Hydrolysis-resistant weather-resistant flame-retardant PC alloy material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a hydrolysis-resistant weather-resistant flame-retardant PC alloy material and a preparation method thereof. The PC alloy material is prepared from the following components in parts by weight: 55 to 80 parts of PC resin, 5 to 15 parts of ABS (Acrylonitrile Butadiene Styrene) resin, 5 to 18 parts of a flame retardant, 0.2 to 1.5 parts of a flame-retardant synergist, 2 to 8 parts of a flexibilizer, 0.5 to 2 parts of a hydrolysis-resistant stabilizer, 0.1 to 1 part of an anti-dripping agent, 0.5 to 1.5 parts of a weather-resistant agent and 0.5 to 2 parts of other processing aids, the hydrolysis-resistant stabilizer is modified butadiene styrene rubber nanoparticles. According to the PC alloy material disclosed by the invention, the organic silicon flame retardant and the phosphate flame retardant with relatively good heat resistance, hydrolysis resistance and stability are compounded, and the modified butadiene styrene rubber nanoparticles are supplemented, so that the PC alloy material has excellent mechanical property, flame retardance and processing fluidity, and has good hydrolysis resistance and weather resistance; the cable can be widely used in the communication industry, the electronic appliance industry, the household appliance industry and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material and a preparation method thereof. Background Art

[0002] Halogen-free flame-retardant PC / ABS alloy materials are widely used in industries such as office equipment, electronic appliances, household appliances and communications due to their high gloss, excellent mechanical properties, flame retardancy and processing properties. However, in order to meet the continuously updated technical requirements of the market, especially for products used outdoors or under certain specific conditions, the products also need to have certain weather resistance and hydrolysis resistance functions to ensure that their performance can still meet the use requirements within a certain period of time when affected by light, heat and water.

[0003] However, adding ABS resin, phosphate flame retardant and toughening agent to polycarbonate will more or less affect the weather resistance of the alloy system. Therefore, it is necessary to carry out weather resistance modification on ordinary flame-retardant PC / ABS alloys.

[0004] Patent technical literature CN113999511A discloses a flame-retardant polycarbonate alloy composition resistant to damp heat. The flame-retardant polycarbonate alloy composition includes polycarbonate, ABS, flame retardant, toughening agent, maleic anhydride-modified polyolefin and anti-dripping agent. The obtained flame-retardant polycarbonate alloy composition has a high flame retardancy level, good mechanical properties and damp heat erosion resistance, and still has good aging stability under damp heat conditions. Although it solves the weather resistance of the flame-retardant alloy to a certain extent, there is basically no research on its hydrolysis resistance. Although the components in the alloy such as ABS resin, toughening agent and flame retardant synergist are helpful for alleviating the hydrolysis effect, due to the poor hydrolysis resistance of polycarbonate itself and the worse hydrolysis resistance after adding phosphate flame retardants, it is necessary to further strengthen the hydrolysis resistance of the flame-retardant PC / ABS alloy.

[0005] Therefore, developing a flame-retardant PC / ABS alloy with weather resistance and hydrolysis resistance has great research significance and application value. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material and a preparation method thereof, so as to provide a PC alloy material with characteristics such as high impact resistance, hydrolysis resistance, good weather resistance, good flame retardancy and easy processing.

