High-performance zinc borate whisker nano aluminum nitride polyarylene sulfide composite functional material and preparation method thereof

Abstract

The invention belongs to the technical field of polymer synthesis, and particularly relates to a high-performance zinc borate whisker nano aluminum nitride polyarylene sulfide composite functional material and a preparation method thereof. The invention provides a preparation method of a high-performance zinc borate whisker nano aluminum nitride polyarylene sulfide composite functional material. The preparation method comprises the following steps: preparing zinc borate whiskers and nano copper borate powder; adding the first component m1 and the second component m2 into a sulfur-containing substance dehydrated by a polar aprotic solvent, and adding nano aluminum nitride emulsion polymerization to prepare a nano aluminum nitride-polyarylene sulfide compound; the composite functional material is prepared from zinc borate whiskers, nano copper borate powder and the nano aluminum nitride-polyarylene sulfide compound under the action of a coupling agent. The composite functional material disclosed by the invention has the characteristics of low density, light weight, high heat conductivity, fast heat dissipation, flame retardance, no combustion at high temperature in case of fire, high strength, stable size and the like, and provides a safe, efficient and reliable terminal material and base station component material for the field of high-frequency communication.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, specifically relating to a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material and its preparation method. Background Technology

[0002] Specialty engineering plastics polyphenylene sulfide (PPS) Polyphenylene sulfide (PPS) is widely used in petrochemicals, electronics, automobiles, and environmental protection due to its excellent corrosion resistance, high temperature resistance, good rigidity, high strength, low specific gravity, chemical resistance, hydrolysis resistance, fire resistance, and self-extinguishing properties. It also boasts a very high service temperature, remaining corrosion-resistant even at 220°C and capable of short-term use up to 260°C. However, PPS is typically used alone in fiber and film forms. In most cases, various additives are selected to modify it, creating multifunctional composite materials. Examples include high-temperature resistant and flame-retardant components for household appliances, lightweight parts for high-speed rail and automobiles, and corrosion-resistant devices in the petrochemical industry. Furthermore, with the expansion of applications, higher performance requirements are being placed on it. For instance, the frequent spontaneous combustion of electric vehicles necessitates materials that are not only lightweight but also flame-retardant. Similarly, communication base stations and antennas require not only low dielectric constant and low electrical loss but also lightweight construction, electromagnetic interference resistance, and radiation resistance, while also being able to dissipate heat during long-term use to avoid losses and hazards caused by localized heating.

[0003] However, current filler-modified polyphenylene sulfide (PPS) composites have limited functionality, generally focusing on improving only one aspect of performance. For example, adding aluminum nitride improves thermal conductivity, adding glass fiber increases mechanical strength, adding magnesium borate whiskers increases strength, using heavy atomic number metals enhances radiation resistance, and using polar fillers improves polarity and hydrophilicity. In the higher frequency communication fields of 5G and 6G, the rapid miniaturization and micro-miniaturization of terminal devices, coupled with higher frequencies leading to faster signal loss, necessitates lighter, lower-loss, faster heat dissipation, and flame-retardant multifunctional composite materials.

[0004] Based on the requirements of multifunctionality and high performance, this invention designs and prepares a type of zinc borate whisker nano-aluminum nitride polyaryl sulfide composite functional material, which has the characteristics of (1) low density and lightweight, (2) high thermal conductivity and fast heat dissipation, (3) flame retardancy and non-combustibility at high temperatures when exposed to fire, and (4) high strength and dimensional stability. This type of high-performance zinc borate whisker nano-aluminum nitride polyaryl sulfide composite functional material is prepared by in-situ composite and extrusion composite methods, providing safe, efficient and reliable terminal materials and base station component materials for the high-frequency communication field. Summary of the Invention

[0005] To address the aforementioned deficiencies, this invention provides a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material and its preparation method. This high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material is prepared through in-situ composite and extrusion composite methods. This composite functional material features low density, lightweight, high thermal conductivity, rapid heat dissipation, flame retardancy (non-combustible at high temperatures), high strength, and dimensional stability, providing safe, efficient, and reliable terminal materials and base station component materials for the high-frequency communication field.

