PES composite material for flame-retardant net film and preparation method of PES composite material

Abstract

The invention discloses a PES composite material for a flame-retardant net film, and relates to the technical field of high polymer materials. The invention discloses a PES composite material for a flame-retardant net film. The flame-retardant and flame-retardant PES material is prepared from the following raw materials in parts by weight: 35 to 55 parts of PES resin, 6 to 12 parts of modified boron nitride nanosheets, 10 to 18 parts of a novel phosphorus-nitrogen-boron flame retardant, 4 to 9 parts of an ethylene-vinyl acetate copolymer, 2 to 6 parts of carbon nanotubes, 1 to 3 parts of a light stabilizer Tinuvin770, 3 to 7 parts of polydimethylsiloxane, 0.8 to 2.5 parts of a nucleating agent NA-11, 1.2 to 3.5 parts of a dispersing agent BYK-110, 3 to 6 parts of maleic anhydride grafted polypropylene and 1 to 4 parts of silver-loaded zinc oxide. And 12-25 parts of deionized water. The PES composite material for the flame-retardant net film has remarkable advantages. The softening point reaches 115 DEG C, and the high-temperature-resistant rubber can be stably used in a high-temperature environment. The tensile strength and the tearing strength are high, large external force can be borne, and damage is not prone to occurring. The air permeability is proper, and the requirements of different scenes can be met. In addition, the antibacterial performance is excellent, the chemical corrosion resistance is high, the self-cleaning performance is achieved, the comprehensive performance is excellent, and the application prospect is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a PES composite material for flame-retardant mesh film and a preparation method thereof. BACKGROUND

[0002] In the field of high polymer materials, the performance of materials for flame-retardant mesh film plays a decisive role in many application scenarios, especially with the continuous improvement of fire safety standards, its importance is increasingly prominent. Traditional flame-retardant mesh film materials generally have performance defects, which are difficult to meet the diversified needs of actual applications. In terms of PES composite materials, these problems are particularly prominent.

[0003] The softening point of existing PES composite materials is low, which makes its stability in high temperature environment poor and is prone to deformation. For example, in the scenarios of electronic device heat dissipation components, high-temperature industrial waste gas filtration, etc., once the material is deformed by heat, not only will it affect the normal operation of the equipment, but also may cause safety hazards, leading to its inability to be widely used in fields with high requirements for heat resistance.

[0004] In terms of mechanical properties, the tensile strength and tear strength of existing materials are not satisfactory. When subjected to a large external force, the material is prone to damage, which not only shortens the service life of the product, but also threatens the safety of the product.

[0005] Precise control of air permeability has always been a technical problem in this field. Different application scenarios, such as air filtration, liquid filtration, ventilation systems, etc., have different requirements for the air permeability of materials. However, existing PES composite materials for flame-retardant mesh film are difficult to meet these diverse needs, and are difficult to achieve ideal results in terms of filtration accuracy, ventilation efficiency, etc., limiting their application expansion in related fields.

[0006] The lack of antibacterial performance is also a major pain point of existing PES composite materials. In fields such as medical health, food packaging, etc. that have very high requirements on sanitary conditions, the limited antibacterial ability of the material cannot effectively inhibit the growth of bacteria, which is easy to cause sanitary problems and poses a potential threat to people's health.

[0007] The chemical corrosion resistance of the material is also not optimistic. When in contact with chemicals such as acids and bases, the performance of existing PES composite materials will rapidly decline, greatly shortening the service life of the material. In the chemical industry, environmental protection and other industries, frequent contact with chemical reagents is the norm, and the poor corrosion resistance of the material makes it necessary to frequently replace related equipment and products, increasing production costs and resource waste.

[0008] In addition, the lack of self-cleaning performance brings many inconveniences to the use of the material. The material surface is easily contaminated with dirt, and frequent cleaning and maintenance are required, which not only increases the use cost, but also consumes a lot of manpower and time. In some special environments where manual cleaning is difficult, such as protective net membranes of high-rise building outer walls, deep-sea filtering equipment, etc., the cleaning problem of the material is more prominent, which seriously affects the use efficiency and application range of the material.

[0009] To sum up, these problems seriously restrict the promotion and application of the PES composite material for flame-retardant net membrane in many fields. In order to meet the urgent needs of the market for high-performance materials, it has become a top priority to develop a PES composite material for flame-retardant net membrane with excellent comprehensive performance. SUMMARY

[0010] In view of the deficiencies of the prior art, the present application provides a PES composite material for flame-retardant net membrane and a preparation method thereof, which solve the above problems.