[0007] For the above purposes, the present invention provides a hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material, which comprises the following components by weight: 55-80 parts of PC resin, 5-15 parts of ABS resin, 5-18 parts of flame retardant, 0.2-1.5 parts of flame retardant synergist, 2-8 parts of toughening agent, 0.5-2 parts of hydrolysis-resistant stabilizer, 0.1-1 part of anti-dripping agent, 0.5-1.5 parts of weathering agent and 0.5-2 parts of other processing aids; The preparation steps of the hydrolysis-resistant stabilizer are as follows: S1: Disperse boron nitride nanosheets in a mixed solution, ultrasonically treat for 1 h, then add hydrochloric acid solution, reflux at 80 °C for 5-6 h, centrifuge and wash until neutral, and vacuum dry at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; In step S1, the dosage ratio of the boron nitride nanosheets, the mixed solution and the hydrochloric acid solution is 5-6 g: 150 mL: 5 mL; In step S1, the particle size of the boron nitride nanosheets is 100-200 nm; S2: Mix cetyltrimethoxysilane with ethanol, dropwise add deionized water, stir at 40 °C for 30 min, then add hydroxylated boron nitride nanosheets, and react at 80 °C for 10-12 h under a nitrogen atmosphere; after the reaction is completed, centrifuge the product, wash it 3 times with ethanol, and vacuum dry at 60 °C for 24 h to obtain vinylated boron nitride nanosheets; In step S2, the dosage ratio of the cetyltrimethoxysilane, ethanol, deionized water and hydroxylated boron nitride nanosheets is 8-10 mL: 50-60 mL: 5-10 mL: 4-5 g; S3: Under a nitrogen atmosphere, stir styrene-butadiene latex, deionized water, OP-10, sodium dodecylbenzenesulfonate, and KPS at 70 °C for 30 min, then dropwise add glycidyl methacrylate and styrene at a rate of 10 mL / h and react at 80 °C for 2-3 h, then dropwise add 6-phenyl-1-hexene and vinylated boron nitride nanosheets at a rate of 5 mL / h and react at 80 °C for 1 h. Finally, add CaCl2 solution to demulsify, filter and wash 3 times with hot distilled water, and then freeze-dry for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are the hydrolysis-resistant stabilizer; In step S3, the dosage ratio of the styrene-butadiene latex, deionized water, OP-10, sodium dodecylbenzenesulfonate, KPS, glycidyl methacrylate, styrene, 6-phenyl-1-hexene and vinylated boron nitride nanosheets is 100-110 g: 150-200 g: 0.5-0.7 g: 0.3-0.4 g: 0.4-0.5 g: 14.5-15.5 g: 15-16 g: 2-3 g: 0.5-1 g; Preferably, the mixed solution in step S1 is a mixture of ethanol and deionized water in a volume ratio of 3:1; Preferably, the concentration of the hydrochloric acid solution in step S1 is 0.1 mol / L; Preferably, the solid content of the styrene-butadiene latex in step S3 is 34%, with a butadiene content of 75 wt% and a particle size of 120 nm; Preferably, the density of the PC resin is 1.18 - 1.21 g / cm 3 , and the melt flow rate (at 300 °C, 1.2 kg) is 2 - 30 g / 10 min; Preferably, the ABS resin is a styrene-butadiene-acrylonitrile terpolymer with a rubber content of 5% - 25%; Preferably, the flame retardant is tetra(2,6-dimethylphenyl) 1,3-phenylene phosphonate.

[0008] Preferably, the flame retardant synergist is a silicone flame retardant.

[0009] Preferably, the toughening agent is a silicone-containing acrylate rubber.

[0010] Preferably, the anti-dripping agent is polytetrafluoroethylene powder coated and modified with a styrene-acrylonitrile AS copolymer.

[0011] Preferably, the weathering agent is a mixture of one or two of benzotriazole ultraviolet absorbers and hindered amine light stabilizers.

[0012] Preferably, the processing aid is a compound of an antioxidant and a lubricant; Preferably, the antioxidant is one of hindered phenol antioxidants or phosphite antioxidants; More preferably, the antioxidant is a mixture of antioxidant 168 and 1076.

[0013] Preferably, the lubricant is one of stearate esters, metal soaps, and amides; More preferably, the lubricant is one of stearate esters (PETs), metal soaps (Cast, Znst), or amides (erucamide).

[0014] Furthermore, the present invention also provides a preparation method of a hydrolysis-resistant and weather-resistant flame-retardant PC alloy material, and the specific steps are as follows: Fully mix PC resin, ABS resin, flame retardant, flame retardant synergist, toughening agent, hydrolysis-resistant stabilizer, anti-dripping agent, weathering agent, and processing aid in a high-speed mixer for 2 - 30 min to obtain a mixture; then knead the mixture to obtain a hydrolysis-resistant and weather-resistant flame-retardant PC alloy material.

[0015] Preferably, the ratio of the length to the diameter of the twin-screw extruder is 40:1, the screw rotation speed is 300 - 500 rpm, and the temperature settings for each zone of the barrel are as follows: the temperature of zone 1 is 30 - 80 °C, the temperature of zone 2 is 230 - 270 °C, the temperature of zone 3 is 230 - 270 °C, the temperature of zone 4 is 230 - 270 °C, the temperature of zone 5 is 230 - 270 °C, the temperature of zone 6 is 230 - 270 °C, the temperature of zone 7 is 230 - 270 °C, the temperature of zone 8 is 230 - 270 °C, the temperature of zone 9 is 230 - 270 °C, the temperature of zone 10 is 230 - 270 °C, and the temperature of the die head is 250 ± 10 °C.

