CN114507356A - Phenolphthalein-based polyaryletherketone-carbon nanotube graft and preparation method thereof, and polyetheretherketone heat-conducting composite material and preparation method thereof - Google Patents
Phenolphthalein-based polyaryletherketone-carbon nanotube graft and preparation method thereof, and polyetheretherketone heat-conducting composite material and preparation method thereof Download PDFInfo
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- CN114507356A CN114507356A CN202210183975.7A CN202210183975A CN114507356A CN 114507356 A CN114507356 A CN 114507356A CN 202210183975 A CN202210183975 A CN 202210183975A CN 114507356 A CN114507356 A CN 114507356A
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- phenolphthalein
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 155
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 155
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 91
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- 241000233788 Arecaceae Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a phenolphthalein-based polyaryletherketone-carbon nanotube graft and a preparation method thereof, and a polyetheretherketone heat-conducting composite material and a preparation method thereof. The invention provides a preparation method of a phenolphthalein-based polyaryletherketone-carbon nanotube graft, which comprises the following steps: under the action of a reducing agent, performing reduction reaction on phenolphthalein-based polyaryletherketone to obtain hydroxylated phenolphthalein-based polyaryletherketone; under the action of an oxidant, carrying out oxidation reaction on the carbon nano tube to obtain a carboxylated carbon nano tube; and mixing the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, the dimethylaminopyridine and the dicyclohexylcarbodiimide with an organic solvent, and carrying out a grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft. The phenolphthalein-based polyaryletherketone-carbon nanotube graft prepared by the method is used as a filler to modify polyetheretherketone, and the obtained polyetheretherketone heat-conducting composite material has excellent heat-conducting capacity.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a phenolphthalein-based polyaryletherketone-carbon nanotube graft and a preparation method thereof, and a polyetheretherketone heat-conducting composite material and a preparation method thereof.
Background
Plastic is widely used as a polymer material, and has gradually replaced metal materials in many fields due to the advantages of light weight, good acid and alkali corrosion resistance, low processing temperature and the like. With the development of communication electronic technology, the volume of integrated circuits is gradually reduced, 5G communication technology is gradually popularized, now higher requirements are provided for the heat dissipation capability of materials, and the low thermal conductivity coefficient of plastics becomes a barrier that can benefit the wider application thereof.
The polyether-ether-ketone as a special engineering plastic has mechanical strength, corrosion resistance, radiation resistance, heat resistance grade, fatigue resistance and the like far exceeding those of common engineering plastics. Meanwhile, the polyetheretherketone also has the problem of low heat conductivity coefficient which is the same as that of other engineering plastics, and is only 0.15-0.20W/K, so that the improvement of the heat conductivity of the polyetheretherketone is very important.
The method of introducing filler is often adopted to improve the heat conductivity of the polymer, the carbon nanotube has better heat conductivity, but when the carbon nanotube is used as the filler, the heat conductivity of the composite material formed by the carbon nanotube and the polymer still needs to be improved.
Disclosure of Invention
The invention aims to provide a phenolphthalein-based polyaryletherketone-carbon nanotube graft and a preparation method thereof, and a polyetheretherketone heat-conducting composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of phenolphthalein-based polyaryletherketone-carbon nanotube graft comprises the following steps:
under the action of a reducing agent, performing reduction reaction on phenolphthalein-based polyaryletherketone to obtain hydroxylated phenolphthalein-based polyaryletherketone;
under the action of an oxidant, carrying out oxidation reaction on the carbon nano tube to obtain a carboxylated carbon nano tube;
and mixing the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, the dimethylaminopyridine and the dicyclohexylcarbodiimide with an organic solvent, and carrying out a grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft.
Preferably, the reducing agent comprises sodium borohydride; the temperature of the reduction reaction is 120-130 ℃, and the time is 0.5-1.5 h.
Preferably, the carbon nanotubes are multi-walled carbon nanotubes; the carbon nano tube has an outer diameter of 40-80 nm and a length of 5-15 μm.
Preferably, the oxidant is a mixture of concentrated nitric acid and concentrated sulfuric acid, the mass fraction of the concentrated nitric acid is 65-68%, the mass fraction of the concentrated sulfuric acid is 96-98%, and the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid in the oxidant is 1: (2.6-3.1); the temperature of the oxidation reaction is 50-52 ℃, and the time is 2-4 h.
Preferably, the temperature of the grafting reaction is 48-52 ℃, and the time is 60-72 h.
The phenolphthalein-based polyaryletherketone-carbon nanotube graft prepared by the preparation method of the technical scheme is provided.
The invention provides a polyether-ether-ketone heat-conducting composite material, which is prepared from polyether-ether-ketone and a phenolphthalein-based polyaryletherketone-carbon nanotube graft according to the technical scheme, wherein the mass fraction of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyether-ether-ketone heat-conducting composite material is 5-30%.
