S1: 190 g of sodium tripolyphosphate, 140 g of 2,5-dihydroxyterephthalic acid, and 3 L of tetrahydrofuran were added to a reaction kettle, stirred at 25°C and 600 r / min for 30 min, 13 g of anhydrous magnesium sulfate was added to the reaction system as a dehydrating agent, and 3 mL of concentrated sulfuric acid with a mass fraction of 98% was added, and stirring was continued for 26 h, the filter cake was washed with deionized water and anhydrous ethanol for 4 times respectively, and vacuum dried at 70°C for 2 h to obtain a phosphoric acid-based monomer.

[0052] S2: 180 g of the phosphoric acid-based monomer, 4 L of N,N-dimethylformamide, and 30 mL of a 1 mol / L glacial acetic acid solution were added to a polytetrafluoroethylene reaction kettle, stirred at 25°C and 600 r / min for 30 min, and ultrasonically dispersed for 60 min, then 50 g of zinc chloride was added and ultrasonically dispersed for 60 min, and reacted at 130°C for 26 h, and then naturally cooled to room temperature, filtered, and the filter cake was washed with deionized water and anhydrous ethanol for 4 times respectively, and vacuum dried at 70°C for 2 h to obtain a flame-retardant functional ligand.

[0053] S3: 60 g of (3-mercaptopropyl)trimethoxysilane, 170 g of the flame-retardant functional precursor, 250 mL of anhydrous ethanol, and 600 mL of deionized water were added to a reaction kettle, stirred at 70°C and 600 r / min for 3 h, filtered, and the filter cake was washed with deionized water and anhydrous ethanol for 4 times respectively, and vacuum dried at 70°C for 2 h to obtain a modified flame-retardant functional ligand.

[0054] S4: 130 g of sodium alginate and 2 L of deionized water were added to a reaction kettle, stirred at 25°C and 1200 r / min for 15 min, then 90 mL of a 50% benzotriazole solution was added, and stirring was continued for 40 min to obtain a mixed solution; 300 mL of the mixed solution was added dropwise into 400 mL of a 7% calcium chloride solution, and stirring was continued for 4 h, then filtered, and the filter cake was washed with deionized water and anhydrous ethanol for 4 times respectively, and vacuum dried at 70°C for 2 h to obtain corrosion-inhibiting microcapsules.

[0055] S5: 90 g of the corrosion-inhibiting microcapsules, 120 mL of acrylic acid, and 2 L of deionized water were added to a reaction kettle, stirred at 25°C and 600 r / min for 30 min, then 10 mL of concentrated sulfuric acid with a mass fraction of 98% was added, heated to 60°C, and stirring was continued for 2 h, then filtered, and the filter cake was washed with deionized water and anhydrous ethanol for 4 times respectively, and vacuum dried at 70°C for 2 h to obtain modified corrosion-inhibiting microcapsules.

[0056] S6: 140 g modified flame-retardant functional ligand, 60 g modified corrosion-inhibiting microcapsule, 15 g 2,2-dimethylol propionic acid, and 5 L tetrahydrofuran were added into a reaction kettle, stirred at 25 °C and 600 r / min for 30 min, and then the obtained solution was poured onto a polytetrafluoroethylene mold, irradiated at 25 °C, 370 nm of ultraviolet light, and 60 mW / cm 2 of light intensity, and cured for 30 min. Then, 5 kg of polycarbonate was added, transferred into a twin-screw extruder, extruded at 220 °C, cooled, and granulated to obtain a high-toughness high-hardness PC material.

[0057] Comparative Example 1: On the basis of Example 3, the phosphonic acid monomer in step S2 was replaced by a mixture of sodium tripolyphosphate and 2,5-dihydroxyterephthalic acid in step S1.

[0058] Comparative Example 2: On the basis of Example 3, the modified flame-retardant functional ligand in step S6 was replaced by the flame-retardant functional ligand in step S2 without step S3.

[0059] Comparative Example 3: On the basis of Example 3, the corrosion-inhibiting microcapsule was replaced by a microcapsule with a silica wall layer and a benzotriazole core layer without step S4.

[0060] The high-toughness high-hardness PC materials obtained in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests, and the results are shown in Table 1.

[0061] 1. Toughness test: The notched impact strength was tested at 23 °C according to the standard ISO 180:2019, wherein the notch type was type A notch.

[0062] 2. Ball indentation surface hardness test: The test was performed according to the standard GBT 3398-1:2008, and the specific test conditions were 358 N / 30 S.