[0006] The technical solution of the present invention:

[0007] The first technical problem to be solved by this invention is to provide a method for preparing a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material. The preparation method is as follows: zinc borate whiskers and nano-copper borate powder are prepared separately by a mixed solvent hot pressing method; then, the first component m1 and the second component m2 are added to a sulfur-containing substance dehydrated by a polar aprotic solvent, and nano-aluminum nitride is added for emulsion polymerization to obtain a nano-aluminum nitride-polyarylene sulfide composite; finally, the zinc borate whiskers, nano-copper borate powder and nano-aluminum nitride-polyarylene sulfide composite are prepared under the action of a coupling agent to obtain the high-performance zinc borate whisker nano-aluminum nitride-polyarylene sulfide composite functional material.

[0008] Wherein, the first component m1 is , , , , and At least one of them.

[0009] Furthermore, the second component m2 is , , , , , , , , , or X represents a halogen.

[0010] Furthermore, X can be F, Cl, Br, or I.

[0011] Furthermore, the sulfur-containing substance is sodium hydrosulfide or sodium sulfide.

[0012] Furthermore, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

[0013] Furthermore, the coupling agent is at least one selected from 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and Kγ-mercaptopropyltrimethoxysilane.

[0014] Furthermore, the nano-aluminum nitride emulsion is prepared by the following method: nano-aluminum nitride is added to a polar organic solvent and ultrasonically dispersed to obtain the nano-aluminum nitride emulsion.

[0015] Furthermore, the polar organic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

[0016] Furthermore, the molar amount of the second component m2 is: the total molar amount of the first component m1 and the second component m2 = 2 - 20%.

[0017] Furthermore, the total molar amount of the first component m1 and the second component m2 is equal to the volume of the polar aprotic solvent = 1 mol: 300-900 mL.

[0018] Furthermore, the total molar amount of the first component m1 and the second component m2 : the molar amount of sulfur-containing substances added = 0.95-1.05 : 1.05-0.95.

[0019] Furthermore, the mass addition amount of the nano-aluminum nitride is: the total mass of the first component m1 and the second component m2 = 2.5-25%, preferably 5-15%.

[0020] Furthermore, the mass ratio of the zinc borate whiskers, nano copper borate powder, and nano aluminum nitride-polyaryl sulfide composite is 20-40:5-10:40-60.

[0021] Furthermore, the mass addition amount of the coupling agent is: the total mass of zinc borate whiskers, nano copper borate powder and nano aluminum nitride-polyaryl sulfide composite = 0.5-5%.

[0022] Furthermore, the preparation method of high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional materials includes the following steps:

[0023] S1. Add boric acid to a mixed solvent and stir until completely dissolved. Then add zinc hydroxide, followed by an acid-base regulator, and stir at room temperature for 1-3 hours. Heat to 150-160 °C and continue the reaction at 0.4-0.6 MPa for 6-10 hours. Cool to room temperature, and then filter, wash, and dry to obtain zinc borate whiskers. Replace zinc hydroxide with copper hydroxide and use the above method to prepare nano-copper borate powder.

[0024] S2. Nano-aluminum nitride is dispersed in a polar organic solvent to prepare a nano-aluminum nitride emulsion. Then, sulfur-containing substances are added to a polar aprotic solvent and dehydrated at 185-215 °C under inert gas protection. The first component m1 and the second component m2 are added to the dehydrated sulfur-containing substances, followed by the nano-aluminum nitride emulsion. The polymerization reaction is carried out at 185-280 °C for 2.5-5 h, and then at 210-300 °C for another 2.5-5 h. The mixture is cooled to below 150 °C, washed, and dried to obtain a nano-aluminum nitride-polyaryl sulfide composite.

[0025] S3. Zinc borate whiskers, nano copper borate powder, and nano aluminum nitride-polyaryl sulfide composite are mixed, and a coupling agent is added for further mixing. The mixture is then extruded, granulated, and vacuum dried to obtain a high-performance zinc borate whisker nano aluminum nitride-polyaryl sulfide composite functional material.

[0026] Furthermore, in step S1, the mixed solvent is water-ethanol-polyethylene glycol, water-ethylene glycol, or water-glycerol.