The invention provides a preparation method of the polyether-ether-ketone heat-conducting composite material in the technical scheme, which comprises the following steps:
mixing the phenolphthalein-based polyaryletherketone-carbon nanotube graft with the polyetheretherketone, and then carrying out hot-pressing molding to obtain the polyetheretherketone heat-conducting composite material.
Preferably, the temperature of the hot-press molding is 370-390 ℃, the pressure is 20-50 MPa, and the heat preservation and pressure maintaining time is 10-15 min.
Preferably, the hot press forming further comprises:
preheating and melting a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and polyetheretherketone; the preheating and melting temperature is 370-390 ℃, and the time is 10-15 min.
The invention provides application of the polyether-ether-ketone heat-conducting composite material in the technical scheme or the polyether-ether-ketone heat-conducting composite material prepared by the preparation method in the technical scheme in the field of heat conduction.
The invention provides a preparation method of a phenolphthalein-based polyaryletherketone-carbon nanotube graft, which comprises the following steps: under the action of a reducing agent, performing reduction reaction on phenolphthalein-based polyaryletherketone to obtain hydroxylated phenolphthalein-based polyaryletherketone; under the action of an oxidant, carrying out oxidation reaction on the carbon nano tube to obtain a carboxylated carbon nano tube; and mixing the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, the dimethylaminopyridine and the dicyclohexylcarbodiimide with an organic solvent, and carrying out a grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft. According to the invention, the carbon nano tube and the phenolphthalein-based polyaryletherketone are connected by using a chemical bond in a manner of introducing active sites into the two substances, and the obtained phenolphthalein-based polyaryletherketone-carbon nano tube graft is used for modifying polyetheretherketone, so that the dispersing capacity of the carbon nano tube in the polyetheretherketone can be improved, the heat conduction mode between the two substances is changed, the interface thermal resistance between the carbon nano tube and the polyetheretherketone is greatly reduced, and the heat conduction capacity of the polyetheretherketone heat conduction composite material is effectively improved; on the basis of improving the heat conduction capability, the high strength, high modulus, high hardness and high corrosion resistance of the polyether-ether-ketone material are still maintained, and a new idea is provided for the use of the polyether-ether-ketone material in the field of heat conduction.
Drawings
FIG. 1 is a reaction scheme diagram relating to reduction reaction in the preparation of a phenolphthalein-based polyaryletherketone-carbon nanotube graft according to the present invention;
FIG. 2 is a reaction scheme diagram relating to the grafting reaction in the preparation of a phenolphthalein-based polyaryletherketone-carbon nanotube graft according to the present invention;
FIG. 3 is an IR spectrum of a phenolphthalein-based polyaryletherketone in example 1 before and after hydroxylation;
FIG. 4 is the nuclear magnetic spectrum of phenolphthalein-based polyaryletherketone in example 1 before and after hydroxylation;
FIG. 5 is an IR spectrum of a carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft according to example 1;
FIG. 6 is a peak separation chart of an X-ray photon spectrometer for the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft in example 1;
FIG. 7 is a scanning electron microscope image of the carboxylated carbon nanotubes and phenolphthalein-based polyaryletherketone-carbon nanotube grafts in example 1;
FIG. 8 is a TEM image of the carboxylated carbon nanotubes and phenolphthalein-based PAEK-carbon nanotube grafts in example 1;
FIG. 9 is a thermogram of the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft in example 1;
FIG. 10 is a comparison graph of the thermal conductivity of a polyetheretherketone thermal conductive composite material prepared with phenolphthalein-based polyaryletherketone-carbon nanotube graft as a filler and a polyetheretherketone thermal conductive composite material prepared with carboxylated carbon nanotubes as a filler.
Detailed Description
The invention provides a preparation method of a phenolphthalein-based polyaryletherketone-carbon nanotube graft, which comprises the following steps:
under the action of a reducing agent, performing reduction reaction on phenolphthalein-based polyaryletherketone to obtain hydroxylated phenolphthalein-based polyaryletherketone;
under the action of an oxidant, carrying out oxidation reaction on the carbon nano tube to obtain a carboxylated carbon nano tube;
and mixing the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, the dimethylaminopyridine and the dicyclohexylcarbodiimide with an organic solvent, and carrying out a grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft.
Unless otherwise specified, the starting materials for the preparation used in the present invention are commercially available products well known to those skilled in the art.
