阅读说明：本技术 一种纳米粉体/聚醚醚酮复合材料及其制备方法 (Nano powder/polyether-ether-ketone composite material and preparation method thereof ) 是由 赵辉 朱正吼 宋晖 刘容羽 于 2021-07-21 设计创作，主要内容包括：本发明提供了一种纳米粉体/聚醚醚酮复合材料及其制备方法,所述纳米粉体/聚醚醚酮复合材料的组成成分包括聚醚醚酮与磁性纳米粉体,所述磁性纳米粉体为纳米四氧化三铁、纳米Fe粉、纳米Ni粉、纳米Co粉及其合金纳米粉体(如FeNi、FeCo等)、或氧化物的一种或两种以上。本发明首先制备磁性纳米粉体/二苯砜复合材料,在由缩聚反应生成PEEK粉末时,PEEK粉末以纳米粉体为晶核长大,能够保证纳米粉体不发生团聚；二苯砜与PEEK不同,可溶于有机溶剂并且熔融温度及粘度较低,易制备纳米颗粒均匀分散的纳米复合材料；PEEK合成反应过程中,纳米粉体一直处于二苯砜中,能够尽量减少粉体的团聚,并且有氮气保护,不会发生氧化反应。(The invention provides a nano powder/polyetheretherketone composite material and a preparation method thereof, wherein the composition components of the nano powder/polyetheretherketone composite material comprise polyetheretherketone and magnetic nano powder, and the magnetic nano powder is one or more than two of nano ferroferric oxide, nano Fe powder, nano Ni powder, nano Co powder and alloy nano powder (such as FeNi, FeCo and the like) thereof, or oxide. The invention firstly prepares the magnetic nano powder/diphenyl sulfone composite material, when the PEEK powder is generated by polycondensation reaction, the PEEK powder grows up by taking the nano powder as crystal nucleus, which can ensure that the nano powder does not agglomerate; the diphenyl sulfone is different from PEEK, can be dissolved in an organic solvent, has lower melting temperature and viscosity, and is easy to prepare a nano composite material with uniformly dispersed nano particles; in the PEEK synthesis reaction process, the nano powder is always in the diphenyl sulfone, the agglomeration of the powder can be reduced as much as possible, and no oxidation reaction occurs under the protection of nitrogen.)

1. A nano powder/polyether-ether-ketone composite material is characterized in that: the composition of the nano powder/polyetheretherketone composite material comprises polyetheretherketone and magnetic nano powder, wherein the magnetic nano powder is one or more of nano ferroferric oxide, nano Fe powder, nano Ni powder, nano Co powder and alloy nano powder or oxide thereof.

2. The nanopowder/polyetheretherketone composite material of claim 1, wherein: the content of the nano powder is 0-50 wt%.

3. A method for preparing the nano powder/polyetheretherketone composite material according to any one of claims 1 to 2, which is characterized in that: the method comprises the following steps:

step 1: surface treatment of the magnetic nanometer powder; firstly, adding magnetic nano powder into absolute ethyl alcohol, then carrying out ultrasonic dispersion, removing redundant absolute ethyl alcohol after centrifugation, then adding a proper amount of acetone/alcohol solvent containing titanate coupling agent or silane coupling agent, carrying out ultrasonic dispersion, and removing redundant acetone by adopting a magnetic separation technology;

step 2: preparing a magnetic nano powder/diphenyl sulfone composite material; dissolving diphenyl sulfone by adopting a proper organic solvent, then adding the magnetic nano powder subjected to surface treatment into the dissolved diphenyl sulfone liquid, and uniformly stirring; finally, mechanically stirring until the organic solvent is completely volatilized and the solid is in a powder state;

and step 3: uniformly mixing a magnetic nano powder/diphenyl sulfone-containing composite material, difluorobenzophenone, hydroquinone, anhydrous sodium carbonate and anhydrous potassium carbonate according to a certain proportion; placing the mixed materials in a reaction kettle, introducing nitrogen for protection after vacuumizing, and connecting a condensing reflux device; heating while stirring, heating to 180 ℃, keeping the temperature for 1h, keeping the temperature for 250 ℃ for 2.5h, keeping the temperature for 320 ℃ for 2.5h, cooling, and taking out a reaction product; crushing to obtain a solid reaction product;

and 4, step 4: and crushing, washing and drying the product to obtain the nano powder/PEEK composite material powder.