[0011] To achieve the above object, the present application is implemented by the following technical scheme: A PES composite material for flame-retardant net membrane comprises the following raw materials by weight: 35-55 parts of PES resin, 6-12 parts of modified boron nitride nanosheet, 10-18 parts of a new phosphorus-nitrogen-boron flame retardant, 4-9 parts of ethylene-vinyl acetate copolymer, 2-6 parts of carbon nanotube, 1-3 parts of light stabilizer Tinuvin770, 3-7 parts of polydimethylsiloxane, 0.8-2.5 parts of nucleating agent NA-11, 1.2-3.5 parts of dispersant BYK-110, 3-6 parts of maleic anhydride grafted polypropylene, 1-4 parts of silver-loaded zinc oxide, and 12-25 parts of deionized water.

[0012] Further, the modified boron nitride nanosheet is prepared according to the following steps: A1, the boron nitride nanosheet is added to anhydrous ethanol, ultrasonic dispersion for 30 min, then 3-aminopropyltrimethoxysilane is added, reflux stirring reaction at 80℃ for 4h, after the reaction, centrifugal separation, washing, drying; then the aminated boron nitride nanosheet is added to a Tris-HCl buffer solution containing dopamine hydrochloride, stirring reaction at room temperature for 12h, after the reaction is completed, filtering, washing, drying, to obtain aminated-dopamine coated boron nitride nanosheet; A2, the aminated-dopamine coated boron nitride nanosheet is added to N,N-dimethylformamide, ultrasonic dispersion for 20 min, then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, reaction at 120℃ for 6h under nitrogen protection, after the reaction is completed, filtering, washing, drying, to obtain phosphaphenanthrene modified boron nitride nanosheet; A3, the phosphorus-containing triphenylphosphine modified boron nitride nanosheets were added into the ethylene glycol solution and ultrasonically dispersed for 15 min; then silver nitrate solution and sodium borohydride were added and reacted at 50℃ for 3 h; after the reaction, the product was filtered, washed and dried to obtain the modified boron nitride nanosheets.

[0013] Further, in the A1 step, the amount ratio of boron nitride nanosheets, anhydrous ethanol, 3-aminopropyltrimethoxysilane, dopamine hydrochloride and Tris-HCl buffer solution was 8 g: 200 mL: 5 g: 2 g: 100 mL; the pH of the Tris-HCl buffer solution was 8.5; the stirring speed was 200 r / min; the centrifugal speed was 1000 r / min, and each centrifugation lasted for 15 min; the aminated boron nitride nanosheets were washed with anhydrous ethanol for 3 times and dried in a vacuum drying oven at 80℃ for 12 h; and the aminated-dopamine coated boron nitride nanosheets were washed with deionized water for 3 times and dried in a vacuum drying oven at 60℃ for 8 h.

[0014] Further, in the A2 step, the amount ratio of N,N-dimethylformamide and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was 150 mL: 7 g; after filtration, the product was washed with a mixed solution of DMF and ethanol in a volume ratio of 1:1 for 3 times, and then dried in a vacuum drying oven at 70℃ for 10 h.

[0015] Further, in the A3 step, the amount ratio of ethylene glycol solution, silver nitrate solution and sodium borohydride was 100 mL: 100 mL: 0.5 g; the concentration of the silver nitrate solution was 0.15 mol / L; after filtration, the product was washed with ethanol for 3 times and dried in a vacuum drying oven at 50℃ for 6 h.

[0016] The siloxane group of 3-aminopropyltrimethoxysilane is hydrolyzed under the action of ethanol and water to generate a silanol group. The silanol group condenses with the hydroxyl group on the surface of the boron nitride nanosheet, thereby introducing an amino group to the surface of the boron nitride nanosheet and realizing amination modification. This step not only enhances the dispersibility of the boron nitride nanosheet in the organic system, but also provides active sites for subsequent reactions.

[0017] In the weakly alkaline Tris-HCl buffer solution, the catechol group of dopamine will undergo a self-polymerization reaction to form a polydopamine coating, which uniformly coats the surface of the aminated boron nitride nanosheet. Polydopamine has good adhesion and biocompatibility, which further improves the surface properties of the boron nitride nanosheet and creates favorable conditions for subsequent loading of other functional groups.