The invention carries out reduction reaction on phenolphthalein-based polyaryletherketone under the action of a reducing agent to obtain the hydroxylated phenolphthalein-based polyaryletherketone. In the present invention, the reducing agent preferably comprises sodium borohydride, and the mass ratio of the reducing agent to the phenolphthalein-based polyaryletherketone is preferably 1: (7.0 to 9.5), more preferably 1: (7.5 to 9.0), and more preferably 1: (8.5-9.0). In the present invention, the reduction reaction is preferably carried out in the presence of an organic solvent, preferably dimethyl sulfoxide (DMSO), more preferably anhydrous DMSO; the preferable dosage ratio of the organic solvent to the phenolphthalein-based polyaryletherketone is 250 mL: (24-26) g, more preferably 250 mL: 25 g. According to the invention, preferably, in a protective atmosphere, a reducing agent is dissolved in an organic solvent to obtain a reducing agent solution; and then mixing the reducing agent solution with phenolphthalein-based polyaryletherketone for reduction reaction. The type of the protective gas for providing the protective atmosphere is not particularly limited in the present invention, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
In the invention, the temperature of the reduction reaction is preferably 120-130 ℃, and more preferably 120-125 ℃; the time is preferably 0.5-1.5 h, and more preferably 1 h; the reduction reaction is preferably carried out in a protective atmosphere. The present invention uses the reduction reaction to modify the surface of phenolphthalein-based polyaryletherketone, so that the carbonyl group on the surface of the phenolphthalein-based polyaryletherketone is reduced to hydroxyl, and the reaction scheme involved is shown in fig. 1.
After the reduction reaction, the obtained product system is preferably naturally cooled to room temperature (25 ℃), then mixed with isopropanol, the obtained mixed feed liquid is filtered, and a filter cake is sequentially washed and dried to obtain the hydroxylated phenolphthalein-based polyaryletherketone. In the present invention, the isopropyl alcohol functions to precipitate a reaction product. In the invention, the washing is preferably washed by ethanol, hydrochloric acid and distilled water in sequence, the washing frequency is preferably 2-3 times, and each washing is preferably washed by ethanol, hydrochloric acid and distilled water in sequence; the concentration of the hydrochloric acid is preferably 3-5 wt%. In the invention, the drying temperature is preferably 120-130 ℃, and more preferably 125-130 ℃; the time is preferably 2.5 to 3.5 hours, and more preferably 3 to 3.5 hours.
The invention carries out oxidation reaction on the carbon nano tube under the action of an oxidant to obtain the carboxylated carbon nano tube. In the invention, the oxidant is preferably a mixture of concentrated nitric acid and concentrated sulfuric acid, the mass fraction of the concentrated nitric acid is preferably 65-68%, the mass fraction of the concentrated sulfuric acid is preferably 96-98%, and the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid in the oxidant is preferably 1: (2.6-3.1), more preferably 1: (2.9-3.1), more preferably 1: (3.0-3.1). In the invention, the carbon nanotube is preferably a multi-wall carbon nanotube, the outer diameter of the carbon nanotube is preferably 40-80 nm, and the length of the carbon nanotube is preferably 5-15 μm. In the present invention, the ratio of the amount of the carbon nanotubes to the oxidant is preferably 1: (6-10), more preferably 1: (7-8), more preferably 1: (7-7.5). The present invention preferably mixes the carbon nanotubes with an oxidizing agent to perform an oxidation reaction.
In the invention, the temperature of the oxidation reaction is preferably 50-52 ℃, and more preferably 51-52 ℃; the time is preferably 2 to 4 hours, and more preferably 3 to 4 hours. After the oxidation reaction, the obtained product system is preferably subjected to suction filtration, and the obtained filter cake is washed and dried in sequence to obtain the carboxylated carbon nanotube. In the invention, the washing is preferably carried out by firstly adopting ethanol and then adopting deionized water to wash until the solution is neutral; the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 92-96 ℃, and more preferably 94-95 ℃; the time is preferably 20 to 24 hours, and more preferably 22 to 24 hours.
After obtaining the hydroxylated phenolphthalein-based polyaryletherketone and the carboxylated carbon nanotube, the invention mixes the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, Dimethylaminopyridine (DMAP), Dicyclohexylcarbodiimide (DCC) and an organic solvent for grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft. In the invention, the mass ratio of the hydroxylated phenolphthalein-based polyaryletherketone to the carboxylated carbon nanotube is preferably (2.85-3.25): (0.95-1.05), more preferably (3-3.2): 1; the mass ratio of the hydroxylated phenolphthalein-based polyaryletherketone to the DMAP to the DCC is preferably (2.95-3.25): (0.42-0.48): (2.8-3.2), more preferably (3-3.2): (0.45-0.47): (3.0-3.2), the DMAP is used as a catalyst, and the DCC is used as a dehydrating agent; the organic solvent is preferably N, N-Dimethylformamide (DMF), and more preferably anhydrous DMF, and the amount of the organic solvent is not particularly limited in the present invention, so as to ensure that the grafting reaction proceeds smoothly. Preferably, the carboxylated carbon nanotube is mixed with part of the organic solvent, and ultrasonic dispersion is carried out to obtain a carboxylated carbon nanotube dispersion liquid; mixing the hydroxylated phenolphthalein-based polyaryletherketone, DMAP (dimethyl acetamide) and DCC (DCC) with the rest of organic solvent, after completely dissolving, mixing the obtained mixed material with the carboxylated carbon nanotube dispersion liquid in a protective atmosphere, and carrying out grafting reaction.
In the invention, the temperature of the grafting reaction is preferably 48-52 ℃, and more preferably 50-52 ℃; the time is preferably 60 to 72 hours, and more preferably 68 to 72 hours. In the present invention, the reaction scheme involved in the grafting reaction is shown in FIG. 2.
