Modified polyaryletherketone composite material with high dimensional stability and high conductivity and preparation method thereof

Abstract

The invention relates to the technical field of composite material processing, in particular to a high-dimensional-stability and high-conductivity modified polyaryletherketone composite material and a preparation method thereof. Comprising the following materials: a modified carbon material with at least one-dimensional scale, bisphenol AF type polyether-ether-ketone as an interface modifier, and PAEK resin; the structure of the modified carbon material is that a nano conductive material is attached to the surface of a carbon nano material in situ, and the nano conductive material is nano conductive metal or nano conductive metal oxide; after uniform mixing, melt blending is performed to obtain granules, and then crystallization molding is performed to obtain a composite material; the conductive carbon material is treated to form a composite conductive structure, and the interface modifier is combined, so that the conductivity and the dimensional stability of the composite material can be greatly improved while filler agglomeration is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite material processing, in particular to a modified polyaryletherketone composite material with high dimensional stability and high conductivity and a preparation method thereof. BACKGROUND

[0002] With the rapid development of high-end industrial fields such as aerospace, precision instruments, biomedical and next-generation communication technologies, the functionality of key structural materials has become increasingly demanding. Ideal materials not only need to serve as load-bearing or packaging components with excellent mechanical properties, thermal stability and chemical stability, but also are expected to integrate sensing, transmission, electromagnetic shielding and other electronic functions to achieve structural and functional integration. In this context, special engineering plastics are gradually expanding from traditional insulating structural parts to functional and precision application scenarios due to their unique performance advantages.

[0003] Polyaryletherketone (PAEK), as one of the materials at the top of the special engineering plastics pyramid, has a molecular backbone composed of alternating aromatic rings, ether bonds and ketone bonds, which endows the material with unparalleled comprehensive performance. Its excellent high-temperature resistance (long-term use temperature exceeding 250℃), outstanding mechanical strength, superior creep resistance, excellent chemical corrosion resistance and inherent flame retardance enable it to maintain stable performance in harsh environments. In addition, PAEK also exhibits good biocompatibility and has been widely used in orthopedic implants and surgical tools. However, its highly stable aromatic ring structure results in high electrical insulation (volume resistivity typically higher than 10 16 Ω·cm) and large molding shrinkage (1.5-3.0%), which greatly limits the direct application of PAEK in precision electronic devices, electrostatic protection, electromagnetic shielding and high-performance sensors. In existing technologies, the addition of conductive fillers can improve electrical conductivity, but uneven distribution of fillers can easily lead to interface stress concentration and cause dimensional distortion. In addition, the high melt viscosity (>1000 Pa·s) of PAEK in traditional processes further exacerbates the problem of uneven filler distribution, resulting in poor continuity of the conductive network and insufficient dimensional stability. SUMMARY

[0004] To improve the technical problems of high insulation and high molding shrinkage of PAEK materials, a modified polyaryletherketone composite material with high dimensional stability and high conductivity and a preparation method thereof are provided. The present application forms a composite conductive structure by treating conductive carbon materials, combined with an interface modifier, which can significantly improve the electrical conductivity and dimensional stability of the composite material while reducing filler aggregation.

[0005] To achieve the above purposes, the present application realizes the following technical solutions:

[0006] A modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity, comprising: a modified carbon material with at least one dimension, an interface modifier, and a PAEK resin.

[0007] The structure of the modified carbon material is that a nano-conductive material is in-situ attached to the surface of a carbon nano-material, and the nano-conductive material is a nano-conductive metal or a nano-conductive metal oxide.

[0008] Further, the composite material comprises 100% by weight of the material: 5%-25% of the modified carbon material with at least one dimension, 1%-3% of the interface modifier, and the balance of the PAEK resin.

[0009] The proportion of the nano-conductive material in the modified carbon material is in the range of 5%-60%, and preferably the proportion of the nano-conductive material in the modified carbon material is 15%-50%.