[0016] Advantages of the present invention: For the PC alloy material of the present invention, an organosilicon flame retardant, a phosphate ester flame retardant with good heat and hydrolysis resistance stability, and a hydrolysis resistance stabilizer are compounded, which can improve the hydrolysis resistance of the flame-retardant PC material system.

[0017] For the PC alloy material of the present invention, modified styrene-butadiene rubber nanoparticles are used as the hydrolysis resistance stabilizer, thereby protecting the macromolecular chains of PC and enabling it to be effectively protected from damage by water and heat, further enhancing the hydrolysis resistance of the flame-retardant PC alloy system.

[0018] For the PC alloy material of the present invention, 6-phenyl-1-hexene and vinylated boron nitride nanosheets are simultaneously added during the preparation of the modified styrene-butadiene rubber nanoparticles. The two can cooperate with each other to form a denser and more stable barrier, which can further enhance the shielding effect on water molecules and ultraviolet rays, improving the flame retardancy, hydrolysis resistance, and anti-aging ability of the PC alloy material. Specific embodiments

[0019] To make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to specific embodiments.

[0020] The sources or properties of the raw materials used in the examples and comparative examples of the present invention are as follows: PC resin: PC 1609T-11, melt index 10 (300 °C * 1.2 kg), Luxi Chemical; ABS resin: ABS 8391, Shanghai Gaojiao; Flame retardant: PX-200, Daihachi, Japan; Flame retardant synergist: organosilicon flame retardant; Toughening agent: Metablen S-2030, Mitsubishi Rayon; Anti-dripping agent: Guangdong Entropy Energy; Weathering agent: a mixture of benzotriazole ultraviolet absorber (UV-326) and hindered amine light stabilizer (HALS-770); Processing aid: a mixture of antioxidant 168 and 1076; Lubricant is Lonza PETs; The aspect ratio of the twin-screw extruder is 40:1, the screw speed is 300 - 500 rpm, and the temperature settings for each zone of the barrel are as follows: the temperature of zone 1 is 30 - 80 °C, the temperature of zone 2 is 230 - 270 °C, the temperature of zone 3 is 230 - 270 °C, the temperature of zone 4 is 230 - 270 °C, the temperature of zone 5 is 230 - 270 °C, the temperature of zone 6 is 230 - 270 °C, the temperature of zone 7 is 230 - 270 °C, the temperature of zone 8 is 230 - 270 °C, the temperature of zone 9 is 230 - 270 °C, the temperature of zone 10 is 230 - 270 °C, and the temperature of the die head is 250 °C.

[0021] Example 1: A hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material, and the specific preparation steps are as follows: (1) Disperse 5 g of boron nitride nanosheets in 150 mL of a mixed solution (ethanol:water = 3:1), ultrasonically treat for 1 h, then add 5 mL of 0.1 mol / L hydrochloric acid solution, reflux at 80 °C for 5 h, centrifuge and wash until neutral, and vacuum dry at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; (2) Mix 8 mL of cetyltrimethoxysilane with 50 mL of ethanol, dropwise add 5 mL of deionized water, stir at 40 °C for 30 min, then add 4 g of hydroxylated boron nitride nanosheets, and react at 80 °C for 10 h under a nitrogen atmosphere; after the reaction is completed, centrifuge the product, wash it 3 times with ethanol, and vacuum dry at 60 °C for 24 h to obtain vinylated boron nitride nanosheets; (3) Under a nitrogen atmosphere, add 100 g of styrene-butadiene latex, 150 g of deionized water, 0.5 g of OP-10, 0.3 g of sodium dodecylbenzenesulfonate, and 0.4 g of KPS, stir at 70 °C for 30 min, then dropwise add 14.5 g of glycidyl methacrylate and 15 g of styrene at a rate of 10 mL / h, react at 80 °C for 2 h, then dropwise add 2 g of 6-phenyl-1-hexene and 0.5 g of vinylated boron nitride nanosheets at a rate of 5 mL / h and react at 80 °C for 1 h. Finally, add a CaCl2 solution to demulsify, filter and wash 3 times with hot distilled water, and then freeze-dry for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are hydrolysis-resistant stabilizers; (4) Mix 50 g of PC resin, 15 g of ABS resin, 18 g of flame retardant, 1.5 g of flame retardant synergist, 8 g of toughening agent, 2 g of hydrolysis-resistant stabilizer, 1.5 g of weather-resistant agent, 0.1 g of anti-dripping agent, and 2 g of processing aid in a high-speed mixer and mix well for 30 min to obtain a mixture; (5) Convey the obtained mixture to a twin-screw extruder through a feeding device. After the mixture is fully melted and kneaded, it is extruded from the die holes of the die head. The extruded strip is cooled in a water bath and then pelletized to obtain the hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material.