After the grafting reaction, the invention preferably filters the obtained system, and sequentially washes and dries the obtained filter cake to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft. In the present invention, the reagent used for the washing is preferably DMF; the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 65-80 ℃, more preferably 70 ℃, and the time of the vacuum drying is preferably 20-30 hours, more preferably 24 hours. In the invention, the grafting ratio of the carbon nanotubes in the phenolphthalein-based polyaryletherketone-carbon nanotube graft is preferably 5-13%, and more preferably 10-13%.
The invention provides a phenolphthalein-based polyaryletherketone-carbon nanotube graft prepared by the preparation method in the technical scheme.
The invention provides a polyether-ether-ketone heat-conducting composite material, which is prepared from polyether-ether-ketone and the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the technical scheme, wherein the mass fraction of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyether-ether-ketone heat-conducting composite material is 5-30%, and specifically can be 5%, 10%, 15%, 20%, 25% or 30%.
The invention provides a preparation method of the polyether-ether-ketone heat-conducting composite material in the technical scheme, which comprises the following steps:
mixing the phenolphthalein-based polyaryletherketone-carbon nanotube graft with the polyetheretherketone, and then carrying out hot-pressing molding to obtain the polyetheretherketone heat-conducting composite material.
In the invention, the preferred mixing mode of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and the polyetheretherketone is wet mixing, specifically, the phenolphthalein-based polyaryletherketone-carbon nanotube graft is mixed with ethanol under the ultrasonic condition to obtain phenolphthalein-based polyaryletherketone-carbon nanotube graft dispersion liquid; mixing the phenolphthalein-based polyaryletherketone-carbon nanotube graft dispersion liquid with polyetheretherketone under the stirring condition, filtering the obtained mixture, and drying the obtained filter cake to obtain a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and polyetheretherketone. In the invention, the time of the ultrasonic treatment is preferably 1.5-2.5 h, and more preferably 2 h; the mass ratio of ethanol to polyetheretherketone is preferably 100: (3-5), more preferably 100: 4; the stirring time is preferably 10-15 h, and more preferably 12 h; the drying temperature is preferably 110-130 ℃, more preferably 120 ℃, and the drying time is preferably 2-4 h, more preferably 3 h.
In the invention, the temperature of the hot-press forming is preferably 370-390 ℃, and more preferably 380-390 ℃; the pressure is preferably 20-50 MPa, and more preferably 29-40 MPa; the heat preservation and pressure maintaining time is preferably 10-15 min, and more preferably 13-15 min. In the invention, before the hot press molding, the mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and the polyetheretherketone is preferably preheated and melted; the preheating and melting temperature is preferably 370-390 ℃, the time is preferably 10-15 min, and the preheating and melting are preferably carried out under the pressure-free condition; and after preheating and melting, adjusting the pressure to 20-50 MPa for hot press molding. In the examples of the present invention, the thermoforming is carried out in particular in a tablet press.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Some of the feedstock sources referred to in the examples below include:
phenolphthalein-based polyaryletherketone powder (Phenolphthalaein polyether ketone, PEK-C, PAEKNM-01) was purchased from New materials Co., Ltd, Palmae, Zhejiang province;
the Multi-walled carbon nanotubes (MWCNTs) have the outer diameter of 40-80 nm, the length of 5-15 mu m and the purity of 97.5 wt%, and are purchased from Shandong Dachang nanometer materials, Inc.;
polyetheretherketone Powder (PEEK) was purchased from vinpoclada plastic engineering research ltd.