[0018] The active phosphorus atom in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacts with active sites such as phenolic hydroxyl groups on the polydopamine coating, so that the phosphaphenanthrene-containing group is grafted to the surface of the boron nitride nanosheet. The phosphaphenanthrene-containing group has excellent flame retardant performance, and the introduction of the group improves the flame retardant ability of the boron nitride nanosheet. Sodium borohydride is used as a reducing agent to reduce silver ions in a silver nitrate solution into silver atoms. These silver atoms aggregate on the surface of the phosphaphenanthrene-containing modified boron nitride nanosheet to form silver nanoclusters. The silver nanoclusters have high antibacterial performance, and endow the boron nitride nanosheet with antibacterial function.

[0019] Further, the new phosphorus-nitrogen-boron flame retardant has the following specific preparation steps: B1. In a three-necked flask, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine, boric acid and N-methylpyrrolidone are added, stirred uniformly, and then heated to 160℃ for 9h.

[0020] B2. After the reaction is completed, the reaction solution is poured into a large amount of deionized water to precipitate, and the precipitate is collected, washed and dried to obtain an intermediate product; B3. The intermediate product is added to ethanol, stirred and dissolved, then pentaerythritol and p-toluenesulfonic acid are added, and the reaction is carried out at 130℃ for 7h. After the reaction is completed, the reaction solution is cooled to room temperature, filtered, washed and dried to obtain the new phosphorus-nitrogen-boron flame retardant.

[0021] Further, in the B1 step, the amount ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine, boric acid and N-methylpyrrolidone is 15g:12g:8g:200mL; in the B2 step, the precipitate is washed with deionized water for 3 times and dried in a 90℃ vacuum drying oven for 12h; in the B3 step, the amount ratio of ethanol, pentaerythritol and p-toluenesulfonic acid is 150mL:6g:1g; after filtration, the product is washed with ethanol for 3 times and dried in a 70℃ vacuum drying oven for 10h.

[0022] Boric acid first dehydrates at high temperature and reacts with the amino group in melamine to form a compound containing boron-nitrogen bonds. At the same time, the phosphorus atom in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide also participates in the reaction and is connected with the boron-nitrogen-containing compound to preliminarily construct a molecular structure containing phosphorus, nitrogen and boron elements, laying a foundation for subsequent reactions. p-Toluenesulfonic acid as a catalyst promotes the reaction of pentaerythritol with the active groups in the molecular structure of the intermediate product. The addition of pentaerythritol further perfects the molecular structure of the flame retardant and enhances the synergistic effect between phosphorus, nitrogen and boron elements. In the combustion process, the phosphorus element can promote the polymer to form carbon, forming a carbon layer with barrier effect; the nitrogen element decomposes to produce non-combustible gas, dilutes the concentration of combustible gas and inhibits the combustion reaction; the boron element forms a glassy substance at high temperature, covering the surface of the material and blocking the transmission of heat and oxygen, thereby synergistically improving the flame retardant performance of the flame retardant.

[0023] A preparation method of a PES composite material for a flame-retardant net film, the specific preparation steps are as follows: S1, first add PES resin into a high-speed mixer and stir for 5 min, then add modified boron nitride nanosheets and carbon nanotubes, increase the stirring speed and stir for 10 min, then add a new phosphorus-nitrogen-boron flame retardant and silver-loaded zinc oxide, continue to stir for 5 min, finally add ethylene-vinyl acetate copolymer, light stabilizer Tinuvin770, polydimethylsiloxane, nucleating agent NA-11, dispersant BYK-110 and maleic anhydride grafted polypropylene into the mixer, and increase the stirring speed for 8 min; S2, add the premixed raw materials into a twin-screw extruder, set the temperature of the extruder so that the raw materials melt and blend at high temperature, and obtain a uniform PES composite material melt; S3, extrude the PES composite material melt through the spinneret of a melt-blown device, under the action of high-temperature high-speed airflow, the melt is stretched into extremely fine fibers and sprayed onto a receiving device to form a melt-blown net film.

[0024] Further, in the S1 step, first stir at a speed of 900 r / min, then increase the speed to 1000 r / min after adding the modified boron nitride nanosheets and carbon nanotubes, and set the speed to 1100 r / min after adding all the substances.