[0027] Furthermore, in step S1, the proportions of each substance in the water-ethanol-polyethylene glycol mixture are: water:ethanol:polyethylene glycol = 50-100 mL: 50-100 mL: 10-25 g.

[0028] Furthermore, in step S1, the proportion of each substance in the water-ethylene glycol mixture is: water: ethylene glycol = 50-100 mL: 50-100 mL.

[0029] Furthermore, in step S1, the ratio of each substance in the water-glycerol mixture is: water:glycerol = 50-100 mL: 50-100 mL.

[0030] Furthermore, in step S1, the acid-base regulator is hydrazine hydrate or guanidine carbonate.

[0031] Furthermore, in step S1, the molar ratio of zinc hydroxide to boric acid is 2.95-3.05:1.95-2.05.

[0032] Further, in step S1, the sample is washed 5-7 times with hot deionized water and dried at 110-130 ℃ for 10-20 h.

[0033] Furthermore, in step S2, the sample is washed 5-7 times with deionized water and dried at 80-120 ℃ for 8-20 h.

[0034] Furthermore, in step S2, the melt index of the nano-aluminum nitride-polyaryl sulfide composite is 1-500 g / 10min.

[0035] Furthermore, in step S2, the nano-aluminum nitride-polyaryl sulfide composite has a random copolymer structure.

[0036] Furthermore, in step S3, during extrusion granulation, the extrusion temperature is 285-325 ℃, the screw speed is 100-300 rpm, the plasticizing time is 1-5 min, the granule diameter is 2-3 mm, and the length is 3-5 mm.

[0037] The second technical problem to be solved by the present invention is to provide a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material, which is prepared by the above-mentioned preparation method.

[0038] The third technical problem to be solved by the present invention is to provide a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material for use in electronics, high-frequency communications or medical devices.

[0039] The present invention has the following beneficial effects:

[0040] The high-performance zinc borate whisker-type aluminum nitride nanocomposite functional material of this invention features low density, lightweight, high thermal conductivity, rapid heat dissipation, flame retardancy, non-combustibility at high temperatures, high strength, and dimensional stability. This type of high-performance zinc borate whisker-type aluminum nitride nanocomposite functional material is prepared through in-situ composite and extrusion composite methods, providing safe, efficient, and reliable terminal materials and base station component materials for the high-frequency communication field. Detailed Implementation

[0041] This invention proposes a method for preparing a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material. The preparation method is as follows: zinc borate whiskers and copper borate nanoparticles are prepared separately by a mixed solvent hot pressing method; then, the first component m1 and the second component m2 are added to a sulfur-containing substance dehydrated by a polar aprotic solvent, and aluminum nitride nanoparticles are added for emulsion polymerization to obtain an aluminum nitride nanoparticle-polyarylene sulfide composite; finally, the zinc borate whiskers, copper borate nanoparticles, and aluminum nitride nanoparticle-polyarylene sulfide composite are prepared under the action of a coupling agent to obtain the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material.

[0042] Its preparation method specifically includes the following steps:

[0043] S1. Add boric acid to a mixed solvent and stir until completely dissolved. Then add zinc hydroxide, followed by an acid-base regulator, and stir at room temperature for 1-3 hours. Heat to 150-160 °C and continue the reaction at 0.4-0.6 MPa for 6-10 hours. Cool to room temperature, and then filter, wash, and dry to obtain zinc borate whiskers. Replace zinc hydroxide with copper hydroxide and use the above method to prepare nano-copper borate powder.

[0044] S2. Nano-aluminum nitride is dispersed in a polar organic solvent to prepare a nano-aluminum nitride emulsion. Then, sulfur-containing substances are added to a polar aprotic solvent and dehydrated at 185-215 °C under inert gas protection. The first component m1 and the second component m2 are added to the dehydrated sulfur-containing substances, followed by the nano-aluminum nitride emulsion. The polymerization reaction is carried out at 185-280 °C for 2.5-5 h, and then at 210-300 °C for another 2.5-5 h. The mixture is cooled to below 150 °C, washed, and dried to obtain a nano-aluminum nitride-polyaryl sulfide composite.