Example 1
(1) Adding 3g of sodium borohydride into 250mL of anhydrous dimethyl sulfoxide, and magnetically stirring under the protection of nitrogen until the sodium borohydride is fully dissolved to obtain a sodium borohydride solution; adding 25g of phenolphthalein-based polyaryletherketone (PEK-C) powder into the sodium borohydride solution, and reacting for 1h at the temperature of 120 ℃ under the protection of nitrogen; stopping heating after the reaction is finished, naturally cooling to room temperature, discharging the obtained product system into isopropanol, performing suction filtration, washing the obtained filter cake with ethanol, dilute hydrochloric acid (the concentration is 3 wt%) and distilled water in sequence, performing 3 washing processes by using ethanol washing, dilute hydrochloric acid washing and distilled water washing as 1 washing process, and drying the washed material at 120 ℃ for 2.5 hours to obtain hydroxylated phenolphthalein-based polyaryletherketone (PEK-C-OH);
(2) mixing 2g of multi-walled carbon nanotubes, 3.59g of concentrated nitric acid and 10.40g of concentrated sulfuric acid (namely the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 2.9), heating to 50 ℃ and reacting for 4 hours, wherein the mass fraction of the concentrated nitric acid is 65%, and the mass fraction of the concentrated sulfuric acid is 98%; after the reaction is finished, performing suction filtration on the obtained product system, washing the obtained filter cake with ethanol, then washing the filter cake with deionized water to be neutral, and performing vacuum drying on the washed material in a vacuum drying oven at 94 ℃ for 24 hours to obtain a carboxylated carbon nanotube (MWCNTs-COOH);
(3) accurately weighing 1g of carboxylated carbon nanotube, adding the 1g of carboxylated carbon nanotube into 200mL of anhydrous N, N-dimethylformamide, and performing ultrasonic dispersion to obtain a carboxylated carbon nanotube dispersion liquid; weighing 3g of hydroxylated phenolphthalein-based polyaryletherketone, 0.45g of dimethylaminopyridine and 3.0g of dicyclohexylcarbodiimide, adding the mixture into 100mL of anhydrous N, N-dimethylformamide, adding a carboxylated carbon nanotube dispersion liquid into the obtained mixed solution after complete dissolution, and reacting for 72 hours at 50 ℃ under the protection of nitrogen; after the reaction is finished, filtering the obtained product system, washing a filter cake by using N, N-dimethylformamide to remove redundant dimethylaminopyridine, dicyclohexylcarbodiimide and unreacted hydroxylated phenolphthalein-based polyaryletherketone, and carrying out vacuum drying on the washed material in a vacuum drying oven at 70 ℃ for 24 hours to obtain a phenolphthalein-based polyaryletherketone-carbon nanotube graft (PEK-C-OH-g-MWCNTs-COOH), wherein the grafting rate of the carboxylated carbon nanotube is 10%;
(4) adding 1g of phenolphthalein polyaryletherketone-carbon nanotube graft into 360mL of ethanol for ultrasonic dispersion for 2h, then adding 9g of Polyetheretherketone (PEEK) powder (namely the mass ratio of the volume of the ethanol to the polyetheretherketone powder is 0.04L: 1g), and mechanically stirring for 12 h; and then filtering the obtained suspension, drying a filter cake for 3h at 120 ℃ to obtain a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and polyetheretherketone, preheating and melting the mixture for 10min at 370 ℃ under a non-pressure condition by using a tablet press, then adjusting the pressure to 20MPa, and pressing the mixture for 10min at 370 ℃ to obtain the polyetheretherketone heat-conducting composite material (PEK-C-OH-g-MWCNTs-COOH/PEEK) with the thickness of 0.6mm and the heat conductivity of 0.46W/(m.K) in the vertical direction (namely the thickness direction).
Example 2
(1) Adding 3.2g of sodium borohydride into 250mL of anhydrous dimethyl sulfoxide, and magnetically stirring under the protection of nitrogen until the sodium borohydride is fully dissolved to obtain a sodium borohydride solution; adding 25g of phenolphthalein-based polyaryletherketone powder into the sodium borohydride solution, and reacting for 1h at 120 ℃ under the protection of nitrogen; stopping heating after the reaction is finished, naturally cooling to room temperature, discharging the obtained product system into isopropanol, performing suction filtration, repeatedly washing the obtained filter cake for 3 times by using ethanol, dilute hydrochloric acid (the concentration is 4 wt%) and distilled water in sequence, and drying the washed material at 125 ℃ for 3 hours to obtain the hydroxylated phenolphthalein-based polyaryletherketone;
(2) mixing 2g of multi-walled carbon nanotubes, 3.60g of concentrated nitric acid and 10.80g of concentrated sulfuric acid (namely the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3), heating to 52 ℃ and reacting for 3 hours, wherein the mass fraction of the concentrated nitric acid is 65%, and the mass fraction of the concentrated sulfuric acid is 98%; after the reaction is finished, carrying out suction filtration on the obtained product system, sequentially washing the obtained filter cake to be neutral by using absolute ethyl alcohol and deionized water, and carrying out vacuum drying on the washed material in a vacuum drying oven at 95 ℃ for 24 hours to obtain a carboxylated carbon nanotube;
(3) accurately weighing 1g of carboxylated carbon nanotube, adding the 1g of carboxylated carbon nanotube into 200mL of anhydrous N, N-dimethylformamide, and performing ultrasonic dispersion to obtain a carboxylated carbon nanotube dispersion liquid; weighing 3g of hydroxylated phenolphthalein-based polyaryletherketone, 0.45g of dimethylaminopyridine and 3.0g of dicyclohexylcarbodiimide, adding the weighed materials into 100mL of anhydrous N, N-dimethylformamide, adding a carboxylated carbon nanotube dispersion liquid into the obtained mixed solution after complete dissolution, and reacting for 72 hours at 50 ℃ under the protection of nitrogen; after the reaction is finished, filtering the obtained product system, washing a filter cake by using N, N-dimethylformamide to remove redundant dimethylaminopyridine, dicyclohexylcarbodiimide and unreacted hydroxylated phenolphthalein-based polyaryletherketone, and carrying out vacuum drying on the washed material in a vacuum drying oven at 70 ℃ for 24 hours to obtain a phenolphthalein-based polyaryletherketone-carbon nanotube graft, wherein the grafting rate of the carboxylated carbon nanotube is 12%;
(4) adding 2g of phenolphthalein polyaryletherketone-carbon nanotube graft into 360mL of ethanol for ultrasonic dispersion for 2h, then adding 8g of polyetheretherketone powder (namely the mass ratio of the volume of the ethanol to the polyetheretherketone powder is 0.045L: 1g), and mechanically stirring for 12 h; and then filtering the obtained suspension, drying a filter cake for 3h at 120 ℃ to obtain a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and the polyetheretherketone, preheating and melting for 12min at 380 ℃ without pressure by using a tablet press, then adjusting the pressure to 29MPa, and pressing for 15min at 378 ℃ to obtain the polyetheretherketone heat-conducting composite material with the thickness of 0.6mm, wherein the heat conductivity in the vertical direction is 0.64W/(m.K).