[0025] Further, in the S2 step, the temperature of the feeding section of the extruder is set to 200-230 DEG C, the compression section is 250-280 DEG C, the melting section is 290-330 DEG C, the homogenization section is 290-330 DEG C, the head section is 280-300 DEG C, and the screw rotation speed is 220-320 r / min; in the S3 step, the PES composite melt temperature is controlled at 300-350 DEG C, the hot air temperature is 280-330 DEG C, the air flow speed is 200-500 m / s, the melt pressure is 1-5 MPa, the receiving device temperature is controlled at 40-50 DEG C, the receiving distance is 15-30 cm, the spinneret hole diameter is 0.1-0.5 mm, and the hole spacing is 0.5-2 mm.

[0026] The application provides a PES composite material for a flame-retardant net film and a preparation method thereof, and has the following beneficial effects: 1. Improved high-temperature resistance: By reasonably selecting and proportioning the PES resin, nucleating agent and other raw materials, and optimizing the preparation process, the softening point of the composite material of the application reaches 115 DEG C. This property enables the material to maintain stable physical properties in high-temperature environments, avoiding problems such as deformation and melting due to excessively high temperatures, and greatly expanding the application range of the material, such as being applicable to high-temperature industrial filtration, aerospace and other fields with extremely high requirements for material heat resistance, ensuring the normal operation and safety of related equipment and products under high-temperature conditions.

[0027] 2. Enhanced mechanical properties: The addition of carbon nanotubes and EVA significantly improves the tensile strength and tear strength of the material. Carbon nanotubes have extremely high strength and modulus, and are uniformly dispersed in the PES matrix to form a reinforcing network structure, effectively bearing external forces, so that the material is not easily deformed and broken when subjected to tensile force. EVA enhances the flexibility and toughness of the material, and is well compatible with PES resin and other additives. When the material is subjected to tearing force, it can effectively disperse stress and prevent crack propagation, improving the overall mechanical properties of the material, prolonging the service life of the product, and reducing the replacement cost caused by material damage.

[0028] 3. Functional diversification: On the one hand, the modified boron nitride nanosheet loaded with nano-silver clusters and the silver-loaded zinc oxide antibacterial agent endow the material with excellent antibacterial properties. It has a high inhibitory and killing effect on various common bacteria and fungi such as Escherichia coli and Staphylococcus aureus, and can be widely used in medical and health, food packaging and other fields with strict hygiene requirements, ensuring people's health and safety. On the other hand, the material also has self-cleaning properties. The polydopamine on the surface of the modified boron nitride nanosheet can undergo a photocatalytic reaction under light, decomposing organic pollutants adsorbed on the surface, reducing the accumulation of dirt on the surface of the material, maintaining the cleanliness and aesthetics of the material, reducing maintenance costs and improving the convenience of using the material.

[0029] 4. Environmental adaptability is enhanced: the synergistic effect of organic silicon-based plasticizers and compatibilizers enhances the intermolecular forces and structural stability of the material, enabling the composite material to effectively resist erosion when exposed to chemicals such as acids, bases, and organic solvents, thereby maintaining the stability of the material's performance. This feature allows the material to be used in environments with chemical corrosion risks such as chemical industry and environmental protection, expanding the material's application scenarios, reducing material failure problems caused by chemical corrosion, and improving the material's reliability and durability. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0031] Example 1: Preparation of PES composite material for flame-retardant net film, the specific preparation steps are as follows: S1, first add 35 parts of PES resin, stir at 900 r / min for 5 min, then add 6 parts of modified boron nitride nanosheet and 2 parts of carbon nanotube, increase the stirring speed to 1000 r / min, stir for 10 min, then add 10 parts of new phosphorus-nitrogen-boron flame retardant and 1 part of silver-loaded zinc oxide, keep stirring at the same speed for 5 min, finally add 4 parts of ethylene-vinyl acetate copolymer, 1 part of light stabilizer Tinuvin770, 3 parts of polydimethylsiloxane, 0.8 parts of nucleating agent NA-11, 1.2 parts of dispersant BYK-110 and 3 parts of maleic anhydride grafted polypropylene into the stirrer, and stir at 1100 r / min for 8 min; S2, add the premixed raw materials into the twin-screw extruder, set the temperature of the feeding section of the extruder to 200℃, the compression section to 250℃, the melting section to 290℃, the homogenization section to 290℃, and the die head section to 280℃, and the screw speed to 220 r / min, to obtain a uniform PES composite material melt; S3, set the spinneret hole diameter to 0.1 mm and the hole spacing to 0.5 mm, extrude the PES composite material melt through the spinneret of the melt-blown equipment, control the PES composite material melt temperature at 300℃, the hot air temperature at 280℃, the air flow speed at 200 m / s, and the melt pressure at 1 MPa, under the action of high temperature and high speed airflow, the melt is stretched into extremely fine fibers and sprayed onto the receiving device at a receiving distance of 15 cm, the receiving device temperature is controlled at 40℃, and the melt-blown net film is formed.