[0045] S3. Zinc borate whiskers, nano copper borate powder, and nano aluminum nitride-polyaryl sulfide composite are mixed, and a coupling agent is added for further mixing. The mixture is then extruded, granulated, and vacuum dried to obtain a high-performance zinc borate whisker nano aluminum nitride-polyaryl sulfide composite functional material.

[0046] The structural formula of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material is as follows: Z1 and Z2 are active side groups, such as hydroxyl, carboxyl, or sulfonic acid groups.

[0047] The first component m1 is , , , , and At least one of them.

[0048] The second component m2 is , , , , , , , , , or ;

[0049] Where X is a halogen.

[0050] Preferably, X is F, Cl, Br or I.

[0051] In the preparation process, zinc borate whiskers are first prepared using a mixed solvent hot-pressing method. Conventional zinc borate preparation requires the introduction of an alkaline solution to adjust the pH, using alkalis such as sodium hydroxide or potassium hydroxide. However, these are highly alkaline and may cause side reactions, such as the conversion of zinc hydroxide into zincate salts. Ammonia is also volatile and difficult to handle. This invention uses hydrazine hydrate and guanidine carbonate as pH adjusters, which not only control the pH of the reaction system but also provide antioxidant protection, ensuring the smooth progress of the reaction. Simultaneously, changes in the viscosity and pressure of the mixed solvent promote the gradual growth of zinc borate crystals, forming whiskers with a large aspect ratio. Besides excellent flame retardancy, these whiskers also possess good mechanical strength, reinforcing the resin. Then, the first component m1 and the second component m2 were added to the sulfur-containing substance dehydrated by a polar aprotic solvent, and nano-aluminum nitride was added for emulsion polymerization to prepare a nano-aluminum nitride-polyaryl sulfide composite. This is because nano-aluminum nitride has an extremely large specific surface area and is very prone to aggregation, making it impossible to uniformly disperse in the polymer using mixed extrusion. Instead, it gradually embeds itself into the molecular chain space of the polymer during polymer formation, forming a uniform composite. The use of a larger monomer component ensures strong attraction between the polyaryl sulfide molecular chains while retaining sufficient space for the embedding of nano-aluminum nitride. As the molecular weight and chain length of the polyaryl sulfide increase, the nano-aluminum nitride gradually embeds itself between the molecular chains. To avoid damaging the aluminum nitride structure, monomers containing strong acidic side groups were avoided, such as those containing carboxyl groups, sulfonic acid groups, or acyl chlorides. Hydroxyl and amino groups, being highly polar and weakly acidic monomers, were preferred. Finally, zinc borate whiskers, nano-copper borate powder, and the nano-aluminum nitride-polyaryl sulfide composite were prepared using a coupling agent to obtain the target product.

[0052] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0053] Example 1:

[0054] A high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material is prepared by the following steps:

[0055] S1. Measure 50 L of water and 50 L of ethanol, weigh 12 kg of polyethylene glycol and mix them. Stir well to obtain a mixed solvent. Add 50 L of the mixed solvent to the reactor, add 10 kg of boric acid, and stir until completely dissolved. Then add 12 kg of zinc hydroxide and 5 kg of 80% hydrazine hydrate. Stir at room temperature for 2 h, gradually increase the temperature to 155 ℃, and the pressure to 0.5 MPa. Continue the reaction for 8 h, and then cool to room temperature. After filtration, a white solid is obtained. Wash it 6 times with hot deionized water, 50 L each time, at 60 ℃. The conductivity of the filtrate after the 6th wash is 4.9 S / m. Dry at 120 ℃ for 16 h to obtain white and fluffy zinc borate whiskers. After SEM scanning, the whisker diameter is 60-150 nm and the length is 25-100 μm. Set aside for later use.

