阅读说明：本技术 一种高导热的纳米Al2O3空心微球改性聚丙烯材料及其制法 (High-thermal-conductivity nano Al2O3Hollow microsphere modified polypropylene material and preparation method thereof ) 是由 周建文 于 2020-05-11 设计创作，主要内容包括：本发明涉及光催化材料技术领域,且公开了一种高导热的纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球改性聚丙烯材料,包括以下配方原料及组分：功能化纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球、抗氧化剂、聚丙烯。该一种高导热的纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球改性聚丙烯材料,比表面积巨大的纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球,与4-苯基苯甲酸的羧基进行酯化偶联,4-苯基苯甲酸接枝的功能化纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球与聚丙烯具有很好地相容性,通过异相成核作用,促进了聚丙烯链段在功能化纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球表面生成核结晶,提高了聚丙烯的结晶温度和结晶度,有效促进了聚丙烯成核结晶过程,具有很好地弯曲强度等机械性能,导热系数很高的纳米Al<Sub>2</Sub>O<Sub>3</Sub>空心微球在聚丙烯中分散均匀,提高了聚丙烯的热导率和导热性能。(The invention relates to the technical field of photocatalytic materials, and discloses a high-thermal-conductivity nano Al 2 O 3 The hollow microsphere modified polypropylene material comprises the following formula raw materials and components: functionalized nano Al 2 O 3 Hollow microspheres, antioxidant and polypropylene. The high-thermal conductivity nano Al 2 O 3 Hollow microsphere modified polypropylene material, nano Al with huge specific surface area 2 O 3 Hollow microsphere, 4-phenylbenzoic acid carboxyl for esterification coupling, 4-phenylbenzoic acid grafted functional nano Al 2 O 3 The hollow microspheres have good compatibility with polypropylene, and the functionalized nano Al of the polypropylene chain segment is promoted through heterogeneous nucleation 2 O 3 The hollow microsphere surface generates nuclear crystals, improves the crystallization temperature and the crystallinity of the polypropylene, effectively promotes the nucleation and crystallization process of the polypropylene, has good mechanical properties such as bending strength and the like, and has high heat conductivity coefficient 2 O 3 The hollow microspheres are uniformly dispersed in the polypropylene, so that the heat conductivity and the heat conductivity of the polypropylene are improved.)

1. High-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material comprises the following raw materials and components, and is characterized in that: functionalized nano Al₂O₃The mass ratio of the hollow microspheres to the antioxidant to the polypropylene is 0.5-2:0.8-1.5: 1000.

2. The nano Al with high thermal conductivity according to claim 1₂O₃The hollow microsphere modified polypropylene material is characterized in that: the antioxidant is a phosphite antioxidant.

3. The nano Al with high thermal conductivity according to claim 1₂O₃The hollow microsphere modified polypropylene material is characterized in that: the functionalized nano Al₂O₃The preparation method of the hollow microsphere comprises the following steps:

(1) adding distilled water and glucose into a polytetrafluoroethylene reaction kettle, heating to 190 ℃ for reaction for 10-15h, filtering, washing and drying to prepare the carbon nano-microspheres;

(2) adding aluminum nitrate and poloxamer as a surfactant into a distilled aqueous solvent, uniformly dispersing by ultrasonic, adding hydrochloric acid to adjust the pH value of the solution to 6, stirring for 3-6h at 20-40 ℃, freeze-drying to remove the solvent, placing a solid product into the distilled aqueous solvent, adding carbon nano microspheres, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene reaction kettle, heating to 160 ℃ for reacting for 4-8h, filtering and drying, placing the solid product into a resistance furnace, heating to 250 ℃ for heat preservation for 30-60min at the heating rate of 1-3 ℃/min, heating to 650 ℃ for 720 ℃ for heat preservation and calcining for 2-4h, wherein the calcined product is nano Al₂O₃Hollow microspheres;

(3) adding nano Al into potassium hydroxide solution with the mass concentration of 2-4 mol/L₂O₃The solution is transferred into a polytetrafluoroethylene reaction kettle after the hollow microspheres are uniformly dispersed by ultrasonic, the reaction is carried out for 10 to 20 hours after the solution is heated to the temperature of 100 ℃ and 150 ℃, the solid product is placed into a toluene solvent, 4-phenylbenzoic acid and a condensing agent 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate are addedHeating to 110-130 ℃, reacting for 10-15h, filtering, washing and drying to prepare the 4-phenylbenzoic acid grafted functional nano Al₂O₃Hollow microspheres.

4. The high thermal conductivity nano Al of claim 3₂O₃The hollow microsphere modified polypropylene material is characterized in that the mass concentration of the glucose aqueous solution is 0.6-1.5 mol/L.

5. The high thermal conductivity nano Al of claim 3₂O₃The hollow microsphere modified polypropylene material is characterized in that: the mass ratio of the aluminum nitrate to the poloxamer to the carbon nano-microspheres is 1:1.5-2.5: 2-4.