Example 3
(1) Adding 2.8g of sodium borohydride into 250mL of anhydrous dimethyl sulfoxide, and magnetically stirring under the protection of nitrogen until the sodium borohydride is fully dissolved to obtain a sodium borohydride solution; adding 25g of phenolphthalein-based polyaryletherketone powder into the sodium borohydride solution, and reacting for 1h at 120 ℃ under the protection of nitrogen; stopping heating after the reaction is finished, naturally cooling to room temperature, discharging the obtained product system into isopropanol, performing suction filtration, repeatedly washing the obtained filter cake for 3 times by using ethanol, dilute hydrochloric acid (the concentration is 5 wt%) and distilled water in sequence, and drying the washed material at 130 ℃ for 3.5 hours to obtain the hydroxylated phenolphthalein-based polyaryletherketone;
(2) mixing 2g of multi-walled carbon nanotubes, 3.5g of concentrated nitric acid and 10.85g of concentrated sulfuric acid (namely the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3.1), heating to 52 ℃ and reacting for 3 hours, wherein the mass fraction of the concentrated nitric acid is 65 percent, and the mass fraction of the concentrated sulfuric acid is 98 percent; after the reaction is finished, filtering the obtained product system, washing the obtained filter cake to be neutral by using absolute ethyl alcohol and deionized water in sequence, and carrying out vacuum drying on the washed material in a vacuum drying oven at 95 ℃ for 24 hours to obtain a carboxylated carbon nano tube;
(3) accurately weighing 1g of carboxylated carbon nanotube, adding the 1g of carboxylated carbon nanotube into 200mL of anhydrous N, N-dimethylformamide, and performing ultrasonic dispersion to obtain a carboxylated carbon nanotube dispersion liquid; weighing 3.2g of hydroxylated phenolphthalein-based polyaryletherketone, 0.47g of dimethylaminopyridine and 3.2g of dicyclohexylcarbodiimide, adding the mixture into 100mL of anhydrous N, N-dimethylformamide, adding the carboxylated carbon nanotube dispersion liquid into the obtained mixed solution after complete dissolution, and reacting for 72 hours at 50 ℃ under the protection of nitrogen; after the reaction is finished, filtering the obtained product system, washing a filter cake by using N, N-dimethylformamide to remove redundant dimethylaminopyridine, dicyclohexylcarbodiimide and unreacted hydroxylated phenolphthalein-based polyaryletherketone, and carrying out vacuum drying on the washed material in a vacuum drying oven at 70 ℃ for 24 hours to obtain a phenolphthalein-based polyaryletherketone-carbon nanotube graft, wherein the grafting rate of the carboxylated carbon nanotube is 13%;
(4) adding 3g of phenolphthalein polyaryletherketone-carbon nanotube graft into 315mL of ethanol for ultrasonic dispersion for 2h, then adding 7g of polyetheretherketone powder (namely the mass ratio of the volume of the ethanol to the polyetheretherketone powder is 0.045L: 1g), and mechanically stirring for 12 h; and then filtering the obtained suspended substance, drying a filter cake for 3h at 120 ℃ to obtain a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and the polyetheretherketone, preheating and melting for 15min at 390 ℃ under a non-pressure condition by using a tablet press, then adjusting the pressure to 40MPa, and pressing for 13min at 390 ℃ to obtain the polyetheretherketone heat-conducting composite material with the thickness of 0.6 mm.
Example 4
The polyetheretherketone thermal composite material is prepared according to the method of the embodiment 3, except that the content of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyetheretherketone thermal composite material is 20%.
Example 5
The polyetheretherketone thermal composite material is prepared according to the method of the embodiment 3, except that the content of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyetheretherketone thermal composite material is 10%.
Example 6
The polyetheretherketone thermal composite material is prepared according to the method of the embodiment 3, except that the content of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyetheretherketone thermal composite material is 5%.
Comparative example 1
The polyetheretherketone thermal composite material is prepared according to the method of example 3, except that the steps (1) and (3) are omitted, that is, the carboxylated carbon nanotubes prepared in the step (2) are directly used as a filler, and the polyetheretherketone thermal composite material is prepared according to the method of the step (4), wherein the content of the carboxylated carbon nanotubes in the polyetheretherketone thermal composite material is 26.10%.