[0056] Replace zinc hydroxide with 11.9 kg of copper hydroxide and prepare nano-copper borate powder with a diameter of 30-100 nm using the above method for later use;

[0057] S2. Add 0.75 kg of nano-aluminum nitride to 5 L of N-methyl-2-pyrrolidone (NMP) and ultrasonically disperse for 2 h to form a uniform nano-aluminum nitride emulsion for later use; add 50 L of NMP, 13 kg of sodium sulfide (60% ferric yellow tablets), and 50 g of NaOH to a 100 L reactor, heat to 196 ℃ under nitrogen protection, fractionate off 4.5 kg of water and solvent, cool to 13 ℃, open the reactor, add 13.96 kg of p-dichlorobenzene and 1.59 kg of 1,5-dibromo-2,6-naphthol (… Then, 5 L of nano-aluminum nitride (NMP) emulsion (containing 0.75 kg of nano-aluminum nitride) was added to the reaction system. After replacing the air with nitrogen, the reaction vessel was sealed. The temperature was gradually increased to 220 °C and reacted for 2.5 h, completing the first stage of the reaction. The temperature was then increased to 260 °C and reacted for 3 h. After cooling to 130 °C, deionized water was slowly added, filtered, and washed 6 times with deionized water at 60 °C. The conductivity of the 6th filtrate was measured to be 4.9 S / m. The product was dried at 110 °C for 12 h to obtain 11.5 kg of white product (nano-aluminum nitride-polyaryl sulfide complex) with a melt index of 150 g / 10 min.

[0058] S3. Mix 3 kg of zinc borate whiskers, 0.6 kg of nano-copper borate powder, and 7 kg of nano-aluminum nitride-polyaryl sulfide composite, and add 0.2 kg of γ-methacryloyloxypropyltrimethoxysilane (KH-570) coupling agent. Extrude and granulate at a temperature of 315 ℃ and a screw speed of 150 rpm. Maintain plasticizing time of 2 min. Cool the extruded composite fiber with high-purity deionized water and cut it into granules with a diameter of 2 mm and a length of 3 mm. Vacuum dry at 120 ℃ for 8 h to obtain high-performance zinc borate whisker nano-aluminum nitride-polyaryl sulfide composite functional material.

[0059] Example 2:

[0060] The preparation method of Example 2 is the same as that of Example 1, except that in step S1, the mixed solvent is a mixture of 50 L of water and 50 L of ethylene glycol, and 5 kg of guanidine carbonate is used instead of hydrazine hydrate; the specific process is as follows:

[0061] Measure 50 L of water and 50 L of ethylene glycol and mix them thoroughly to obtain a mixed solvent. Add 50 L of the mixed solvent to a reactor, along with 10 kg of boric acid. Stir until completely dissolved, then add 12 kg of zinc hydroxide and 5 kg of guanidine carbonate. Stir at room temperature for 2 h, gradually increase the temperature to 155 ℃ and the pressure to 0.5 MPa, and continue the reaction for 8 h. Cool to room temperature. After filtration, a white solid is obtained. Wash it 6 times with hot deionized water, 50 L each time, at 60 ℃. The conductivity of the filtrate after the 6th wash is 4.7 S / m. Dry at 120 ℃ for 16 h to obtain white, fluffy zinc borate whiskers. SEM scanning shows that the whisker diameter is 50-160 nm and the length is 30-100 μm. Set aside for later use.

[0062] Example 3:

[0063] The preparation method of Example 3 is the same as that of Example 1, except that in step S3, the amount of zinc borate whiskers is 4 kg and the amount of coupling agent is 0.3 kg.

[0064] Example 4:

[0065] The preparation method of Example 4 is the same as that of Example 1, except that in step S2, 1.5 kg of nano-aluminum nitride is added to 7.5 L of N-methyl-2-pyrrolidone (NMP) and ultrasonically dispersed for 2 h to form a uniform nano-aluminum nitride emulsion for later use. The melt index of the obtained nano-aluminum nitride-polyaryl sulfide composite is 105 g / 10 min.

[0066] Example 5:

[0067] The preparation method of Example 5 is the same as that of Example 1, except that in step S2, 14.33 kg of p-dichlorobenzene and 1,5-dibromo-2,6-naphthol are added. 0.8 kg. The resulting nano-aluminum nitride-polyaryl sulfide composite had a melt index of 135 g / 10 min.

[0068] Example 6:

[0069] The preparation method of Example 6 is the same as that of Example 1, except that in step S2, 13.6 kg of p-dichlorobenzene and 1,5-dibromo-2,6-naphthol are added. 2.38 kg. The melt index of the obtained nano-aluminum nitride-polyaryl sulfide composite was 180 g / 10 min.