[0032] Example 2: Preparation of PES composite material for flame-retardant net film, the specific preparation steps are as follows: S1, first add 55 parts of PES resin, stirring at 900 r / min for 5 min, then add 12 parts of modified boron nitride nanosheet and 6 parts of carbon nanotube, increase the speed to 1000 r / min, stir for 10 min, then add 18 parts of new phosphorus-nitrogen-boron flame retardant and 4 parts of silver-loaded zinc oxide, keep stirring for 5 min, finally add 9 parts of ethylene-vinyl acetate copolymer, 3 parts of light stabilizer Tinuvin770, 7 parts of polydimethylsiloxane, 2.5 parts of nucleating agent NA-11, 3.5 parts of dispersant BYK-110 and 6 parts of maleic anhydride grafted polypropylene into the blender, stirring at 1100 r / min for 8 min; S2, the premixed raw materials are added into the twin-screw extruder, the temperature of the feeding section of the extruder is set to 230°C, the compression section is 280°C, the melting section is 330°C, the homogenization section is 330°C, and the head section is 300°C, and the screw speed is 320 r / min, to obtain a uniform PES composite melt; S3, set the spinneret hole diameter to 0.5 mm and the hole spacing to 2 mm, extrude the PES composite melt through the spinneret of the melt-blown equipment, control the PES composite melt temperature at 350°C, the hot air temperature at 330°C, the air flow speed at 500 m / s, and the melt pressure at 5 MPa, under the action of high temperature and high speed airflow, the melt is stretched into extremely fine fibers and sprayed onto the receiving device at a receiving distance of 30 cm, the receiving device temperature is controlled at 50°C, and the melt-blown net film is formed.

[0033] Example 3, preparation of flame-retardant net film PES composite material, the specific preparation steps are as follows: S1, first add 45 parts of PES resin, stirring at 900 r / min for 5 min, then add 9 parts of modified boron nitride nanosheet and 4 parts of carbon nanotube, increase the speed to 1000 r / min, stir for 10 min, then add 14 parts of new phosphorus-nitrogen-boron flame retardant and 2 parts of silver-loaded zinc oxide, keep stirring for 5 min, finally add 6 parts of ethylene-vinyl acetate copolymer, 2 parts of light stabilizer Tinuvin770, 5 parts of polydimethylsiloxane, 1.5 parts of nucleating agent NA-11, 2.2 parts of dispersant BYK-110 and 4 parts of maleic anhydride grafted polypropylene into the blender, stirring at 1100 r / min for 8 min; S2, the premixed raw materials are added into the twin-screw extruder, the temperature of the feeding section of the extruder is set to 230°C, the compression section is 280°C, the melting section is 330°C, the homogenization section is 330°C, and the head section is 300°C, and the screw speed is 320 r / min, to obtain a uniform PES composite melt; S3, set the spinneret aperture to 0.3mm, the hole spacing to 1.2mm, extrude the PES composite melt through the spinneret of the melt-blowing equipment, control the PES composite melt temperature at 325℃, the hot air temperature at 305℃, the air flow speed at 350m / s, and the melt pressure at 3MPa, under the action of the high-temperature high-speed air flow, the melt is stretched into extremely fine fibers and sprayed onto the receiving device at a receiving distance of 22cm, control the receiving device temperature at 45℃, to form a melt-blown web.