4. The method for preparing the nano powder/polyetheretherketone composite material according to claim 3, wherein the method comprises the following steps: firstly, preparing a diphenyl sulfone magnetic nano composite material, and selecting acetone as an organic solvent in the step 2; dissolving diphenylsulfone in acetone, adding the surface-treated magnetic nano powder, keeping the temperature at 60 ℃, mechanically stirring for 1 hour, keeping the temperature at 85 ℃, mechanically stirring to volatilize acetone to a solid powder state, and connecting a condensation reflux device to recover volatilized acetone.

Technical Field

The invention belongs to the field of thermoplastic composite materials, and particularly relates to a nano powder/polyether-ether-ketone composite material and a preparation method thereof.

Background

Polyetheretherketone (PEEK) is a rigid semi-crystalline polymer with excellent overall properties of heat resistance, wear resistance, fatigue resistance, irradiation resistance, peel resistance, creep resistance, dimensional stability, impact resistance, chemical resistance, non-toxicity, flame retardancy, etc., and two ether bonds and carbonyl groups in its structure provide flexibility and excellent manufacturability for the material. Therefore, PEEK is widely used in various fields such as electronics, electricity, aerospace, automobiles, energy and other industries, medical treatment, and the like.

Nanomaterials (nano-materials), due to their dimensions already close to the wavelength of light and to the special effect of having a large surface, often exhibit properties different from those exhibited by the substance in its bulk state, such that they exhibit characteristic properties in many respects, such as electrical, magnetic, optical, thermal, electrical conductivity, etc. The method has very important significance for obtaining better performance by adopting the nano modified polyether-ether-ketone.

The preparation method of the prior nanometer powder modified polyether-ether-ketone composite material comprises the steps of carrying out ball milling or high-speed stirring, and then adopting double screw extrusion granulation, or hot pressing and injection molding; however, since the PEEK is high in melting temperature, the melted PEEK has high viscosity, is insoluble in any solvent, has poor wettability, large specific surface area of the nano powder and surface effect, and the nano powder is easy to agglomerate due to the self characteristics, the nano powder particles are easy to agglomerate in the PEEK matrix, and the bonding condition of the nano powder prepared by the traditional method and the PEEK interface is poor. Therefore, the development of a novel polyether-ether-ketone nano composite material is very important.

Disclosure of Invention

The invention provides a nano powder/polyether-ether-ketone composite material and a preparation method thereof, aiming at overcoming the defects in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme: the nanometer powder/polyetheretherketone composite material comprises polyetheretherketone and magnetic nanometer powder, wherein the magnetic nanometer powder is one or a combination of more than two of nanometer ferroferric oxide, nanometer iron powder, nanometer nickel powder, nanometer cobalt powder and nanometer iron-nickel alloy powder.

Preferably, the content of the nano powder is 0-50 wt%.

The preparation method of the magnetic nano powder/polyether-ether-ketone composite material comprises the following steps:

step 1: surface treatment of the magnetic nanometer powder; firstly, adding magnetic nano powder into absolute ethyl alcohol, then carrying out ultrasonic dispersion, removing redundant absolute ethyl alcohol by adopting a magnetic separation technology and centrifugation, then adding a proper amount of acetone/alcohol solvent containing titanate coupling agent or silane coupling agent, and volatilizing redundant solvent by adopting ultrasonic dispersion and magnetic separation technology;

step 2: preparing a magnetic nano powder/diphenyl sulfone composite material; dissolving diphenyl sulfone by adopting a proper organic solvent, then adding the magnetic nano powder subjected to surface treatment into the dissolved diphenyl sulfone liquid, and uniformly stirring; finally, mechanically stirring until the organic solvent is completely volatilized and the solid is in a powder state;

preferably, the organic solvent is selected from acetone; dissolving diphenylsulfone in acetone, adding the surface-treated magnetic nano powder, keeping the temperature at 60 ℃, mechanically stirring for 1 hour, keeping the temperature at 85 ℃, mechanically stirring to volatilize acetone to a solid powder state, and connecting a condensation reflux device to recover volatilized acetone.

