CN115125634B - Method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fiber based on electrostatic spinning technology, polyarylether composite material and application - Google Patents
Method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fiber based on electrostatic spinning technology, polyarylether composite material and application Download PDFInfo
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Abstract
The invention provides a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, a polyarylether composite material and application, and belongs to the technical field of composite materials. Mixing polyaryletherketone imine, a filler and an organic solvent to obtain a spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material; and (3) carrying out electrostatic spinning on the spinning solution to obtain the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber. The filler in the polyarylether composite fiber provided by the invention has an oriented arrangement structure, can construct an excellent electric conduction and heat conduction network, provides a stable transmission channel for phonons and electrons, reduces interface thermal resistance, and is beneficial to heat flow; meanwhile, the electromagnetic wave shielding structure is beneficial to enhancing the reflection and absorption loss of electromagnetic waves, thereby improving the shielding efficiency. Therefore, the polyarylether composite material prepared based on the polyarylether composite fiber has excellent heat conducting performance and electromagnetic shielding performance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, a polyarylether composite material and application.
Background
With the advent of the 5G era, communication equipment has higher operating speed and larger information storage capacity, and densification, integration, light weight, high power density and the like become development characteristics of electronic communication equipment, but the development characteristics will cause electronic circuits and elements to generate huge heat, and if the heat is difficult to dissipate in time, the stability of signal transmission and the service life of the electronic elements will be affected. In addition, the health of people and the stability of communication transmission are seriously damaged by the problem of electromagnetic wave interference generated therewith. The polymer has excellent mechanical properties, corrosion resistance, thermal stability, light weight and easy processability, so that the development of the heat-conducting electromagnetic shielding polymer matrix composite material has important application research significance and application value.
The polyarylether is aromatic thermoplastic special engineering plastic, has excellent high temperature resistance, good biocompatibility, mechanical property, electrical insulation property, chemical corrosion resistance, radiation resistance, friction resistance, flame retardance and the like, and is widely applied to the fields of aerospace, electronics and electricity, medical treatment, petrochemical industry, machinery, automobiles and the like. However, the polyarylether itself has poor heat dissipation and anti-electromagnetic interference capability, which limits its application in heat dissipation and electromagnetic shielding. Therefore, the improvement of the thermal conductivity and electromagnetic shielding performance of the polyarylether composite material is imminent.
Researches show that adding the filler and making the filler oriented and arranged and constructing a good heat conducting network are effective strategies for enhancing the electric heating performance of the composite material. For example, chinese patent CN108485277B discloses an orientation-aligned high thermal conductive interface material, which is specifically prepared by applying a magnetic field and an electric field to the raw materials of a thermal conductive interface material and thermally curing, and the method utilizes the driving action of the electric field and the magnetic field to orient and align the conductive and magnetic particles in a composite material system, thereby perfecting the thermal conductive network in the composite material system and obtaining the orientation-aligned high thermal conductive interface material. Chinese patent CN111393798B discloses an orientation arrangement graphene/epoxy resin high thermal conductive composite material, which is prepared by using graphene soaking film fragments as thermal conductive fillers, pouring the thermal conductive fillers together with epoxy resin for thermosetting, and completing orientation arrangement of the thermal conductive fillers in the process. However, the method has certain limitations on the polyarylether composite system because the polyarylether resins mostly have poor dissolving capacity and high processing temperature, and in addition, the polyarylether resins are thermoplastic materials, and the method is difficult to prepare the polyarylether composite materials with oriented filler arrangement.
Disclosure of Invention
The invention aims to provide a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, a polyarylether composite material and application.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, which comprises the following steps of:
mixing polyaryletherketone imine, a filler and an organic solvent to obtain a spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material;
and (3) carrying out electrostatic spinning on the spinning solution to obtain the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber.
Preferably, the graphene nanosheet material is an unfunctionalized graphene nanosheet or a functionalized graphene nanosheet; the functionalized graphene nanosheet is one or more of an amino graphene nanosheet, a carboxyl graphene nanosheet and a hydroxyl graphene nanosheet.
Preferably, the thickness of the graphene nanosheet material is 1 to 20nm, and the size of the plate diameter is 1 to 20 μm.
Preferably, the mass of the filler is 1-30% of the total mass of the filler and the polyaryletherketone imine; the mass fraction of the graphene nanosheet material in the filler is 10-50%.
Preferably, the total content of the polyaryletherketone imine and the filler in the spinning solution is 7-20 wt%.
Preferably, the method of electrospinning the spinning solution comprises: and (3) placing the spinning solution into an injector, placing the injector containing the spinning solution into a propeller, then carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber.
Preferably, the conditions of the electrospinning include: the propelling speed of the propeller is 0.01-0.20 mL/min, and the distance between the needle point of the syringe and the collecting plate is 5-20 cm; the voltage is 5-25 kV.
The invention provides a high-thermal-conductivity electromagnetic shielding polyarylether composite fiber prepared by the preparation method in the technical scheme, which comprises a polyarylether matrix and a filler which is oriented, arranged and dispersed in the polyarylether matrix.
The invention provides a polyarylether composite material which is obtained by pressing the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber in the technical scheme.
The invention provides application of the polyarylether composite material in the technical scheme in the fields of aerospace, automobiles or electronic packaging.