Comparative example 2
The polyetheretherketone thermal composite material was prepared according to the method of comparative example 1, except that the content of the carboxylated carbon nanotubes in the polyetheretherketone thermal composite material was 17.40%.
Comparative example 3
The polyetheretherketone thermal composite material was prepared according to the method of comparative example 1, except that the content of the carboxylated carbon nanotubes in the polyetheretherketone thermal composite material was 8.70%.
Comparative example 4
The polyetheretherketone thermal composite material was prepared according to the method of comparative example 1, except that the content of the carboxylated carbon nanotubes in the polyetheretherketone thermal composite material was 4.35%.
Comparative example 5
The polyetheretherketone material was prepared by the hot press molding method of step (4) of example 3 using polyetheretherketone powder as a raw material without adding any filler.
Characterization and Performance testing
FIG. 3 is an IR spectrum before and after hydroxylation of a phenolphthalein-based polyaryletherketone in example 1 at 1650cm-1The absorption peak is the characteristic peak of aromatic ketone (Ar-CO-Ar) carbonyl in phenolphthalein-based polyaryletherketone, and in the spectrum of hydroxylated phenolphthalein-based polyaryletherketone, 1650cm is corresponded to-1The peak at (b) substantially disappeared, 1766cm-1Is the characteristic absorption peak of C ═ O of five-membered lactone ring in phenolphthalein-based polyaryletherketone and hydroxylated phenolphthalein-based polyaryletherketone, and is 3500cm in hydroxylated phenolphthalein-based polyaryletherketone-1The peak value is enlarged, which indicates that a large amount of hydroxyl groups are indeed generated after the phenolphthalein-based polyaryletherketone is reduced by sodium borohydride, and other molecular structures in the phenolphthalein-based polyaryletherketone are not damaged, and the method preliminarily proves that the hydroxylated phenolphthalein-based polyaryletherketone is successfully prepared.
FIG. 4 is the nuclear magnetic spectrum of the phenolphthalein-based polyaryletherketone before and after hydroxylation in example 1, the chemical shift of hydrogen on the benzene ring is generally concentrated between 6 and 8, while at 5.7ppm the hydroxylated phenolphthalein-based polyaryletherketone has a peak more than that of the phenolphthalein-based polyaryletherketone before hydroxylation, which is the chemical shift peak of hydrogen in a dibenzyl group.
FIG. 5 is the IR spectrum of the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft of example 1, wherein 1764cm-1The characteristic absorption peak of C ═ O of the hydroxylated phenolphthalein polyaryletherketone five-membered lactone ring is positioned, and in the infrared spectrogram of the phenolphthalein polyaryletherketone-carbon nanotube graft, 1725cm is-1A new peak due to the generation of carbonyl (C ═ O) in the ester group appears, and therefore, it can be proved that the molecular chain of the hydroxylated phenolphthalein polyaryletherketone is successfully grafted on the carboxylated carbon nanotube.
FIG. 6 is the peak images of the X-ray photon spectrometer of the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft in example 1, wherein (a) is before grafting and (b) is after grafting. The results show that the proportion of-COOH after grafting is reduced and the proportion of C-OH is increased, which further proves that the hydroxylated phenolphthalein polyaryletherketone is successfully grafted to the surface of the carboxylated carbon nanotube.
FIG. 7 is a scanning electron microscope image of the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft of example 1, wherein (a) is before grafting and (b) is after grafting. It can be seen that the tube length of the carboxylated carbon nanotube is longer, the surface is relatively smooth, but the winding between the tubes is particularly serious, and the distribution between the tubes in the phenolphthalein-based polyaryletherketone-carbon nanotube graft is more dispersed, so that the winding phenomenon is greatly reduced.
FIG. 8 is a transmission electron microscope image of the carboxylated carbon nanotubes and phenolphthalein-based polyaryletherketone-carbon nanotube grafts in example 1 (left side before grafting and right side after grafting) showing that the diameter of the carboxylated carbon nanotubes is increased and the surface roughness is also increased, which further confirms that the hydroxylated phenolphthalein-based polyaryletherketone is successfully grafted onto the carboxylated carbon nanotubes.
FIG. 9 is a thermogram of the carboxylated carbon nanotube and phenolphthalein-based polyaryletherketone-carbon nanotube graft in example 1, wherein (a) is a TGA curve, and (b) is a DTG curve. The results show that the phenolphthalein-based polyaryletherketone shows excellent thermal stability, the initial thermal decomposition temperature (the temperature corresponding to 5% of thermal weight loss) is up to 488 ℃, while the hydroxylated phenolphthalein-based polyaryletherketone has the initial thermal decomposition temperature of only 328 ℃ due to the existence of-OH, but the phenolphthalein-based polyaryletherketone-carbon nanotube graft shows relatively high thermal stability, the initial thermal decomposition temperature is 471 ℃, which completely meets the temperature (about 370 ℃) when processing polyetheretherketone.