And step 3: uniformly mixing a magnetic nano powder/diphenyl sulfone-containing composite material, difluorobenzophenone, hydroquinone, anhydrous sodium carbonate and anhydrous potassium carbonate according to a certain proportion; placing the mixed materials in a reaction kettle, introducing nitrogen for protection after vacuumizing, and connecting a condensing reflux device; heating while stirring, heating to 180 ℃, keeping the temperature for 1h, keeping the temperature for 250 ℃ for 2.5h, keeping the temperature for 320 ℃ for 2.5h, cooling, and taking out a reaction product; crushing to obtain a solid reaction product;

and 4, step 4: the product is crushed, washed (sequentially washed by hot alcohol or acetone and water) and dried to obtain the nano powder/PEEK composite material powder.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention firstly prepares the magnetic nano powder/diphenyl sulfone composite material, when the PEEK powder is generated by polycondensation reaction, the PEEK powder grows up by taking the nano powder as crystal nucleus, and can ensure that the nano powder does not agglomerate.

(2) Unlike PEEK, diphenyl sulfone is soluble in organic solvents and has low melting temperature and viscosity, and can easily prepare magnetic nanocomposite materials with uniformly dispersed nanoparticles.

(3) In the PEEK synthesis reaction process, the magnetic nano powder is always in the diphenyl sulfone, the agglomeration of the powder can be reduced as much as possible, and the oxidation reaction can not occur due to the protection of nitrogen.

Detailed Description

The present invention will be further described with reference to the following embodiments.

Example 1

This example provides a Fe₃O₄Preparation of polyether-ether-ketone nano composite material.

(1)Fe₃O₄Surface treatment of nano powder: firstly, adding a proper amount of absolute ethyl alcohol into Fe3O4 nano powder, performing ultrasonic dispersion for 30 minutes, centrifuging, and adding a proper amount of mixed solution of titanate coupling agent and acetone; then ultrasonic treatment is carried out for 30 minutes, and the mixture is centrifuged for standby.

(2)Fe₃O₄Preparing a powder modified diphenyl sulfone nano composite material: first, diphenylsulfone was dissolved with acetone: putting the diphenyl sulfone powder into a beaker, adding a proper amount of acetone, putting the beaker into a water bath kettle at the temperature of 60 ℃, and stirring to dissolve until the diphenyl sulfone is completely dissolved.

Nano Fe after surface treatment₃O₄The powder is uniformly dispersed in diphenyl sulfone: fe in acetone solvent₃O₄Pouring the powder into diphenyl sulfone dissolved in acetone, keeping the temperature at 60 ℃, mechanically stirring for 1 hour, keeping the temperature at 85 ℃, and mechanically stirring to volatilize the acetone to a solid powder state.

(3) Mixing Fe₃O₄Uniformly mixing a diphenylsulfone magnetic nano composite material, 4' -difluorobenzophenone and hydroquinone according to a certain proportion, placing the mixture in a flask, connecting a condensation reflux device, introducing nitrogen into the flask, and stirring the mixture to 180 ℃ while heating; adding the mixed powder of anhydrous sodium carbonate and anhydrous potassium carbonate, and uniformly stirring;

(4) heating to 180 ℃ and preserving heat for 1h, preserving heat for 2.5h at 250 ℃, preserving heat for 2.5h at 320 ℃, cooling and taking out a reaction product to obtain a solid reaction product.

(5) The product is crushed, washed (by acetone (twice), water (twice) and acetone (twice) in sequence) and dried to obtain Fe₃O₄A PEEK nanocomposite powder.

Example 2

The embodiment provides a preparation method of a FeNi/polyetheretherketone nanocomposite.