[0010] Further, the carbon nano-material is one or more of carbon nanotubes, carbon nanorods, and carbon fibers with oxygen-containing groups (hydroxyl and / or carboxyl) on the surface.

[0011] The nano-conductive metal is one or more of nano-silver, nano-gold, and nano-copper generated in-situ on the surface of the carbon nano-material.

[0012] The nano-conductive metal oxide is one or more of nano-indium tin oxide, nano-tin antimony oxide, and nano-aluminum-doped zinc oxide generated in-situ on the surface of the carbon nano-material.

[0013] Further, the carbon nano-material is selected from one or more of carbon nanotubes with a diameter less than 50 nm and an aspect ratio greater than 500, carbon nanorods with a diameter less than 50 nm and an aspect ratio greater than 500, and carbon fibers with a diameter less than 300 nm and a length of at least 1 μm; and the average particle size of the nano-conductive material is not more than 200 nm.

[0014] Further, the modified carbon material is obtained by the following steps: forming a functionalized carbon nano-material with oxygen-containing groups (hydroxyl and / or carboxyl) on the surface of the carbon nano-material, adsorbing metal ions with the oxygen-containing groups as anchoring sites, and then growing a nano-conductive material in-situ on the surface of the functionalized carbon nano-material by one or more of a chemical reduction method, a coprecipitation method, a hydrothermal method, and a solvothermal method, and then performing heat treatment or not to obtain the modified carbon material with the structure of the nano-conductive material in-situ attached to the surface of the carbon nano-material.

[0015] Further, when the structure of the modified carbon material is a nanometer conductive metal attached to the surface of the carbon nanomaterial in situ, the modified carbon material is obtained by dispersing the functionalized carbon nanomaterial in one or more of a solution of a water-soluble silver source, a water-soluble gold source, and a water-soluble copper source, forming a reaction solution with a concentration of 5-10 g / L, heating to 60-100°C under a protective atmosphere, adding a reducing agent, stirring for 0.5-4 h to perform a reduction reaction, and cooling, washing, and drying to obtain the modified carbon material with the structure of a nanometer conductive metal attached to the surface of the carbon nanomaterial in situ.

[0016] The reducing agent is selected from sodium citrate and / or ascorbic acid; the water-soluble silver source is a nitrate; the water-soluble gold source is chloroauric acid; and the water-soluble copper source is copper sulfate or copper acetate.

[0017] Further, when the structure of the modified carbon material is a nanometer conductive metal oxide attached to the surface of the carbon nanomaterial in situ, the modified carbon material is obtained by dispersing the functionalized carbon nanomaterial in a water-soluble raw material solution, forming a reaction solution with a concentration of 5-10 g / L, adding a basic precipitant dropwise under stirring until the end point pH value is greater than 8, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, performing a hydrothermal reaction at 120-200°C for 6-24 h, cooling, washing, and drying, and then high-temperature calcining at 300-800°C for 1-5 h to obtain the modified carbon material with the structure of a nanometer conductive metal oxide attached to the surface of the carbon nanomaterial in situ.

[0018] The water-soluble raw material solution is one of a mixed solution of tin tetrachloride (SnCl4) and antimony trichloride (SbCl3) prepared according to an atomic ratio of Sn:Sb = 90:10-95:5, a mixed solution of indium trichloride (InCl3) and tin tetrachloride (SnCl4) prepared according to an atomic ratio of In:Sn = 90:10, and a mixed solution of zinc acetate ((CH3COO)2Zn·2H2O) and aluminum nitrate (Al(NO3)3·9H2O) or aluminum isopropoxide (Al(O-iPr)3) prepared according to an atomic ratio of Zn:Al = 95:5-98:2.