[0022] Example 2: A hydrolytically resistant, weather-resistant and flame-retardant PC alloy material, and the specific preparation steps are as follows: (1) Disperse 5.5 g of boron nitride nanosheets in 150 mL of a mixed solution (ethanol: water = 3:1), ultrasonically treat for 1 h, then add 5 mL of 0.1 mol / L hydrochloric acid solution, reflux at 80 °C for 6 h, centrifuge and wash until neutral, and vacuum dry at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; (2) Mix 9 mL of cetyltrimethoxysilane with 55 mL of ethanol, add 8 mL of deionized water dropwise, stir at 40 °C for 30 min, then add 4.5 g of hydroxylated boron nitride nanosheets, and react at 80 °C for 11 h under a nitrogen atmosphere; after the reaction is completed, centrifuge the product, wash it 3 times with ethanol, and vacuum dry at 60 °C for 24 h to obtain vinylated boron nitride nanosheets; (3) Under a nitrogen atmosphere, add 105 g of styrene-butadiene latex, 160 g of deionized water, 0.6 g of OP-10, 0.35 g of sodium dodecylbenzenesulfonate, and 0.5 g of KPS, stir at 70 °C for 30 min, then dropwise add 15 g of glycidyl methacrylate and 15.5 g of styrene at a rate of 10 mL / h, react at 80 °C for 3 h, then dropwise add 2.5 g of 6-phenyl-1-hexene and 0.8 g of vinylated boron nitride nanosheets at a rate of 5 mL / h and react at 80 °C for 1 h. Finally, add a CaCl2 solution to demulsify, filter and wash 3 times with hot distilled water, and then freeze-dry for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are hydrolytically resistant stabilizers; (4) Mix 69.4 g of PC resin, 10 g of ABS resin, 13 g of flame retardant, 0.5 g of flame retardant synergist, 3.5 g of toughening agent, 1.5 g of hydrolytically resistant stabilizer, 1 g of weathering agent, 0.6 g of anti-dripping agent, and 1 g of processing aid in a high-speed mixer and mix well for 30 min to obtain a mixture; (5) Convey the obtained mixture to a twin-screw extruder through a feeding device, extrude the mixture from the die holes of the die after sufficient melting and kneading, and pelletize the extruded strip after cooling in a water bath to obtain the hydrolytically resistant, weather-resistant and flame-retardant PC alloy material.

[0023] Example 3: A hydrolytically resistant, weather-resistant and flame-retardant PC alloy material, and the specific preparation steps are as follows: (1) Disperse 6 g of boron nitride nanosheets in 150 mL of a mixed solution (ethanol: water = 3:1), ultrasonically treat for 1 h, then add 5 mL of 0.1 mol / L hydrochloric acid solution, reflux at 80 °C for 6 h, centrifuge and wash until neutral, and vacuum dry at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; (2) Mix 10 mL of cetyltrimethoxysilane with 60 mL of ethanol, add 10 mL of deionized water dropwise, stir at 40 °C for 30 min, then add 5 g of hydroxylated boron nitride nanosheets, and react at 80 °C for 12 h under a nitrogen atmosphere. After the reaction is completed, centrifuge the product, wash it three times with ethanol, and dry it in vacuum at 60 °C for 24 h to obtain vinylated boron nitride nanosheets; (3) Under a nitrogen atmosphere, add 110 g of styrene-butadiene latex, 200 g of deionized water, 0.7 g of OP-10, 0.4 g of sodium dodecylbenzenesulfonate, and 0.5 g of KPS, stir at 70 °C for 30 min, then add 15.5 g of glycidyl methacrylate and 16 g of styrene dropwise at a rate of 10 mL / h, react at 80 °C for 3 h, then add 3 g of 6-phenyl-1-hexene and 1 g of vinylated boron nitride nanosheets dropwise at a rate of 5 mL / h and react at 80 °C for 1 h. Finally, add a CaCl2 solution to demulsify, filter and wash three times with hot distilled water, and then freeze-dry for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are hydrolysis-resistant stabilizers; (4) Mix 80 g of PC resin, 5 g of ABS resin, 5 g of flame retardant, 0.2 g of flame retardant synergist, 2 g of toughening agent, 0.5 g of hydrolysis-resistant stabilizer, 0.5 g of weather-resistant agent, 1 g of anti-dripping agent, and 0.5 g of processing aid in a high-speed mixer and mix well for 30 min to obtain a mixture; (5) Convey the obtained mixture to a twin-screw extruder through a feeding device. After the mixture is fully melted and kneaded, it is extruded from the die orifice of the die head. The extruded strip is cooled in a water bath and then pelletized to obtain the hydrolysis-resistant, weather-resistant, and flame-retardant PC alloy material.