6. The high thermal conductivity nano Al of claim 3₂O₃The hollow microsphere modified polypropylene material is characterized in that: the nano Al₂O₃The mass ratio of the hollow microspheres to the 4-phenylbenzoic acid to the 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:4-10: 3-6.

7. The nano Al with high thermal conductivity according to claim 1₂O₃The hollow microsphere modified polypropylene material is characterized in that: the high heat-conducting nano Al₂O₃The preparation method of the hollow microsphere modified polypropylene material comprises the following steps:

(1) adding functional nano Al into a double-screw extruder₂O₃Carrying out melt blending and extrusion granulation on the hollow microspheres, the phosphite antioxidant and the polypropylene to prepare the high-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material.

Technical Field

The invention relates to the technical field of photocatalytic materials, in particular to high-thermal-conductivity nano Al₂O₃A hollow microsphere modified polypropylene material and a preparation method thereof.

Background

The polypropylene is a polymer prepared by addition polymerization of propylene as a monomer, has stable acid-base resistance, salt solution resistance and solvent resistance, is a thermoplastic synthetic resin with excellent performance, is widely applied to fiber products such as clothes, blankets and the like, medical instruments, vehicles, chemical containers and other products, but has poor crystallization performance, so that the mechanical properties such as tensile strength, bending strength and the like are poor, the thermal conductivity of the polypropylene is very low, the thermal conductivity is very poor, and the practical application of the polypropylene material is limited.

At present, the modification method of polypropylene mainly comprises copolymerization modification, grafting modification, filling modification, blending modification and the like, inorganic nano materials such as graphene, carbon nano tubes, nano alumina and the like can be added as nucleating agent fillers to adjust the nucleation process of the polypropylene, but the inorganic nano materials such as the nano alumina have lower specific surface area, very high surface energy and poor compatibility with the polypropylene, are easy to agglomerate and agglomerate in a polypropylene matrix, and can seriously affect the mechanical property of the polypropylene.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides the nano Al with high heat conductivity₂O₃The hollow microsphere modified polypropylene material and its preparation process solve the problem of nanometer Al₂O₃The compatibility with polypropylene is poor, and the problem of poor crystallization nucleation performance of polypropylene is solved.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: high-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material comprises the following raw materials and components: functionalized nano Al₂O₃The mass ratio of the hollow microspheres to the antioxidant to the polypropylene is 0.5-2:0.8-1.5: 1000.

Preferably, the antioxidant is a phosphite antioxidant.

Preferably, the functionalized nano Al₂O₃The preparation method of the hollow microsphere comprises the following steps:

(1) adding distilled water and glucose into a reaction bottle, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, heating to 190 ℃ at 160 ℃, reacting for 10-15h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the carbon nano-microsphere.

(2) Adding distilled water solvent, aluminum nitrate and surfactant poloxamer into a reaction bottle, ultrasonically dispersing uniformly, adding hydrochloric acid to adjust the pH value of the solution to 6, placing the solution in a constant-temperature water bath kettle, stirring at 20-40 deg.C for 3-6 hr, freeze drying the solution to remove solvent, placing the solid product in distilled water solvent, adding carbon nano-microspheres, uniformly dispersing by ultrasonic wave, transferring the solution into a polytetrafluoroethylene reaction kettle, heating to 160 ℃ in an oven, reacting for 4-8h, cooling the solution to room temperature, filtering to remove the solvent, drying, placing the solid product in a resistance furnace, the heating rate is 1-3 ℃/min, the temperature is increased to 250 ℃, the heat preservation treatment is carried out for 30-60min, heating to 650-720 ℃, and carrying out heat preservation and calcination for 2-4h to obtain the calcined product, namely the nano Al.₂O₃Hollow microspheres.

(3) Adding a potassium hydroxide solution with the substance amount concentration of 2-4 mol/L into a reaction bottle, and adding nano Al₂O₃Transferring the solution into a polytetrafluoroethylene reaction kettle after uniform ultrasonic dispersion, placing the reaction kettle in an oven to be heated to the temperature of 100 ℃ for reaction for 10-20h, filtering the solution to remove the solvent, washing the solid product by using distilled water, placing the solid product into a toluene solvent, adding 4-phenylbenzoic acid and a condensing agent 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, placing the solid product into an oil bath pot to be heated to the temperature of 110 ℃ for reaction by using distilled water and ethanol at a constant speed for 10-15h, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and preparing the 4-phenylbenzoic acid grafted functionalized nano Al grafted₂O₃Hollow microspheres.

Preferably, the concentration of the substance of the aqueous glucose solution is 0.6 to 1.5 mol/L.

Preferably, the mass ratio of the aluminum nitrate to the poloxamer to the carbon nano-microspheres is 1:1.5-2.5: 2-4.

Preferably, the nano Al₂O₃Hollow microsphere, 4-phenylbenzoic acid and 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethyluronium hexafluorophosphateThe amount ratio is 1:4-10: 3-6.