[0070] Example 7:

[0071] The preparation method of Example 7 is the same as that of Example 1, except that in step S2, 1,5-dibromo-2,6-naphthol ( Replace with 3,3'-dichlorobenzidine ( The amount used was 1.27 kg. The resulting nano-aluminum nitride-polyaryl sulfide composite had a melt index of 125 g / 10 min.

[0072] Example 8:

[0073] The preparation method of Example 8 is the same as that of Example 1, except that in step S2, 13.96 kg of p-dichlorobenzene is replaced with 13.2 kg of p-dichlorobenzene and 4,4'-dibromobiphenyl. (X=Br) 1.56 kg. The resulting nano-aluminum nitride-polyaryl sulfide composite had a melt index of 150 g / 10 min.

[0074] Example 9:

[0075] The preparation method of Example 9 is the same as that of Example 1, except that in step S3, the amount of nano copper borate powder used is 1.2 kg.

[0076] Example 10:

[0077] The preparation method of Example 10 is the same as that of Example 1, except that in step S3, γ-methacryloyloxypropyltrimethoxysilane (KH-570) is replaced with 3-aminopropyltriethoxysilane (KH550) coupling agent, and the amount of γ-methacryloyloxypropyltrimethoxysilane is 0.4 kg.

[0078] Comparative Example 1:

[0079] A conventional polyphenylene sulfide is prepared by the following steps:

[0080] Add 50 L NMP, 13 kg sodium sulfide (60% low-iron yellow tablets), and 50 g NaOH to a 100 L reactor. Heat to 196 °C under nitrogen protection. Distill off 4.5 kg of water and solvent. Cool to 13 °C, open the reactor, add 14.7 kg of p-dichlorobenzene, replace the air with nitrogen, and then seal the reactor. Gradually raise the temperature to 220 °C and react for 2.5 h to complete the first stage of the reaction. Raise the temperature to 260 °C and react for 3 h. Cool to 130 °C and slowly add deionized water. Filter. Wash 6 times with deionized water at 60 °C. The conductivity of the 6th filtrate was 4.9 S / m. Dry the product at 110 °C for 12 h to obtain 10 kg of white product with a melt index of 230 g / 10 min.

[0081] Comparative Example 2:

[0082] Using the polyphenylene sulfide obtained in Example 1 and commercially available zinc borate micro / nano powder, a composite material containing 40% zinc borate was extruded according to the extrusion granulation method in step S3 of Example 1.

[0083] Comparative Example 3:

[0084] The preparation method of Comparative Example 3 is the same as that of Example 1, except that nano-aluminum nitride is removed.

[0085] Comparative Example 4:

[0086] The preparation method of Comparative Example 4 is the same as that of Example 1, except that zinc borate whiskers are not prepared, and nano zinc borate with a diameter of 100-300 nm is used directly.

[0087] Comparative Example 5:

[0088] The preparation method of Comparative Example 5 is the same as that of Example 1, except that the nano copper borate powder is removed.

[0089] Performance testing:

[0090] The products obtained in Examples 1-10 and Comparative Examples 1-5 were injection molded into mechanical splines or electronic components using an injection molding machine, or sculpted into various required parts using a hot press. The barrel and mold were preheated according to the set process temperature requirements. The barrel temperature must be maintained for at least 20 minutes after reaching the process temperature to ensure uniform temperature throughout the barrel. The injection temperature was 315-345 ℃, the mold temperature was 130-160 ℃, the barrel temperature was 300-350 ℃, the injection pressure was 60-130 MPa, the back pressure was 0.5-1.5 MPa, the screw speed was 50-200 rpm, the sheet metal hot pressing temperature was 315-345 ℃, the pressure was 50-120 MPa, the holding time in the mold frame was 15-90 minutes, and the sheet metal thickness was 1.0-25.0 mm. The sheet metal was used for testing dielectric constant and loss coefficient. The dimensions of the injection-molded parts and test strips are determined according to actual needs. The dimensions of the mechanical test strips are as follows: Tensile test: length: greater than 165 mm; width: 13±1 mm; thickness: 4.0±0.2 mm; Bending test: length: 127±2 mm; width: 10±1 mm; thickness: different requirements for different thicknesses; Impact test: length: 64±2 mm; width: 10±1 mm; thickness: different requirements for different thicknesses, and sample preparation shall be carried out in accordance with national standards. The antenna vibrator is injection-molded into a cube with dimensions of 30x30x30 mm and is subjected to electroplating testing.