(1) Surface treatment of FeNi nano powder: firstly, adding a proper amount of absolute ethyl alcohol into FeNi nano powder, performing ultrasonic dispersion for 30 minutes, centrifuging, and adding a proper amount of mixed solution of a silane coupling agent and alcohol; then ultrasonic treatment is carried out for 30 minutes, and the mixture is centrifuged for standby.

(2) Preparation of the FeNi/diphenyl sulfone nanocomposite: first dissolve diphenyl sulfone with hot alcohol: putting the diphenyl sulfone powder into a beaker, adding a proper amount of alcohol, putting the beaker into a water bath kettle at the temperature of 60 ℃, and stirring to dissolve until the diphenyl sulfone is completely dissolved. Adding the FeNi nano powder after surface treatment into diphenyl sulfone dissolved in hot alcohol, keeping the temperature at 60 ℃, mechanically stirring for 1 hour, keeping the temperature at 85 ℃, and mechanically stirring to volatilize alcohol to a solid powder state.

(3) Mixing the FeNi/diphenyl sulfone nano composite material, 4' -difluorobenzophenone, hydroquinone, anhydrous sodium carbonate and anhydrous potassium carbonate uniformly according to a certain proportion. Placing the mixed materials in a reaction kettle, introducing nitrogen for protection after vacuumizing, and connecting a condensing reflux device; heating while stirring, heating to 180 ℃, keeping the temperature for 1h, keeping the temperature for 250 ℃ for 2.5h, keeping the temperature for 320 ℃ for 2.5h, cooling, and taking out a reaction product; crushing to obtain a solid reaction product;

(4) and (3) crushing and washing the product (sequentially washing with acetone (twice), water (twice) and acetone (twice)), and drying to obtain FeNi/PEEK nano composite material powder.

Example 3

This example provides a Hydroxyapatite (HAP)/Fe₃O₄Preparation of polyether-ether-ketone nano composite material.

(1)HAP/Fe₃O₄Surface treatment of nano powder: firstly, preparing HAP coated Fe by adopting a liquid-phase coprecipitation method₃O₄Adding a proper amount of absolute ethyl alcohol into the nano composite powder, performing ultrasonic dispersion for 30 minutes, centrifuging, and adding a proper amount of mixed solution of titanate coupling agent and acetone; then ultrasonic treatment is carried out for 30 minutes, and the mixture is centrifuged for standby.

(2)HAP/Fe₃O₄The preparation of the nano composite powder modified diphenyl sulfone nano composite material comprises the following steps: first, diphenylsulfone was dissolved with acetone: putting the diphenyl sulfone powder into a beaker, adding a proper amount of acetone, putting the beaker into a water bath kettle at the temperature of 60 ℃, and stirring to dissolve until the diphenyl sulfone is completely dissolved.

Uniformly dispersing the surface-treated nano composite powder into diphenyl sulfone: HAP/Fe in acetone solvent₃O₄The composite powder is poured into diphenyl sulfone dissolved by acetone, the temperature is kept at 60 ℃, the mechanical stirring is carried out for 1 hour, then the temperature is kept at 85 ℃, and the mechanical stirring is carried out to volatilize the acetone until the solid powder state is reached.

(3) Will contain HAP/Fe₃O₄Uniformly mixing the composite powder/diphenyl sulfone nano composite material, 4' -difluorobenzophenone and hydroquinone according to a certain proportion, placing the mixture in a flask, connecting a condensation reflux device, introducing nitrogen into the flask, and stirring the mixture to 180 ℃ while heating; adding the mixed powder of anhydrous sodium carbonate and anhydrous potassium carbonate, and uniformly stirring;

(4) heating to 180 ℃ and preserving heat for 1h, preserving heat for 2.5h at 250 ℃, preserving heat for 2.5h at 320 ℃, cooling and taking out a reaction product to obtain a solid reaction product.

(5) The product is crushed, washed (by acetone (twice), water (twice) and acetone (twice), and dried to obtain HAP/Fe3O4/PEEK nanocomposite powder.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.