Preferably, the high thermal conductivity nano Al₂O₃The preparation method of the hollow microsphere modified polypropylene material comprises the following steps:

(1) adding functional nano Al into a double-screw extruder₂O₃Carrying out melt blending and extrusion granulation on the hollow microspheres, the phosphite antioxidant and the polypropylene to prepare the high-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the high-thermal conductivity nano Al₂O₃The hollow microsphere modified polypropylene material takes carbon nano-microspheres as sacrificial templates to prepare nano Al with huge specific surface area₂O₃Hollow microsphere is etched by strong alkaline solution to increase nano Al₂O₃The content of active hydroxyl on the surface of the hollow microsphere is easily esterified and coupled with carboxyl of 4-phenylbenzoic acid under the action of a condensing agent 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate to prepare the 4-phenylbenzoic acid grafted functionalized nano Al₂O₃Hollow microspheres.

The high-thermal conductivity nano Al₂O₃Hollow microsphere modified polypropylene material with functional nano Al₂O₃The hollow microsphere is used as a nucleating agent, and the benzene ring on the surface and the methyl in the polypropylene chain segment form the interaction of CH-pi bonds, so that the functionalized nano Al₂O₃The hollow microsphere has good compatibility with polypropylene and good dispersity in polypropylene matrix, and promotes the polypropylene chain segment to be functionalized with nano Al through heterogeneous nucleation₂O₃The surface of the hollow microsphere generates the nuclear crystal, so that the crystallization temperature and the crystallinity of the polypropylene can be obviously improved, the crystallization process of the polypropylene at higher temperature is promoted, crystals with higher perfection degree are formed, the nucleation and crystallization process of the polypropylene is effectively promoted, and the polypropylene with good crystallinity has the mechanical properties of good bending strength and the likeNano Al with high performance and heat conductivity₂O₃The hollow microspheres are uniformly dispersed in the polypropylene to form a three-dimensional heat-conducting network, so that the heat conductivity and heat-conducting property of the polypropylene are obviously improved.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: high-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material comprises the following raw materials and components: functionalized nano Al₂O₃The mass ratio of the hollow microspheres to the phosphite antioxidant to the polypropylene is 0.5-2:0.8-1.5: 1000.

Functionalized nano Al₂O₃The preparation method of the hollow microsphere comprises the following steps:

(1) adding distilled water and glucose into a reaction bottle, controlling the mass concentration of a substance to be 0.6-1.5 mol/L, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, heating to 190 ℃ for reaction for 10-15h, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the carbon nano microsphere.

(2) Adding distilled water solvent, aluminum nitrate and poloxamer as surfactant into a reaction bottle, uniformly dispersing by ultrasonic, adding hydrochloric acid to adjust the pH value of the solution to 6, placing the solution into a constant-temperature water bath, uniformly stirring for 3-6h at 20-40 ℃, freeze-drying the solution to remove the solvent, placing a solid product into the distilled water solvent, adding carbon nano microspheres, wherein the mass ratio of the aluminum nitrate to the poloxamer to the carbon nano microspheres is 1:1.5-2.5:2-4, uniformly dispersing by ultrasonic, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into an oven, heating to 160 ℃ for reaction for 4-8h, cooling the solution to room temperature, filtering to remove the solvent, drying, placing the solid product into a resistance furnace, heating to 250 ℃ at the rate of 1-3 ℃/min, heating to 180 ℃, carrying out heat preservation treatment for 30-60min, heating to 650-720 ℃, and carrying out heat preservation and calcination for 2-4h to obtain the calcined product, namely the nano Al₂O₃Hollow microspheres.

(3) Adding a potassium hydroxide solution with the substance amount concentration of 2-4 mol/L into a reaction bottle, and adding nano Al₂O₃Uniformly dispersing the hollow microspheres by ultrasonic, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, heating to the temperature of 100 ℃ and 150 ℃, reacting for 10-20h, filtering the solution to remove the solvent, washing the solid product by using distilled water, placing the solid product into a toluene solvent, adding 4-phenylbenzoic acid and a condensing agent 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, wherein the nano Al is nano Al₂O₃The mass ratio of the hollow microspheres to the 4-phenylbenzoic acid to the 2- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate is 1:4-10:3-6, the mixture is placed in an oil bath pot, heated to 110 ℃ and 130 ℃, stirred at a constant speed for reaction for 10-15h, the solution is filtered to remove the solvent, and the solid product is washed by distilled water and ethanol to prepare the 4-phenylbenzoic acid grafted functional nano Al₂O₃Hollow microspheres.

High heat conduction nano Al₂O₃The preparation method of the hollow microsphere modified polypropylene material comprises the following steps:

(1) adding functional nano Al into a double-screw extruder₂O₃Carrying out melt blending and extrusion granulation on the hollow microspheres, the phosphite antioxidant and the polypropylene to prepare the high-thermal-conductivity nano Al₂O₃The hollow microsphere modified polypropylene material.