[0034] Example 4, preparation of modified boron nitride nanosheets, the specific preparation steps are as follows: A1, 8g of boron nitride nanosheets were added to 200mL of anhydrous ethanol and ultrasonically dispersed for 30min, then 5g of 3-aminopropyltrimethoxysilane was added, and the reaction was stirred at 80℃ with a stirring speed of 200r / min for 4h, after the reaction was completed, centrifugation was carried out at a speed of 1000r / min, each time for 15min, the precipitate was washed with anhydrous ethanol for 3 times, and dried in a vacuum drying oven at 80℃ for 12h; then the amino-boron nitride nanosheets were added to 100mL of Tris-HCl buffer solution with pH of 8.5 and containing 2g of dopamine hydrochloride, and stirred at room temperature for 12h, after the reaction was completed, filtration was carried out, and washed with deionized water for 3 times, and dried in a vacuum drying oven at 60℃ for 8h, to obtain amino-dopamine coated boron nitride nanosheets; A2, the amino-dopamine coated boron nitride nanosheets were added to 150mL of N,N-dimethylformamide, ultrasonically dispersed for 20min, then 7g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, and reacted at 120℃ for 6h under nitrogen protection, after the reaction was completed, filtration was carried out, and washed with a mixed solution of DMF and ethanol with a volume ratio of 1:1 for 3 times, then dried in a vacuum drying oven at 70℃ for 10h, to obtain phosphaphenanthrene modified boron nitride nanosheets; A3, the phosphaphenanthrene modified boron nitride nanosheets were added to 100mL of ethylene glycol solution, ultrasonically dispersed for 15min, then 100mL of silver nitrate solution with a concentration of 0.15mol / L and 0.5g of sodium borohydride were added, and reacted at 50℃ for 3h, after the reaction was completed, filtration was carried out, washed with ethanol for 3 times, and dried in a vacuum drying oven at 50℃ for 6h, to obtain modified boron nitride nanosheets.

[0035] Example 5, preparation of a new type of phosphorus-nitrogen-boron flame retardant, the specific preparation steps are as follows: B1, in a three-necked flask, 15g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 12g of melamine, 8g of boric acid and 200mL of N-methylpyrrolidone were added, after stirring uniformly, the temperature was raised to 160℃ and reacted for 9h; B2, after the reaction, the reaction solution was poured into a large amount of deionized water, the precipitate was separated out, filtered, collected, washed with deionized water for 3 times, and dried in a vacuum drying oven at 90 DEG C for 12h to obtain an intermediate product; B3, the intermediate product was added into 150mL ethanol, stirred and dissolved, then 6g pentaerythritol and 1g p-toluenesulfonic acid were added, and reacted at 130 DEG C for 7h, after the reaction, cooled to room temperature, filtered, washed with ethanol for 3 times, and dried in a vacuum drying oven at 70 DEG C for 10h to obtain a novel phosphorus-nitrogen-boron flame retardant.

[0036] Comparative Example 1, a PES composite for flame-retardant mesh film was prepared, and the specific preparation steps were as follows: The remaining steps were unchanged, only the modified boron nitride nanosheet of Example 2 was replaced with boron nitride nanosheet without any treatment, and a PES composite for flame-retardant mesh film was prepared.

[0037] Comparative Example 2, a PES composite for flame-retardant mesh film was prepared, and the specific steps were as follows: The remaining steps were unchanged, only the novel phosphorus-nitrogen-boron flame retardant of Example 2 was replaced with ammonium phosphate without any treatment, and a PES composite for flame-retardant mesh film was prepared.