[0019] The basic precipitant is a 0.5-2 mol / L sodium hydroxide solution or an aqueous ammonia solution; when nanometer indium tin oxide is needed to be generated in situ, the end point pH = 8.5-9.5; when nanometer tin antimony oxide is needed to be generated in situ, the end point pH = 8.0-9.0; and when nanometer aluminum-doped zinc oxide is needed to be generated in situ, the end point pH = 8.0-9.0.

[0020] Furthermore, a method for functionalizing carbon nanomaterials by giving the surface of the carbon nanomaterials oxygen-containing groups is as follows: the carbon nanomaterials are ultrasonically treated at 140-150°C for 1-2 hours with a mixed acid of nitric acid and sulfuric acid in a volume ratio of 1:2-4, washed with water until neutral, and then dried to obtain functionalized carbon nanomaterials.

[0021] The PAEK resin is selected from one or more of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK).

[0022] The interface modifier is a sulfonated bisphenol AF type polyether ether ketone. Bisphenol AF type polyether ether ketone powder with an average particle size of less than 1 mm is mixed with 95wt%-98wt% concentrated sulfuric acid at a ratio of 1 g: 5-20 mL. The mixture is stirred and reacted at 40-60℃ for 0.5-4 h. The product is precipitated with cold water, washed, and dried to obtain the sulfonated bisphenol AF type polyether ether ketone. The degree of sulfonation is controlled to be approximately 30%-50%.

[0023] The M of the bisphenol AF type polyether ether ketone n =1-3×10 5 g / mol, M w =5-8×10 5 g / mol, PDI = 1-3.5.

[0024] For example, the chemical structure of bisphenol AF type polyether ether ketone can be:

[0025] ;

[0026] The conventional method for preparing polyether ether ketone involves, under a protective atmosphere, bisphenol AF and 4,4'-difluorobenzophenone in an equimolar ratio in the presence of anhydrous sodium carbonate and / or anhydrous potassium carbonate (100%-120% of the molar amount of bisphenol AF) in a sulfolane solvent and a dehydrating agent. The mixture is first heated to 130-150°C and refluxed until the theoretical water yield is reached. The dehydrating agent is then evaporated, and the temperature is raised to 190-220°C for polymerization for 3-8 hours. After the reaction is complete, the product is precipitated using a poor solvent (such as water), washed, and dried to obtain bisphenol AF-type polyether ether ketone.

[0027] The second aspect of the present invention provides a method for preparing a modified polyaryletherketone composite material with high dimensional stability and high conductivity, comprising the following steps: mixing a modified carbon material having at least one dimension, an interface modifier, and PAEK resin according to a formula, followed by melt blending to obtain granules, and then crystallizing them.

[0028] The modified carbon material is composed of a carbon nanomaterial with an in-situ attached nano-conductive material on its surface, wherein the nano-conductive material is a nano-conductive metal or a nano-conductive metal oxide.

[0029] The melt blending is achieved using a twin-screw extruder with the following parameters: melt blending temperature 350-400℃, vacuum devouring pressure less than 10kPa;

[0030] The crystallization process involves placing the obtained granules in a molding die and pressing them under pressure of at least 8 MPa and heating them at 380-400°C for 10-40 minutes, followed by cooling at a rate of less than 3°C / min to induce crystallization.

[0031] Beneficial technical effects: This invention functionalizes nano-carbon materials with oxygen-containing groups, and then generates nano-conductive materials in situ on their surface to form a composite synergy, creating a "skeleton-bridging" composite conductive structure. This reduces stress concentration caused by filler agglomeration while reducing the amount of filler added. Combined with sulfonated polyether ether ketone as an interface modifier, the sulfonic acid groups form strong hydrogen bonds with the carboxyl groups on the filler surface, while the fluoride molecular chains can better integrate with the matrix resin. This allows the composite material to maintain high conductivity while significantly improving interfacial shear strength, and controlling the thermal expansion coefficient and volume shrinkage rate of the composite material at a low level. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0033] Unless otherwise specifically stated, the numerical values ​​set forth in these embodiments do not limit the scope of the invention. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that values ​​expressed, for example, as "within the range of ab" or "between the range of ab," do not include the endpoint values ​​a and b; values ​​expressed as "for ab," "is ab," or "ab" include the endpoint values ​​a and b.