[0063] 3. Limiting oxygen index: The test was performed according to the standard GB 2406-80 (plastics).

[0064] 4. Xenon lamp aging: The test conditions were 420 nm wavelength, 0.08 W / m 2 of irradiation intensity, and irradiation for 1000 h.

[0065] Table 1: Performance test table of high-toughness high-hardness PC materials

[0066]

[0067] As can be seen from Table 1, the high-toughness high-hardness PC material obtained in Examples 1-3 has significantly better notched impact strength and ball indentation surface hardness, and significantly lower limiting oxygen index and xenon lamp aging change than the comparative examples, indicating that the high-toughness high-hardness PC material prepared in the application has excellent strength, toughness, flame retardance and aging resistance.

[0068] In Comparative Example 1, the phosphoric acid group monomer is replaced by a mixture of sodium tripolyphosphate and 2,5-dihydroxyterephthalic acid in step S1. The flame retardance decreases, the unesterified phosphoric acid groups cannot form a coordination structure with zinc chloride, losing the ability to catalyze carbonization, the mechanical properties decrease, the mixture cannot build a rigid network, the PC segment flexibility increases, the aging resistance is poor, the ultraviolet absorption ability of the phosphonate-zinc ligand is lacking, and the material is more susceptible to photodegradation.

[0069] In Comparative Example 2, the modified flame-retardant functional ligand is replaced by the flame-retardant functional ligand in S2. The toughness is lost, the three-dimensional crosslinking network of (3-mercaptopropyl)trimethoxysilane is lacking, the stress transfer efficiency decreases, the flame retardance weakens, the unmodified ligand has poor dispersibility and is prone to agglomeration, leading to local flame retardance failure, the aging performance decreases, the absence of mercapto-ene click reaction makes the material interface bonding weak and susceptible to environmental erosion.

[0070] In Comparative Example 3, the corrosion inhibition microcapsule is replaced by a wall layer of silica and a core layer of benzotriazole. The repair function fails, the silica shell layer has high brittleness, and breaks prematurely during processing, the benzotriazole is released prematurely, the hardness decreases significantly, the silica has poor compatibility with PC, forming a stress concentration point, and the flame retardant synergistic effect disappears. The lack of reaction path for phosphoric acid groups and calcium ions prevents the formation of a repair calcium complex.

[0071] Although embodiments of the application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the application.

Claims

1. A method for preparing a high-toughness and high-hardness PC material, characterized in that: The steps include: Step 1: Sodium tripolyphosphate is reacted with 2,5-dihydroxyterephthalic acid to produce a phosphate monomer, which is then coordinated with zinc chloride under hydrothermal conditions to obtain a flame retardant functional ligand; Step 2: treating the flame retardant functional ligand with (3-mercaptopropyl)trimethoxysilane to obtain a modified flame retardant functional ligand; Step 3: Sodium alginate and paraffin are combined to form corrosion-inhibiting microcapsules and then grafted with acrylic acid to obtain modified corrosion-inhibiting microcapsules; Step 4: The modified flame retardant functional ligand and the modified corrosion inhibition microcapsule undergo a thiol-ene click reaction and are mixed with polycarbonate to obtain a PC material with high toughness and high hardness.

2. The method for preparing a high-toughness and high-hardness PC material according to claim 1, characterized in that: The specific preparation steps of the phosphate monomer are as follows: Sodium tripolyphosphate, 2,5-dihydroxyterephthalic acid and tetrahydrofuran are added to a reaction kettle, and stirred at 20-25°C and 500-600 r / min for 20-30 minutes. Anhydrous magnesium sulfate as a dehydrating agent and 98% concentrated sulfuric acid are added to the reaction system, and stirring is continued for 24-26 hours. The mixture is filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-4 times respectively, and vacuum dried at 60-70°C for 1-2 hours to obtain a phosphate monomer.

3. The method for preparing a high toughness and high hardness PC material according to claim 2, characterized in that: The dosage ratio of the sodium tripolyphosphate, 2,5-dihydroxyterephthalic acid, tetrahydrofuran, anhydrous magnesium sulfate and concentrated sulfuric acid is 180-190 g: 120-140 g: 2-3 L: 12-13 g: 2-3 mL.