[0038] Test item Test method Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Softening point (℃) GB / T1633-2000 "Determination of Vicat Softening Temperature (VST) of Thermoplastics" 113 115 114 80 85 Tensile strength (MPa) GB / T1040.2-2006 "Determination of tensile properties of plastics - Part 2: test conditions for moulded and extruded plastics" 50 55 53 35 40 Tear strength (kN / m) GB / T529-2008 "Determination of tear strength of vulcanized or thermoplastic rubber (trouser, right angle and crescent shaped test piece)" 40 45 43 30 32 Air permeability (mm / s) GB / T5453-1997 "Determination of air permeability of textile fabrics" 50 55 52 30 40 Antibacterial rate (%) GB / T20944.3-2008 "Evaluation and testing of antibacterial finished products - Part 3: oscillation method" (test for E. coli and S. aureus) 97 99 98 50 60 Chemical corrosion resistance Soak the material in 10% hydrochloric acid solution, 10% sodium hydroxide solution, acetone, observe the quality change and performance change after 72h immersion at room temperature Quality change less than 5% Quality change less than 5% Quality change less than 5% Quality change 15% Quality change 12% Self-cleaning performance By simulating daily pollution, smearing oil stains and other organic matter on the surface of the material, placing it in sunlight for a certain period of time, observing the decomposition of oil stains Oil stains decomposed obviously, surface cleanliness recovered 80% Oil stains decomposed obviously, surface cleanliness recovered 85% Oil stains decomposed obviously, surface cleanliness recovered 83% Oil stains basically did not decompose Oil stains basically did not decompose Flame retardant performance Test according to GB / T2408-2008 "Determination of the flammability of plastic materials - horizontal and vertical method" V-0 V-0 V-0 V-2 V-1 The file tested the multiple performances of the PES composite for flame-retardant mesh film, and after comparing the comparative examples and the comparative examples, it was found that the performance of the example was excellent, the softening point reached 113-115 DEG C, and it could be stably used in high temperature environment; the tensile and tear strengths were high, and were 50-55MPa and 40-45kN / m respectively, and the resistance to external force breaking was strong; the air permeability was 50-55mm / s, which could meet the needs of different scenes; the antibacterial rate reached 97-99%, which effectively inhibited the growth of bacteria; the chemical corrosion resistance was good, and the mass change in acid, alkali and acetone was less than 5%; the self-cleaning performance was outstanding, the oil stain was decomposed under light, and the surface cleanliness was restored by more than 80%; the flame retardant performance reached V-0 level, and the fire safety was high. The performance of the comparative example was poor, the softening point was only 80-85 DEG C, the tensile and tear strengths were low, the air permeability was not ideal, the antibacterial rate was only 50-60%, the chemical corrosion resistance was poor, the mass change was 12-15%, there was no self-cleaning ability, the flame retardant grade was V-1 or V-2 level, and the advantages of the composite material of the application were fully highlighted.

[0039] The above content is only an example and description of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the application.

Claims

1. A PES composite material for flame-retardant mesh, characterized in that: It contains the following raw materials in parts by weight: 35-55 parts PES resin, 6-12 parts modified boron nitride nanosheets, 10-18 parts novel phosphorus-nitrogen-boron flame retardant, 4-9 parts ethylene-vinyl acetate copolymer, 2-6 parts carbon nanotubes, 1-3 parts light stabilizer Tinuvin 770, 3-7 parts polydimethylsiloxane, 0.8-2.5 parts nucleating agent NA-11, 1.2-3.5 parts dispersant BYK-110, 3-6 parts maleic anhydride grafted polypropylene, 1-4 parts silver-loaded zinc oxide, and 12-25 parts deionized water.

2. The PES composite material for flame-retardant mesh as described in claim 1, characterized in that: The modified boron nitride nanosheets are prepared using the following specific steps: A1. Boron nitride nanosheets were added to anhydrous ethanol and ultrasonically dispersed for 30 min. Then, 3-aminopropyltrimethoxysilane was added, and the mixture was refluxed and stirred at 80 °C for 4 h. After the reaction was completed, the nanosheets were centrifuged, washed, and dried. Next, the aminated boron nitride nanosheets were added to a Tris-HCl buffer solution containing dopamine hydrochloride and stirred at room temperature for 12 h. After the reaction was completed, the nanosheets were filtered, washed, and dried to obtain aminated-dopamine-coated boron nitride nanosheets. A2. Add the aminated-dopamine-coated boron nitride nanosheets to N,N-dimethylformamide, ultrasonically disperse for 20 min, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and react at 120℃ for 6 h under nitrogen protection. After the reaction is completed, filter, wash and dry to obtain phosphaphenanthrene-modified boron nitride nanosheets. A3. Add the phosphorus-containing phenanthrene-modified boron nitride nanosheets to an ethylene glycol solution and ultrasonically disperse for 15 min; then add silver nitrate solution and sodium borohydride, and react at 50 °C for 3 h. After the reaction is complete, filter, wash and dry to obtain modified boron nitride nanosheets.

3. The PES composite material for flame-retardant mesh film according to claim 2, characterized in that: In step A1, the ratio of boron nitride nanosheets, anhydrous ethanol, 3-aminopropyltrimethoxysilane, dopamine hydrochloride, and Tris-HCl buffer solution is 8g:200mL:5g:2g:100mL; the pH of the Tris-HCl buffer solution is 8.5; the stirring speed is 200r / min; the centrifugation speed is 1000r / min, and each centrifugation lasts for 15 minutes; the amino-modified boron nitride nanosheets are washed three times with anhydrous ethanol and dried in a vacuum drying oven at 80℃ for 12h; the amino-dopamine-coated boron nitride nanosheets are washed three times with deionized water and dried in a vacuum drying oven at 60℃ for 8h.