[0034] Experimental methods not specified in the following examples are generally performed according to national standards; if there is no corresponding national standard, they are performed according to general standard requirements or general methods.

[0035] Preparation Example 1

[0036] The preparation method of bisphenol AF type polyether ether ketone includes the following steps:

[0037] 0.5 mol of bisphenol AF, 0.5 mol of 4,4'-difluorobenzophenone, 0.55 mol of anhydrous sodium carbonate (200 mesh), 300 mL of sulfolane solvent, and 60 mL of xylene as a dehydrating agent were added to the reaction vessel. Under a protective atmosphere of nitrogen deoxygenation, the mixture was first heated to 150 °C for reflux to remove water until the theoretical water output was reached. The reaction was continued at this temperature for 30 min. The xylene was then evaporated by heating, and the temperature was then increased to 220 °C for polymerization for 5.5 h. After the reaction was completed, the product was precipitated with water, washed, and dried to obtain bisphenol AF type polyether ether ketone. The molecular weight of the product was determined by GPC. n =2.7×10 5 g / mol, M w =7.9×10 5 g / mol, PDI=2.92.

[0038] Preparation Example 2

[0039] The bisphenol AF type polyether ether ketone obtained in Preparation Example 1 was pulverized to an average particle size of less than 500 micrometers. It was then added to 98wt% concentrated sulfuric acid at a ratio of 1g:10mL. After stirring and dissolving at 50°C, the reaction was continued for 3 hours. The product was precipitated by cold water, washed, and dried to obtain the sulfonated bisphenol AF type polyether ether ketone, which was designated as SF-PEEK-1.

[0040] Preparation Example 3

[0041] The bisphenol AF type polyether ether ketone obtained in Preparation Example 1 was pulverized to an average particle size of less than 500 micrometers. It was then added to 98wt% concentrated sulfuric acid at a ratio of 1g:10mL. After stirring and dissolving at 40°C, the reaction was continued for 4 hours. The product was precipitated by cold water, washed, and dried to obtain the sulfonated bisphenol AF type polyether ether ketone, which was designated as SF-PEEK-2.

[0042] Preparation Example 4

[0043] The bisphenol AF type polyether ether ketone obtained in Preparation Example 1 was pulverized to an average particle size of less than 500 micrometers. It was then added to 98wt% concentrated sulfuric acid at a ratio of 1g:15mL. After stirring and dissolving at 60°C, the reaction was continued for 2 hours. The product was precipitated by cold water, washed, and dried to obtain the sulfonated bisphenol AF type polyether ether ketone, which was designated as SF-PEEK-3.

[0044] Preparation Example 5

[0045] The modified carbon material in this case consists of multi-walled carbon nanotubes with in-situ attached silver nanoparticles. The preparation process is as follows:

[0046] Multi-walled carbon nanotubes (inner diameter 10-40 nm, aspect ratio greater than 500) were dispersed in a mixed acid of nitric acid and sulfuric acid with a volume ratio of 1:3. The amount of multi-walled carbon nanotubes and mixed acid was 1 g / 10 mL. The mixture was ultrasonically treated at 150 °C for 1 h, washed with water until neutral, and then dried to obtain multi-walled carbon nanotubes with oxygen-containing groups (hydroxyl and / or carboxyl groups).