[0024] Comparative Example 1: A PC alloy material, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, add 105 g of styrene-butadiene latex, 160 g of deionized water, 0.6 g of OP-10, 0.35 g of sodium dodecylbenzenesulfonate, and 0.5 g of KPS, stir at 70 °C for 30 min, then add 15 g of glycidyl methacrylate and 15.5 g of styrene dropwise at a rate of 10 mL / h, react at 80 °C for 3 h, then add 2.5 g of 6-phenyl-1-hexene dropwise at a rate of 5 mL / h and react at 80 °C for 1 h. Finally, add a CaCl2 solution to demulsify, filter and wash three times with hot distilled water, and then freeze-dry for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are hydrolysis-resistant stabilizers; (2) Mix 69.4 g of PC resin, 10 g of ABS resin, 13 g of flame retardant, 0.5 g of flame retardant synergist, 3.5 g of toughening agent, 1.5 g of hydrolysis-resistant stabilizer, 1 g of weather-resistant agent, 0.6 g of anti-dripping agent, and 1 g of processing aid in a high-speed mixer and mix well for 30 min to obtain a mixture; (3) The obtained mixture is conveyed into a twin-screw extruder through a feeding device. After the mixture is fully melted and kneaded, it is extruded from the die orifice of the die head. The extruded strip is cooled in a water tank and then pelletized to obtain the hydrolytic-resistant, weather-resistant and flame-retardant PC alloy material.

[0025] Comparative Example 2: A PC alloy material, and the specific preparation steps are as follows: (1) 5.5 g of boron nitride nanosheets are dispersed in 150 mL of a mixed solution (ethanol: water = 3:1), ultrasonicated for 1 h, then 5 mL of 0.1 mol / L hydrochloric acid solution is added, refluxed at 80 °C for 6 h, centrifuged and washed until neutral, and vacuum dried at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; (2) 9 mL of cetyltrimethoxysilane is mixed with 55 mL of ethanol, 8 mL of deionized water is added dropwise, stirred at 40 °C for 30 min, then 4.5 g of hydroxylated boron nitride nanosheets are added, and reacted at 80 °C for 11 h under a nitrogen atmosphere; after the reaction is completed, the product is centrifuged, washed 3 times with ethanol, and vacuum dried at 60 °C for 24 h to obtain vinylated boron nitride nanosheets; (3) Under a nitrogen atmosphere, 105 g of styrene-butadiene latex, 160 g of deionized water, 0.6 g of OP-10, 0.35 g of sodium dodecylbenzenesulfonate, 0.5 g of KPS are stirred at 70 °C for 30 min, then 15 g of glycidyl methacrylate and 15.5 g of styrene are added dropwise at a rate of 10 mL / h, reacted at 80 °C for 3 h, then 0.8 g of vinylated boron nitride nanosheets are added and reacted at 80 °C for 1 h, and finally a CaCl2 solution is added to demulsify, filtered and washed 3 times with hot distilled water, and freeze-dried for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which are hydrolytic-resistant stabilizers; (4) 69.4 g of PC resin, 10 g of ABS resin, 13 g of flame retardant, 0.5 g of flame retardant synergist, 3.5 g of toughening agent, 1.5 g of hydrolytic-resistant stabilizer, 1 g of weathering agent, 0.6 g of anti-dripping agent and 1 g of processing aid are mixed and fully mixed in a high-speed mixer for 30 min to obtain a mixture; (5) The obtained mixture is conveyed into a twin-screw extruder through a feeding device. After the mixture is fully melted and kneaded, it is extruded from the die orifice of the die head. The extruded strip is cooled in a water tank and then pelletized to obtain the hydrolytic-resistant, weather-resistant and flame-retardant PC alloy material.