4. The method for preparing a high toughness and high hardness PC material according to claim 1, characterized in that: The specific preparation steps of the flame retardant functional ligand are as follows: Adding a phosphoric acid monomer, N,N-dimethylformamide and a 1 mol / L glacial acetic acid solution into a polytetrafluoroethylene reactor, stirring at 20-25°C and 500-600 r / min for 20-30 minutes, ultrasonically dispersing for 40-60 minutes, then adding zinc chloride, ultrasonically dispersing for 45-60 minutes, keeping the reaction at 125-130°C for 24-26 hours, naturally cooling to room temperature, filtering, washing the filter cake with deionized water and anhydrous ethanol for 2-4 times, respectively, and vacuum drying at 60-70°C for 1-2 hours to obtain a flame retardant functional ligand; The usage ratio of the phosphoric acid monomer, N,N-dimethylformamide, glacial acetic acid solution and zinc chloride is 170-180 g: 3-4 L: 27-30 mL: 40-50 g.

5. The method for preparing a high-toughness and high-hardness PC material according to claim 1, characterized in that: The specific preparation steps of the modified flame retardant functional ligand are as follows: Add (3-mercaptopropyl)trimethoxysilane, flame retardant functional precursor, anhydrous ethanol and deionized water into a reaction kettle, stir at 50-70°C and 500-600 r / min for 2-3 hours, filter, wash the filter cake with deionized water and anhydrous ethanol 2-4 times respectively, and vacuum dry at 60-70°C for 1-2 hours to obtain a modified flame retardant functional ligand; The usage ratio of the (3-mercaptopropyl)trimethoxysilane, the flame retardant functional precursor, anhydrous ethanol and deionized water is 50-60g:160-170g:200-250mL:500-600mL.

6. The method for preparing a high toughness and high hardness PC material according to claim 1, characterized in that: The specific preparation steps of the corrosion-inhibiting microcapsules are as follows: Sodium alginate and deionized water are added to a reactor, stirred at 20-25°C and 1000-1200 r / min for 10-15 minutes, then 80-90 mL of a 40-50% by mass benzotriazole solution is added, and stirring is continued for 30-40 minutes to obtain a mixed solution; the mixed solution is dropped into a 5-7% by mass calcium chloride solution, stirring is continued for 3-4 hours, and filtered. The filter cake is washed with deionized water and anhydrous ethanol for 2-4 times, respectively, and vacuum dried at 60-70°C for 1-2 hours to obtain corrosion-inhibiting microcapsules; The usage ratio of the sodium alginate, deionized water and benzotriazole solution is 120-130 g: 1-2 L: 80-90 mL; the usage ratio of the mixed solution and calcium chloride solution is 200-300 mL: 300-400 mL.

7. The method for preparing a high toughness and high hardness PC material according to claim 1, characterized in that: The specific preparation steps of the modified corrosion inhibition microcapsules are as follows: Add corrosion-inhibiting microcapsules, acrylic acid and deionized water into a reactor, stir at 20-25°C and 500-600 r / min for 20-30 minutes, then add 98% concentrated sulfuric acid, heat to 50-60°C, continue stirring and react for 1-2 hours, filter, wash the filter cake with deionized water and anhydrous ethanol for 2-4 times respectively, and dry under vacuum at 60-70°C for 1-2 hours to obtain modified corrosion-inhibiting microcapsules; The usage ratio of the corrosion-inhibiting microcapsules, acrylic acid, deionized water and concentrated sulfuric acid is 80-90 g: 100-120 mL: 1-2 L: 8-10 mL.

8. The method for preparing a high-toughness and high-hardness PC material according to claim 1, characterized in that: The specific preparation steps of the high toughness and high hardness PC material are as follows: Add the modified flame retardant functional ligand, modified corrosion inhibition microcapsule, 2,2-dihydroxymethyl propionic acid and tetrahydrofuran into the reactor, stir for 20-30 minutes at 20-25℃ and 500-600r / min, then pour the obtained solution onto a polytetrafluoroethylene mold, and heat it at 20-25℃, ultraviolet light 365-370nm and light intensity 50-60mW / cm 2 The obtained product is irradiated under the conditions of 500-600°C and photocured for 25-30 minutes. The mercapto-ene click reaction is induced by ultraviolet light. Then, polycarbonate is added and the product is transferred to a twin-screw extruder. The product is extruded at 200-220°C, cooled, and granulated to obtain a PC material with high toughness and hardness.

9. The method for preparing a high-toughness and high-hardness PC material according to claim 8, characterized in that: The usage ratio of the modified flame retardant functional ligand, the modified corrosion inhibition microcapsule, 2,2-dihydroxymethylpropionic acid, tetrahydrofuran and polycarbonate is 130-140g: 50-60g: 12-15g: 4-5L: 4-5kg.

10. A high toughness and high hardness PC material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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