And (3) carrying out a thermal conductivity test on the materials prepared in the embodiments 3-6 and the comparative examples 1-5, wherein the material prepared in the embodiments 3-6 is marked as PEK-C-OH-g-MWCNTs-COOH/PEEK, the material prepared in the comparative examples 1-4 is marked as MWCNTs-COOH/PEEK, and the material prepared in the comparative example 5 is the material with the content of 0, namely the phenolphthalein based polyaryletherketone-carbon nanotube graft (PEK-C-OH-g-MWCNTs-COOH) or the carboxylated carbon nanotube (MWCNTs-COOH). FIG. 10 is a comparison graph of thermal conductivities of a polyetheretherketone thermal conductive composite material prepared by using a phenolphthalein-based polyaryletherketone-carbon nanotube graft as a filler and a polyetheretherketone thermal conductive composite material prepared by using a carboxylated carbon nanotube as a filler, wherein a triangular legend in FIG. 10 represents an in-plane thermal conductivity of PEK-C-OH-g-MWCNTs-COOH/PEEK, a square legend represents an out-of-plane thermal conductivity (i.e., a vertical thermal conductivity) of PEK-C-OH-g-MWCNTs-COOH/PEEK, and a circular legend represents an out-of-plane thermal conductivity (i.e., a vertical thermal conductivity) of MWCNTs-COOH/PEEK. As can be seen from fig. 10, the carboxylated carbon nanotubes and the hydroxylated phenolphthalein-based polyaryletherketone are subjected to a grafting reaction to obtain a phenolphthalein-based polyaryletherketone-carbon nanotube graft, and the polyetheretherketone is modified by using the phenolphthalein-based polyaryletherketone-carbon nanotube graft as a filler, so that compared with the modification of polyetheretherketone by directly using the carboxylated carbon nanotubes as a filler, the obtained polyetheretherketone heat-conducting composite material has significantly improved heat-conducting performance. The specific data are shown in Table 1.
TABLE 1 thermal conductivity test results of PEK-C-OH-g-MWCNTs-COOH/PEEK and MWCNTs-COOH/PEEK
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of phenolphthalein-based polyaryletherketone-carbon nanotube graft comprises the following steps:
under the action of a reducing agent, performing reduction reaction on phenolphthalein-based polyaryletherketone to obtain hydroxylated phenolphthalein-based polyaryletherketone;
under the action of an oxidant, carrying out oxidation reaction on the carbon nano tube to obtain a carboxylated carbon nano tube;
and mixing the hydroxylated phenolphthalein-based polyaryletherketone, the carboxylated carbon nanotube, the dimethylaminopyridine and the dicyclohexylcarbodiimide with an organic solvent, and carrying out a grafting reaction to obtain the phenolphthalein-based polyaryletherketone-carbon nanotube graft.
2. The method of claim 1, wherein the reducing agent comprises sodium borohydride; the temperature of the reduction reaction is 120-130 ℃, and the time is 0.5-1.5 h.
3. The method of claim 1, wherein the carbon nanotubes are multi-walled carbon nanotubes; the carbon nano tube has an outer diameter of 40-80 nm and a length of 5-15 μm.
4. The preparation method according to claim 1, wherein the oxidant is a mixture of concentrated nitric acid and concentrated sulfuric acid, the mass fraction of the concentrated nitric acid is 65-68%, the mass fraction of the concentrated sulfuric acid is 96-98%, and the mass ratio of the concentrated nitric acid to the concentrated sulfuric acid in the oxidant is 1: (2.6-3.1); the temperature of the oxidation reaction is 50-52 ℃, and the time is 2-4 h.
5. The preparation method according to claim 1, wherein the temperature of the grafting reaction is 48-52 ℃ and the time is 60-72 h.
6. The phenolphthalein-based polyaryletherketone-carbon nanotube graft prepared by the preparation method of any one of claims 1 to 5.
7. A polyether-ether-ketone heat-conducting composite material is prepared from polyether-ether-ketone and the phenolphthalein-based polyaryletherketone-carbon nanotube graft of claim 6, wherein the mass fraction of the phenolphthalein-based polyaryletherketone-carbon nanotube graft in the polyether-ether-ketone heat-conducting composite material is 5-30%.
8. The preparation method of the polyetheretherketone thermal composite material of claim 7, comprising the steps of:
mixing the phenolphthalein-based polyaryletherketone-carbon nanotube graft with the polyetheretherketone, and then carrying out hot-pressing molding to obtain the polyetheretherketone heat-conducting composite material.
9. The preparation method according to claim 8, wherein the hot press forming temperature is 370-390 ℃, the pressure is 20-50 MPa, and the holding time is 10-15 min.
10. The production method according to claim 8 or 9, further comprising, before the hot press molding:
preheating and melting a mixture of the phenolphthalein-based polyaryletherketone-carbon nanotube graft and polyetheretherketone; the preheating and melting temperature is 370-390 ℃, and the time is 10-15 min.
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