[0091] The test items and standards are as follows: (1) Density (g / cm³) 3 (1) Test method: GB / T 1033; (2) Molding shrinkage (%), test method GB / T 15585; (3) Water absorption (%), test method GB / T 2914; (4) Tensile strength (MPa), test method GB / T 1040; (5) Elongation at break (%), test method GB / T 1040; (6) Flexural strength (MPa), test method GB / T 9341; (7) Flexural modulus (GPa), test method GB / T 9341; (8) Notched impact strength of cantilever beam (KJ / m 2 (9) Melting point (°C), test method GB / T 4608; (10) Thermal conductivity (W / mK), test method ASTM E146; (11) Heat distortion temperature (1.8 MPa) (°C), test method GB / T 1634; (12) Dielectric constant (1 GHz), test method GB / T 1409; (13) Dissipation factor (1 GHz), test method GB / T 1409; (14) Electrical strength (KV / mm), test method GB / T1408; (15) Flame retardant rating, test method UL94-2023; (16) Antibacterial efficiency (%), test method GB / T 31402-2023.

[0092] The test results are shown in Tables 1 and 2.

[0093] Table 1 Performance test results of the products obtained in Examples 1-7

[0094]

[0095] Table 2 Performance test results of the products obtained in Examples 9-10 and Comparative Examples 1-5

[0096]

[0097] As shown in Tables 1 and 2, the traditional polyphenylene sulfide in Comparative Example 1 has low strength, extremely low thermal conductivity, and weaker antibacterial properties than the embodiments. In Comparative Example 2, compared with zinc borate whiskers, the composite material reinforced with zinc borate micro / nano powder has low strength, is brittle, has extremely low thermal conductivity, and weaker antibacterial properties than the embodiments. In Comparative Example 3, the composite material after removing nano-aluminum nitride shows a sharp decrease in thermal conductivity, making it unsuitable for applications requiring heat dissipation. In Comparative Example 4, compared with zinc borate whiskers, the composite material reinforced with micro / nano zinc borate has low strength and is brittle. In Comparative Example 5, the composite material after removing nano-copper borate powder shows reduced antibacterial performance, making it unsuitable for long-term effectiveness in humid or microbial environments.

[0098] It should be noted that while the preferred embodiments of the present invention are provided in this specification, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. These embodiments are not intended to impose additional limitations on the content of the present invention; their purpose is to provide a more thorough and comprehensive understanding of the disclosure of the present invention. Furthermore, the above-described technical features can be combined with each other to form various embodiments not listed above, all of which are considered to be within the scope of the present invention. Moreover, those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing a high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material, characterized in that, The preparation method is as follows: zinc borate whiskers and copper borate nanoparticles are prepared by hot pressing with a mixed solvent; then, the first component m1 and the second component m2 are added to sulfur-containing substances that have been dehydrated by a polar aprotic solvent, and aluminum nitride nanoparticles are added for emulsion polymerization to obtain aluminum nitride nanoparticles-polyarylene sulfide composites; finally, zinc borate whiskers, copper borate nanoparticles, and aluminum nitride nanoparticles-polyarylene sulfide composites are combined with a coupling agent to obtain high-performance zinc borate whisker aluminum nitride nanoparticles-polyarylene sulfide composite functional materials. Wherein, the first component m1 is , , , , and At least one of them; Furthermore, the second component m2 is , , , , , , , , , or X represents a halogen.

2. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 1, characterized in that, X is F, Cl, Br, or I; Furthermore, the sulfur-containing substance is sodium hydrosulfide or sodium sulfide; Furthermore, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane. Furthermore, the coupling agent is at least one selected from 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and Kγ-mercaptopropyltrimethoxysilane.

3. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 1, characterized in that, The nano-aluminum nitride emulsion is prepared by the following method: nano-aluminum nitride is added to a polar organic solvent and ultrasonically dispersed to obtain the nano-aluminum nitride emulsion; Furthermore, the polar organic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

4. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 1, characterized in that, The molar amount of the second component m2: the total molar amount of the first component m1 and the second component m2 = 2 - 20%; Furthermore, the total molar amount of the first component m1 and the second component m2 is equal to the volume of the polar aprotic solvent (1 mol) in the range of 300-900 mL. Furthermore, the total molar amount of the first component m1 and the second component m2 : the molar amount of sulfur-containing substances added = 0.95-1.05 : 1.05-0.95; Furthermore, the mass addition amount of the nano-aluminum nitride is: the total mass of the first component m1 and the second component m2 = 2.5-25%, preferably 5-15%.

5. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 1, characterized in that, The mass ratio of zinc borate whiskers, nano copper borate powder and nano aluminum nitride-polyaryl sulfide composite is 20-40:5-10:40-60. Furthermore, the mass addition amount of the coupling agent is: the total mass of zinc borate whiskers, nano copper borate powder and nano aluminum nitride-polyaryl sulfide composite = 0.5-5%.

6. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 1, characterized in that, The preparation method includes the following steps: S1. Add boric acid to a mixed solvent and stir until completely dissolved. Then add zinc hydroxide, followed by an acid-base regulator, and stir at room temperature for 1-3 hours. Heat to 150-160 °C and continue the reaction at 0.4-0.6 MPa for 6-10 hours. Cool to room temperature, and then filter, wash, and dry to obtain zinc borate whiskers. Replace zinc hydroxide with copper hydroxide and use the above method to prepare nano-copper borate powder. S2. Nano-aluminum nitride is dispersed in a polar organic solvent to prepare a nano-aluminum nitride emulsion. Then, sulfur-containing substances are added to a polar aprotic solvent and dehydrated at 185-215 °C under inert gas protection. The first component m1 and the second component m2 are added to the dehydrated sulfur-containing substances, followed by the nano-aluminum nitride emulsion. The polymerization reaction is carried out at 185-280 °C for 2.5-5 h, and then at 210-300 °C for another 2.5-5 h. The mixture is cooled to below 150 °C, washed, and dried to obtain a nano-aluminum nitride-polyaryl sulfide composite. S3. Zinc borate whiskers, nano copper borate powder, and nano aluminum nitride-polyaryl sulfide composite are mixed, and a coupling agent is added for further mixing. The mixture is then extruded, granulated, and vacuum dried to obtain a high-performance zinc borate whisker nano aluminum nitride-polyaryl sulfide composite functional material.

7. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 6, characterized in that, In step S1, the mixed solvent is water-ethanol-polyethylene glycol, water-ethylene glycol, or water-glycerol; Furthermore, in step S1, the proportions of each substance in the water-ethanol-polyethylene glycol mixture are: water:ethanol:polyethylene glycol = 50-100 mL: 50-100 mL: 10-25 g; Furthermore, in step S1, the ratio of each substance in the water-ethylene glycol mixture is: water: ethylene glycol = 50-100 mL: 50-100 mL; Furthermore, in step S1, the ratio of each substance in the water-glycerol mixture is: water:glycerol = 50-100 mL: 50-100 mL; Furthermore, in step S1, the acid-base regulator is hydrazine hydrate or guanidine carbonate; Furthermore, in step S1, the molar ratio of zinc hydroxide to boric acid is 2.95-3.05:1.95-2.05; Further, in step S1, the sample is washed 5-7 times with hot deionized water and dried at 110-130 ℃ for 10-20 h.

8. The preparation method of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 6, characterized in that, In step S2, wash with deionized water 5-7 times and dry at 80-120 ℃ for 8-20 h; Furthermore, in step S2, the melt index of the nano-aluminum nitride-polyaryl sulfide composite is 1-500 g / 10 min; Furthermore, in step S2, the nano-aluminum nitride-polyaryl sulfide composite is a random copolymer structure; Furthermore, in step S3, during extrusion granulation, the extrusion temperature is 285-325 ℃, the screw speed is 100-300 rpm, the plasticizing time is 1-5 min, the granule diameter is 2-3 mm, and the length is 3-5 mm.

9. A high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.

10. The use of the high-performance zinc borate whisker nano-aluminum nitride polyarylene sulfide composite functional material according to claim 9 in electronic, high-frequency communication or medical devices.

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