[0026] Comparative Example 3: A PC alloy material, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, 105 g of styrene-butadiene latex, 160 g of deionized water, 0.6 g of OP-10, 0.35 g of sodium dodecylbenzenesulfonate, and 0.5 g of KPS were stirred at 70 °C for 30 min. Subsequently, 15 g of glycidyl methacrylate and 15.5 g of styrene were added dropwise at a rate of 10 mL / h, and the reaction was carried out at 80 °C for 3 h. Finally, a CaCl2 solution was added for demulsification, and after filtering and washing three times with hot distilled water, it was freeze-dried for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which were the hydrolysis-resistant stabilizer; (2) 69.4 g of PC resin, 10 g of ABS resin, 13 g of flame retardant, 0.5 g of flame retardant synergist, 3.5 g of toughening agent, 1.5 g of hydrolysis-resistant stabilizer, 1 g of weathering agent, 0.6 g of anti-dripping agent, and 1 g of processing aid were mixed and thoroughly mixed in a high-speed mixer for 30 min to obtain a mixture; (3) The obtained mixture was transported to a twin-screw extruder through a feeding device. After the mixture was fully melted and kneaded, it was extruded from the die holes of the die head. The extruded strip was cooled in a water bath and then pelletized to obtain the hydrolysis-resistant, weathering-resistant, and flame-retardant PC alloy material.

[0027] Comparative Example 4: A PC alloy material, which is different from Example 2 in that cetyltrimethoxysilane is replaced by 5-hexenyltrimethoxysilane. The specific preparation steps are as follows: (1) 5.5 g of boron nitride nanosheets were dispersed in 150 mL of a mixed solution (ethanol:water = 3:1), ultrasonicated for 1 h, then 5 mL of 0.1 mol / L hydrochloric acid solution was added, and the mixture was refluxed at 80 °C for 6 h, centrifuged and washed until neutral, and vacuum-dried at 80 °C for 12 h to obtain hydroxylated boron nitride nanosheets; (2) 9 mL of 5-hexenyltrimethoxysilane was mixed with 55 mL of ethanol, 8 mL of deionized water was added dropwise, and the mixture was stirred at 40 °C for 30 min. Subsequently, 4.5 g of hydroxylated boron nitride nanosheets were added, and the reaction was carried out at 80 °C for 11 h under a nitrogen atmosphere; after the reaction was completed, the product was centrifuged, washed three times with ethanol, and vacuum-dried at 60 °C for 24 h to obtain alkenylated boron nitride nanosheets; (3) Under a nitrogen atmosphere, 105 g of styrene-butadiene latex, 160 g of deionized water, 0.6 g of OP-10, 0.35 g of sodium dodecylbenzenesulfonate, and 0.5 g of KPS were stirred at 70 °C for 30 min. Subsequently, 15 g of glycidyl methacrylate and 15.5 g of styrene were added dropwise at a rate of 10 mL / h, and the reaction was carried out at 80 °C for 3 h. Then, 2.5 g of 6-phenyl-1-hexene and 0.8 g of alkenylated boron nitride nanosheets were added dropwise at a rate of 5 mL / h and reacted at 80 °C for 1 h. Finally, a CaCl2 solution was added for demulsification, and after filtering and washing three times with hot distilled water, it was freeze-dried for 48 h for standby to obtain modified styrene-butadiene rubber nanoparticles, which were the hydrolysis-resistant stabilizer; (4) Mix 69.4 g of PC resin, 10 g of ABS resin, 13 g of flame retardant, 0.5 g of flame retardant synergist, 3.5 g of toughening agent, 1.5 g of hydrolysis-resistant stabilizer, 1 g of weather-resistant agent, 0.6 g of anti-dripping agent and 1 g of processing aid in a high-speed mixer and mix well for 30 min to obtain a mixture; (5) Convey the obtained mixture to a twin-screw extruder through a feeding device. After the mixture is fully melted and kneaded, it is extruded from the die orifice of the die head. The extruded strip is cooled in a water tank and pelletized to obtain the hydrolysis-resistant and weather-resistant flame-retardant PC alloy material.