[0047] The obtained functionalized multi-walled carbon nanotubes were added to an aqueous solution of silver nitrate, with a concentration of 5 g / L. The amount of silver nitrate used was calculated based on the Ag loading being 20% ​​of the mass of the functionalized multi-walled carbon nanotubes. After ultrasonic treatment in an ultrasonic cleaner for 30 min, the mixture was stirred at room temperature for 1 h to allow silver ions to be fully adsorbed onto the surface of the carbon nanotubes. Under a nitrogen protective atmosphere, the mixture was heated to 80 °C, and ascorbic acid solution (molar ratio of ascorbic acid to silver ions was 1.5:1) was added dropwise. The mixture was stirred for another 2 h to carry out the reduction reaction. After the reaction was completed, the mixture was naturally cooled to room temperature and washed multiple times with deionized water and ethanol by centrifugation. Finally, the mixture was dried in a vacuum drying oven at 60 °C for 12 h to obtain a modified carbon material with in-situ silver nanoparticles attached to the surface of carbon nanotubes.

[0048] Preparation Example 6

[0049] The modified carbon material in this case has a structure of in-situ attached copper nanotubes on the surface of multi-walled carbon nanotubes. The preparation process is as follows:

[0050] Multi-walled carbon nanotubes (inner diameter 10-40 nm, aspect ratio greater than 500) were dispersed in a mixed acid of nitric acid and sulfuric acid with a volume ratio of 1:3. The amount of multi-walled carbon nanotubes and mixed acid was 1 g / 8 mL. The mixture was ultrasonically treated at 145 °C for 1.5 h, washed with water until neutral, and then dried to obtain multi-walled carbon nanotubes with oxygen-containing groups (hydroxyl and / or carboxyl groups).

[0051] Under nitrogen protection, the obtained functionalized multi-walled carbon nanotubes were added to an aqueous solution of copper acetate. The concentration of the functionalized multi-walled carbon nanotubes in the aqueous solution of copper acetate was 8 g / L. The amount of copper acetate used was calculated based on the loading of Cu being 35% of the mass of the functionalized multi-walled carbon nanotubes. PVP30 was then added as a stabilizer (concentration of 1 wt% in the system). After ultrasonic treatment in an ultrasonic cleaner for 30 min, the mixture was stirred at room temperature for 1 h to allow copper ions to be fully adsorbed onto the surface of the carbon nanotubes. The mixture was then heated to 80 °C, and ascorbic acid solution (molar ratio of ascorbic acid to silver ions was 2:1, and the addition was completed over 15-20 minutes) was added dropwise. The mixture was stirred for 3 h to carry out the reduction reaction. After the reaction was completed, the mixture was naturally cooled to room temperature. It was then centrifuged and washed multiple times with deionized water and ethanol, freeze-dried, and then vacuum-dried at 60 °C to obtain a modified carbon material with in-situ attached nano-copper on the surface of carbon nanotubes.

[0052] Preparation Example 7

[0053] The modified carbon material in this case consists of multi-walled carbon nanotubes with in-situ attached aluminum-doped zinc oxide nanoparticles. The preparation process is as follows:

[0054] Multi-walled carbon nanotubes (inner diameter 10-40 nm, aspect ratio greater than 500) were dispersed in a mixed acid of nitric acid and sulfuric acid with a volume ratio of 1:3. The amount of multi-walled carbon nanotubes and mixed acid was 1 g / 5 mL. The mixture was ultrasonically treated at 140 °C for 2 h, washed with water until neutral, and then dried to obtain multi-walled carbon nanotubes with oxygen-containing groups (hydroxyl and / or carboxyl groups).