4. The PES composite material for flame-retardant mesh as described in claim 2, characterized in that: In step A2, the ratio of N,N-dimethylformamide to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 150 mL: 7 g. After filtration, the product is washed three times with a mixed solution of DMF and ethanol in a volume ratio of 1:1, and then dried in a vacuum drying oven at 70 °C for 10 h.

5. The PES composite material for flame-retardant mesh as described in claim 2, characterized in that: In step A3, the ratio of ethylene glycol solution, silver nitrate solution, and sodium borohydride is 100 mL: 100 mL: 0.5 g; the concentration of silver nitrate solution is 0.15 mol / L; the product is filtered, washed three times with ethanol, and dried in a vacuum drying oven at 50°C for 6 hours.

6. The PES composite material for flame-retardant mesh as described in claim 1, characterized in that: The specific preparation steps for the novel phosphorus-nitrogen-boron flame retardant are as follows: B1. In a three-necked flask, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine, boric acid and N-methylpyrrolidone, stir well and then heat to 160℃ and react for 9 hours. B2. After the reaction is complete, pour the reaction solution into a large amount of deionized water to precipitate. Filter, collect the precipitate, wash and dry to obtain the intermediate product. B3. The intermediate product was added to ethanol and stirred to dissolve. Then pentaerythritol and p-toluenesulfonic acid were added and reacted at 130°C for 7 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed and dried to obtain a novel phosphorus-nitrogen-boron flame retardant.

7. The PES composite material for flame-retardant mesh as described in claim 6, characterized in that: In step B1, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine, boric acid, and N-methylpyrrolidone is 15g:12g:8g:200mL; in step B2, the precipitate is washed three times with deionized water and dried in a vacuum drying oven at 90℃ for 12h; in step B3, the ratio of ethanol, pentaerythritol, and p-toluenesulfonic acid is 150mL:6g:1g; after filtration, the precipitate is washed three times with ethanol and dried in a vacuum drying oven at 70℃ for 10h.

8. A method for preparing a flame-retardant PES composite material for a mesh film, characterized in that: The specific preparation steps are as follows: S1. First, add PES resin to the high-speed mixer and stir for 5 minutes. Then, add modified boron nitride nanosheets and carbon nanotubes, increase the speed and stir for 10 minutes. Next, add the novel phosphorus-nitrogen-boron flame retardant and silver-loaded zinc oxide, and continue stirring for 5 minutes. Finally, add ethylene-vinyl acetate copolymer, light stabilizer Tinuvin 770, polydimethylsiloxane, nucleating agent NA-11, dispersant BYK-110 and maleic anhydride-grafted polypropylene to the mixer and increase the speed and stir for 8 minutes. S2. Add the premixed raw materials into a twin-screw extruder, set the extruder temperature to melt and blend the raw materials at high temperature, and obtain a uniform PES composite material melt. S3. The PES composite material melt is extruded through the spinneret of the meltblown equipment. Under the action of high temperature and high speed airflow, the melt is stretched into extremely fine fibers and sprayed onto the receiving device to form a meltblown mesh.

9. The method for preparing a flame-retardant PES composite material for a mesh according to claim 8, characterized in that: In step S1, the stirring speed is first 900 r / min. After adding modified boron nitride nanosheets and carbon nanotubes, the stirring speed is increased to 1000 r / min. After all the substances are added, the stirring speed is set to 1100 r / min.

10. The method for preparing a flame-retardant PES composite material for a mesh according to claim 8, characterized in that: In step S2, the extruder's feeding section temperature is set to 200-230℃, compression section to 250-280℃, melting section to 290-330℃, homogenization section to 290-330℃, and die head section to 280-300℃, with a screw speed of 220-320 r / min. In step S3, the PES composite material melt temperature is controlled at 300-350℃, the hot air temperature at 280-330℃, the airflow velocity at 200-500 m / s, the melt pressure at 1-5 MPa, the receiving device temperature at 40-50℃, the receiving distance at 15-30 cm, the spinneret orifice diameter at 0.1-0.5 mm, and the orifice spacing at 0.5-2 mm.