[0028] Performance Test Specimen injection molding: Dry the materials obtained in the examples and comparative examples in a blast drying oven at 80 - 90 °C for 3 - 4 h, and then inject and mold the dried particle materials on an injection molding machine to prepare specimens; Flame retardancy: Test according to the UL-94 standard, and the thickness of the specimen is 1.5 mm; Impact strength: Inspect according to the ASTM D256 standard. The specimen type is type I, and the specimen size (mm) is (63 ± 2) × (12.45 ± 0.2) × (3.1 ± 0.2); the notch type is type A; Hydrolysis resistance: Boil in water (70 °C / 168 h) according to the UL 746C standard, then take out the specimen and test its impact strength; Xenon lamp aging test method: Test for 1000 h according to the UL 746C standard, then take out the specimen and test its impact strength. The test results are shown in Table 1: Table 1 Performance Test Results UL-94 UL-94 (Boiling Water) UL-94 (Xenon Lamp Aging) Impact Strength (J / m) Impact Strength (J / m) after Boiling Water Impact Strength (J / m) after Xenon Lamp Aging Example 1 V-0 V-0 V-0 591 401 512 Example 2 V-0 V-0 V-0 612 402 522 Example 3 V-0 V-0 V-0 590 395 520 Comparative Example 1 V-0 V-1 V-1 572 312 437 Comparative Example 2 V-0 V-1 V-1 588 360 481 Comparative Example 3 V-0 V-2 V-1 540 256 390 Comparative Example 4 V-0 V-0 V-0 605 380 510 Data analysis: It can be seen from the data of the examples in Table 1 that for the PC alloy material of the present invention, after adding appropriate amounts of flame retardant, weather-resistant agent and hydrolysis-resistant stabilizer, it is found that the flame retardancy, hydrolysis resistance and weather resistance of the PC alloy material are significantly improved, and it can still maintain a relatively excellent level after boiling in water and xenon lamp aging.

[0029] It can be seen from Example 2 and Comparative Example 1 in Table 1 that adding vinylated boron nitride nanosheets in the process of preparing modified styrene-butadiene rubber nanoparticles further improves the flame retardancy, hydrolysis resistance and anti-aging ability of the PC alloy material. This is mainly because boron nitride nanosheets, as a physical barrier, have a certain barrier effect. Its layered structure can hinder the penetration of water molecules. At the same time, boron nitride nanosheets themselves have a certain ability to absorb ultraviolet light, which can ensure that the carbonate bond is protected from photo-oxidative cleavage, and can form a dense ceramic layer during combustion to isolate the transfer of oxygen and heat.

[0030] It can be seen from Example 2 and Comparative Example 2 in Table 1 that adding 6-phenyl-1-hexene during the preparation of modified styrene-butadiene rubber nanoparticles improves the flame retardancy, hydrolysis resistance and anti-aging ability of the PC alloy material to a certain extent. This is mainly because the long-chain aromatic hydrocarbon (hydrophobic benzene group) of 6-phenyl-1-hexene can not only shield the water molecule diffusion path, but also enhance the carbon layer continuity, and can stabilize free radicals through the conjugation effect, delaying the oxidation chain reaction, thus improving its anti-aging ability.

[0031] It can be seen from Example 2 and Comparative Examples 1, 2, and 3 in Table 1 that adding 6-phenyl-1-hexene and vinylated boron nitride nanosheets simultaneously during the preparation of modified styrene-butadiene rubber nanoparticles improves the flame retardancy, hydrolysis resistance and anti-aging ability of the PC alloy material slightly. This shows that 6-phenyl-1-hexene and vinylated boron nitride nanosheets have a certain synergistic effect, can form a denser and more stable barrier, and can further enhance the shielding effect on water molecules and ultraviolet rays.

[0032] It can be known from Example 2 and Comparative Example 4 in Table 1 that by controlling the grafting lengths of 6-phenyl-1-hexene and vinylated boron nitride nanosheets during the preparation of modified styrene-butadiene rubber nanoparticles, the anti-aging and hydrolysis resistance of the PC alloy material can be further improved. This may be because 6-phenyl-1-hexene and vinylated boron nitride nanosheets can form an inner and outer double-layer structure on the surface of styrene-butadiene particles.