[0055] The obtained functionalized multi-walled carbon nanotubes were added to a mixed aqueous solution of zinc acetate and aluminum nitrate. The concentration of the functionalized multi-walled carbon nanotubes in the silver nitrate aqueous solution was 5 g / L. The amount of AZO was calculated based on the AZO loading being 25% of the mass of the functionalized multi-walled carbon nanotubes. Then, based on the AZO amount, the amounts of zinc acetate and aluminum nitrate were prepared according to the Zn:Al atomic ratio of 97:3. After ultrasonic treatment in an ultrasonic cleaner for 30 min, continuous stirring for 1 h, and then heating to 60℃ and holding at that temperature, 1 mol / L aluminum nitrate was added dropwise. Ammonia water was used for co-precipitation. The pH value of the solution was monitored in real time with a pH meter and the pH value was precisely controlled between 8.5 and 9.0. After reaching the target pH, the solution was stirred at 60°C for 2 hours to age the precipitate. After separating the precipitate, it was washed three times with deionized water and anhydrous ethanol alternately to thoroughly remove impurities such as ammonium ions and nitrate ions. The precipitate was dried in an oven at 80°C for 12 hours to obtain the precursor powder. Then, under nitrogen protection, the temperature was increased to 500°C at 3°C / min and calcined for 2 hours. After cooling along the path, the modified carbon material with the structure of in-situ attached nano-AZO on the surface of carbon nanotubes was obtained.

[0056] Example 1

[0057] This case study describes a method for preparing a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity, including the following steps:

[0058] In Preparation Example 5, 12 wt% of a modified carbon material with in-situ attached silver nanoparticles on the surface of carbon nanotubes, 2 wt% of an interface modifier SF-PEEK-1, and the balance up to 100 wt% of PEEK resin were mixed evenly. The mixture was then melt-blended and extruded using a twin-screw extruder at 360-390°C and a vacuum devouring pressure of less than 10 kPa to obtain granules. The granules were then placed in a molding die and molded under a pressure of 10 MPa and a heating temperature of 380°C for 30 min. After that, the mixture was cooled at a rate of less than 3°C / min to induce crystallization, resulting in a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity.

[0059] Example 2

[0060] This case study describes a method for preparing a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity, including the following steps:

[0061] In Preparation Example 6, 18 wt% of a modified carbon material with in-situ attached copper nanotubes, 2 wt% of an interface modifier SF-PEEK-2, and the balance up to 100 wt% of PEEK resin were mixed evenly. The mixture was then melt-blended and extruded using a twin-screw extruder at 360-390°C and a vacuum devouring pressure of less than 10 kPa to obtain granules. The granules were then placed in a molding die and molded at 15 MPa and 380°C for 30 min. Afterward, the mixture was cooled at a rate of less than 3°C / min to induce crystallization, resulting in a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity.

[0062] Example 3

[0063] This case study describes a method for preparing a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity, including the following steps:

[0064] In Preparation Example 7, 25 wt% of a modified carbon material with in-situ attached nano-AZO on the surface of carbon nanotubes, 3 wt% of an interface modifier SF-PEEK-3, and the balance up to 100 wt% of PEEK resin were mixed evenly. The mixture was then melt-blended and extruded using a twin-screw extruder at 360-390°C and a vacuum devouring pressure of less than 10 kPa to obtain granules. The granules were then placed in a molding die and molded at 12 MPa and 380°C for 40 min. After that, the mixture was cooled at a rate of less than 3°C / min to induce crystallization, resulting in a modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity.

[0065] Comparative Example 1

[0066] The preparation process in this case is the same as in Example 1, except that the modified carbon material is replaced with 10wt% of multi-walled carbon nanotubes (inner diameter 10-40nm, aspect ratio greater than 500) and 2wt% of silver nanoparticles (20-50nm).

[0067] Comparative Example 2

[0068] The preparation process in this case is the same as in Example 1, except that the modified carbon material is replaced with 12wt% of multi-walled carbon nanotubes (inner diameter 10-40nm, aspect ratio greater than 500).

[0069] Comparative Example 3

[0070] The preparation process in this case is the same as in Example 1, except that the modified carbon material is replaced with 12wt% of nano-silver particles (20-50nm).

[0071] Comparative Example 4

[0072] The preparation process in this case is the same as in Example 1, except that the interface modifier is sulfonated polyether ether ketone (sulfonation degree 45%).