[0033] Those of ordinary skill in the art should understand that the discussion of any above embodiment is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material, characterized in that, Calculated by weight parts, it includes the following components: 55 - 80 parts of PC resin, 5 - 15 parts of ABS resin, 5 - 18 parts of flame retardant, 0.2 - 1.5 parts of flame retardant synergist, 2 - 8 parts of toughening agent, 0.5 - 2 parts of hydrolysis-resistant stabilizer, 0.1 - 1 part of anti-dripping agent, 0.5 - 1.5 parts of weathering agent and 0.5 - 2 parts of other processing aids; The preparation steps of the hydrolysis-resistant stabilizer are as follows: S1: Disperse boron nitride nanosheets in a mixed solution, perform ultrasonic treatment, then add hydrochloric acid solution, reflux at 80 °C, and purify to obtain hydroxylated boron nitride nanosheets; In step S1, the dosage ratio of the boron nitride nanosheets, mixed solution, and hydrochloric acid solution is 5 - 6 g: 150 mL: 5 mL; S2: Mix cetyltrimethoxysilane with ethanol and deionized water, then add hydroxylated boron nitride nanosheets, react at 80 °C for 10 - 12 h in a nitrogen atmosphere, and purify to obtain vinylated boron nitride nanosheets; In step S2, the dosage ratio of cetyltrimethoxysilane, ethanol, deionized water, and hydroxylated boron nitride nanosheets is 8 - 10 mL: 50 - 60 mL: 5 - 10 mL: 4 - 5 g; S3: Under a nitrogen atmosphere, mix styrene-butadiene rubber latex, deionized water, OP-10, sodium dodecylbenzenesulfonate, and KPS, stir at 70 °C, then add glycidyl methacrylate and styrene, react at 80 °C for 2 - 3 h, then add 6-phenyl-1-hexene and vinylated boron nitride nanosheets, react at 80 °C for 1 h, and finally add CaCl2 solution to demulsify and purify to obtain modified styrene-butadiene rubber nanoparticles, which are the hydrolysis-resistant stabilizer; In step S3, the dosage ratio of styrene-butadiene rubber latex, deionized water, OP-10, sodium dodecylbenzenesulfonate, KPS, glycidyl methacrylate, styrene, 6-phenyl-1-hexene, and vinylated boron nitride nanosheets is 100 - 110 g: 150 - 200 g: 0.5 - 0.7 g: 0.3 - 0.4 g: 0.4 - 0.5 g: 14.5 - 15.5 g: 15 - 16 g: 2 - 3 g: 0.5 - 1 g.

2. The hydrolytic resistance, weather resistance and flame retardant PC alloy material according to claim 1, wherein In step S1, the particle size of the boron nitride nanosheets is 100 - 200 nm; the mixed solution is composed of ethanol and deionized water mixed according to a volume ratio of 3:1; the concentration of the hydrochloric acid solution is 0.1 mol / L.

3. The hydrolytic resistance, weather resistance and flame retardant PC alloy material according to claim 1, characterized in that, In step S3, the solid content of the styrene-butadiene rubber latex is 34%, the butadiene content is 75 wt%, and the particle size is 120 nm.

4. The hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material according to claim 1, characterized in that, The density of the PC resin is 1.18 - 1.21 g / cm 3 , and the melt flow rate (at 300 °C, 1.2 kg) is 2 - 30 g / 10 min.

5. The hydrolytic resistance, weather resistance and flame retardant PC alloy material according to claim 1, characterized in that, The ABS resin is a styrene-butadiene-acrylonitrile terpolymer, and the rubber content is 5% - 25%.

6. The hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material according to claim 1, wherein, The flame retardant is tetra(2,6-dimethylphenyl) 1,3-phenylene phosphate, and the flame retardant synergist is an organosilicon flame retardant.

7. The hydrolytic resistance, weather resistance and flame retardant PC alloy material according to claim 1, characterized in that, The toughening agent is a silicone-containing acrylate rubber; the anti-dripping agent is a polytetrafluoroethylene powder coated and modified with a styrene-acrylonitrile AS copolymer; the weathering agent is a mixture of one or two of benzotriazole ultraviolet absorbers and hindered amine light stabilizers.

8. The hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material according to claim 1, characterized in that, The processing aids are a compound of an antioxidant and a lubricant.

9. A preparation method of a hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material according to any one of claims 1-8, characterized in that, The specific steps are as follows: PC resin, ABS resin, flame retardant, flame retardant synergist, toughening agent, hydrolysis-resistant stabilizer, anti-dripping agent, weathering agent and processing aid are fully mixed in a high-speed mixer for 2 - 30 minutes to obtain a mixture; subsequently, the mixture is kneaded to obtain a hydrolysis-resistant, weathering-resistant and flame-retardant PC alloy material.

10. The preparation method of the hydrolysis-resistant, weather-resistant and flame-retardant PC alloy material according to claim 9, characterized in that, The aspect ratio of the twin-screw extruder is 40:1, the screw speed is 300 - 500 rpm, and the temperatures of each zone of the barrel are set as follows: the temperature of the first zone is 30 - 80 °C, the temperature of the second zone is 230 - 270 °C, the temperature of the third zone is 230 - 270 °C, the temperature of the fourth zone is 230 - 270 °C, the temperature of the fifth zone is 230 - 270 °C, the temperature of the sixth zone is 230 - 270 °C, the temperature of the seventh zone is 230 - 270 °C, the temperature of the eighth zone is 230 - 270 °C, the temperature of the ninth zone is 230 - 270 °C, the temperature of the tenth zone is 230 - 270 °C, and the die temperature is 250 ± 10 °C.