[0073] Comparative Example 5

[0074] The preparation process in this case is the same as in Example 1, except that the interface modifier is the fluorinated polyether ether ketone used in Preparation Example 1.

[0075] Test case

[0076] The performance of the composite materials in the above cases was tested, and the results are shown in Table 1.

[0077] Table 1 Properties of Composite Materials

[0078]

[0079] As shown in Table 1, this invention functionalizes multi-walled carbon nanotubes with oxygen-containing groups, and then generates a composite synergistic conductive structure of nano-conductive materials in situ on their surface. Combined with sulfonated polyether ether ketone as an interface modifier, the sulfonic acid groups form strong hydrogen bonds with the carboxyl groups on the filler surface, while the fluoride molecular chains can better integrate with the matrix resin. This reduces filler agglomeration in the composite material and enables high conductivity with a low filler addition amount, while significantly improving the interfacial shear strength and controlling the thermal expansion coefficient and volume shrinkage rate of the composite material at a low level.

[0080] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity, characterized in that, The materials include: modified carbon materials with at least one dimension, interface modifiers, and PAEK resin; The modified carbon material has a structure in which a nano-conductive material is attached in situ to the surface of the carbon nanomaterial, and the nano-conductive material is a nano-conductive metal or a nano-conductive metal oxide.

2. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 1, characterized in that, The composite material comprises 100% by weight of the following materials: 5%-25% modified carbon material with at least one dimension, 1%-3% interface modifier, and the balance being PAEK resin. The proportion of the nano-conductive material in the modified carbon material is in the range of 5%-60%.

3. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 2, characterized in that, The carbon nanomaterial is one or more of carbon nanotubes, carbon nanorods, and carbon fibers with oxygen-containing groups on their surface; The nano-conductive metal is one or more of nano-silver, nano-gold, and nano-copper generated in situ on the surface of the carbon nanomaterial. The nano-conductive metal oxide is formed in situ on the surface of the carbon nanomaterial by one or more of nano-indium tin oxide, nano-tin antimony oxide, and nano-aluminum-doped zinc oxide.

4. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 2, characterized in that, The carbon nanomaterial is selected from one or more of the following: carbon nanotubes with a diameter less than 50 nm and an aspect ratio greater than 500, carbon nanorods with a diameter less than 50 nm and an aspect ratio greater than 500, and carbon fibers with a diameter less than 300 nm and a length of at least 1 μm; the average particle size of the nanoconductive material does not exceed 200 nm.

5. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to any one of claims 1-4, characterized in that, The modified carbon material is obtained by the following steps: forming functionalized carbon nanomaterials by giving the surface of the carbon nanomaterials oxygen-containing groups; adsorbing metal ions using the oxygen-containing groups as anchoring sites; growing nano-conductive materials in situ on the surface of the functionalized carbon nanomaterials by one or more of the following methods: chemical reduction, co-precipitation, hydrothermal, and solvothermal; and performing heat treatment or no heat treatment to obtain a modified carbon material with the structure of nano-conductive materials attached to the surface of carbon nanomaterials in situ.

6. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 5, characterized in that, When the structure of the modified carbon material is that the conductive metal nanoparticles are attached to the surface of the carbon nanomaterials in situ, the modified carbon material is obtained by the following steps: dispersing the functionalized carbon nanomaterials in one or more solutions of water-soluble silver source, water-soluble gold source, and water-soluble copper source to form a reaction solution with a concentration of 5-10 g / L; heating to 60-100°C under a protective atmosphere; adding a reducing agent; stirring to carry out a reduction reaction for 0.5-4 h; cooling, washing, and drying to obtain the modified carbon material with the structure of conductive metal nanoparticles attached to the surface of the carbon nanomaterials in situ. The reducing agent is selected from sodium citrate and / or ascorbic acid; the water-soluble silver source is nitrate; the water-soluble gold source is chloroauric acid; and the water-soluble copper source is copper sulfate or copper acetate.

7. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 5, characterized in that, When the structure of the modified carbon material is that the carbon nanomaterial has nano-conductive metal oxides attached to its surface in situ, the modified carbon material is obtained by the following steps: dispersing the functionalized carbon nanomaterial in a water-soluble raw material solution to form a reaction solution with a concentration of 5-10 g / L, adding an alkaline precipitant dropwise under stirring until the final pH value is greater than 8, transferring it to a high-pressure reactor lined with polytetrafluoroethylene and carrying out a hydrothermal reaction at 120-200℃ for 6-24 h, cooling, washing, drying, and then calcining at 300-800℃ for 1-5 h to obtain the modified carbon material with the structure of nano-conductive metal oxides attached to its surface in situ; The water-soluble raw material solution is one of the following: a mixed solution of tin tetrachloride and antimony trichloride prepared in an atomic ratio of Sn:Sb = 90:10-95:5; a mixed solution of indium trichloride and tin tetrachloride prepared in an atomic ratio of In:Sn = 90:10; or a mixed solution of zinc acetate and aluminum nitrate or aluminum isopropoxide prepared in an atomic ratio of Zn:Al = 95:5-98:

2. The alkaline precipitant is a 0.5-2 mol / L sodium hydroxide solution or an ammonia solution; when in-situ generation of nano-indium tin oxide is required, the endpoint pH is 8.5-9.5; when in-situ generation of nano-tin antimony oxide is required, the endpoint pH is 8.0-9.0; when in-situ generation of nano-aluminum-doped zinc oxide is required, the endpoint pH is 8.0-9.

0.

8. The modified polyaryletherketone composite material with high dimensional stability and high conductivity according to claim 5, characterized in that, A method for functionalizing carbon nanomaterials by giving the surface of the carbon nanomaterials oxygen-containing groups: the carbon nanomaterials are ultrasonically treated with a mixture of nitric acid and sulfuric acid in a volume ratio of 1:2-4 at 140-150°C for 1-2 hours, washed with water until neutral, and then dried to obtain functionalized carbon nanomaterials.

9. The modified polyaryletherketone composite material with high dimensional stability and high electrical conductivity according to any one of claims 1-4, characterized in that, The PAEK resin is selected from one or more of polyetheretherketone, polyetherketone, polyetherketoneketone, polyetheretherketoneketone, and polyetherketoneetherketoneketone. The interface modifier is a sulfonated bisphenol AF type polyether ether ketone. Bisphenol AF type polyether ether ketone powder with an average particle size of less than 1 mm is added to 95 wt%-98 wt% concentrated sulfuric acid at a ratio of 1 g: 5-20 mL. The mixture is stirred and reacted at 40-60℃ for 0.5-4 h. The product is precipitated with cold water, washed, and dried to obtain the sulfonated bisphenol AF type polyether ether ketone. The M of the bisphenol AF type polyether ether ketone n =1-3×10 5 g / mol, Mw = 5-8 × 10 5 g / mol, PDI = 1-3.

5.

10. A method for preparing a modified polyaryletherketone composite material with high dimensional stability and high conductivity, applicable to the preparation of the composite material according to any one of claims 1-9, comprising the following steps: mixing a modified carbon material having at least one dimension, an interface modifier, and PAEK resin according to a formula, followed by melt blending to obtain granules, and then crystallizing them. The modified carbon material is composed of a carbon nanomaterial with an in-situ attached nano-conductive material on its surface, wherein the nano-conductive material is a nano-conductive metal or a nano-conductive metal oxide. The melt blending is achieved using a twin-screw extruder with the following parameters: melt blending temperature 350-400℃, vacuum devouring pressure less than 10kPa; The crystallization molding process involves placing the obtained granules in a molding die and molding them under pressure of at least 8 MPa and a heating temperature of 380-400°C for 10-40 minutes, followed by cooling at a rate of less than 3°C / min.

Images