The invention provides a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, which comprises the following steps of: mixing polyaryletherketone imine, a filler and an organic solvent to obtain a spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material; and (3) carrying out electrostatic spinning on the spinning solution to obtain the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber. The filler in the polyarylether composite fiber provided by the invention has an oriented arrangement structure, can construct an excellent electric conduction and heat conduction network, provides a stable transmission channel for phonons and electrons, reduces interface thermal resistance, and is beneficial to heat flow; meanwhile, the electromagnetic wave shielding structure is beneficial to enhancing the reflection and absorption loss of electromagnetic waves, thereby improving the shielding efficiency. Specifically, the polyarylether composite fiber is prepared by adopting an electrostatic spinning technology, and in the electrostatic spinning process, a one-dimensional carbon nanotube material and a two-dimensional graphene nanosheet material form an oriented arrangement structure under the traction action of electrostatic force, so that a heat conducting network with good interconnectivity is very favorably constructed, heat flows and diffuses rapidly, and a stable channel is provided for high-speed phonon transmission; the good lapping effect of the filler in the orientation arrangement structure is beneficial to further perfecting the connectivity of a heat conduction path, greatly reducing the interface thermal resistance between the polyarylether matrix and the filler, and reducing the scattering of phonons. Meanwhile, the orientation arrangement structure provides a relatively compact heat conduction network or passage, which is beneficial to enabling heat to flow rapidly and increasing the mean free path of phonons. Therefore, the polyarylether composite material prepared based on the polyarylether composite fiber has excellent heat conducting performance and electromagnetic shielding performance.
Furthermore, the carbon nanotube material and the functionalized graphene nanosheets are cooperatively filled with the polyaryletherketone imine, so that the overlapping effect among the fillers can be improved, the transmission path of the fillers is perfected, and the interface thermal resistance is reduced, thereby being beneficial to the transmission of phonons. And the functionalized graphene nanosheets and the polyaryletherketone imine have the interaction of hydrogen bonds and pi-pi, so that the interface compatibility between the filler and the polyaryletherketone base is improved, the interface defects are reduced, the phonon transmission rate is increased, the Van der Waals scattering of phonons is reduced, and the interface thermal resistance is reduced. Therefore, the polyarylether composite material provided by the invention has excellent heat-conducting property and electromagnetic shielding property.
Drawings
FIG. 1 is a schematic view of a process for preparing a polyarylether composite according to the present invention;
FIG. 2 is a scanning electron microscope image of a polyarylether composite fiber prepared in example 1;
FIG. 3 is a transmission electron microscope image of a polyarylether composite fiber prepared in example 3;
FIG. 4 is a graph of electromagnetic shielding performance of the polyarylether fibre composite prepared in example 4;
FIG. 5 is a thermogravimetric analysis of polyarylether fibre composite prepared in example 5.
Detailed Description
The invention provides a method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology, which comprises the following steps of:
mixing polyaryletherketone imine, a filler and an organic solvent to obtain a spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material;
and (3) carrying out electrostatic spinning on the spinning solution to obtain the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
Firstly, the polyaryletherketone imine for preparing the polyaryletherketone composite fiber is explained in detail, and in the invention, the preparation method of the polyaryletherketone imine preferably comprises the following steps:
aniline, 4 '-difluorobenzophenone, toluene and a molecular sieve are mixed for substitution reaction to obtain N-phenyl (4, 4' -difluorodiphenyl) ketimine;
mixing the N-phenyl (4, 4' -difluorodiphenyl) ketimine, a phenolic compound, a catalyst, an organic solvent and a water-carrying agent, and carrying out polymerization reaction to obtain polyaryletherketimine; the phenolic compound is hydroquinone or 4,4' -biphenol.
The invention mixes aniline, 4 '-difluorobenzophenone, toluene and molecular sieve for substitution reaction to obtain N-phenyl (4, 4' -difluorodiphenyl) ketimine. In the present invention, the molar ratio of 4,4' -difluorobenzophenone to aniline is preferably 1: (1 to 1.5), more preferably 1: (1.1 to 1.5), more preferably 1: (1.3-1.5). In the present invention, the toluene is used as a solvent, the molecular sieve is used for removing water and preventing bumping in the toluene, and the amounts of the water and the bumping can satisfy the requirement of the substitution reaction, and the present invention is not particularly limited thereto. In the present invention, the substitution reaction is preferably carried out under reflux conditions; the time of the substitution reaction is preferably 6 to 48 hours, and more preferably 20 to 24 hours; the substitution reaction is preferably carried out in a protective atmosphere, the type of protective gas for providing the protective atmosphere is not particularly limited, and the protective atmosphere can be specifically nitrogen; the substitution reaction is preferably carried out under stirring conditions. After the substitution reaction, the invention preferably performs solid-liquid separation on the obtained product to remove the molecular sieve, evaporates the obtained filtrate to remove the solvent, and recrystallizes the obtained crude product in methanol to obtain N-phenyl (4, 4' -difluorodiphenyl) ketimine as yellow crystals.
After N-phenyl (4, 4 '-difluorodiphenyl) ketimine is obtained, the invention mixes the N-phenyl (4, 4' -difluorodiphenyl) ketimine, phenolic compound, catalyst, organic solvent and water-carrying agent, and carries out polymerization reaction, thus obtaining polyaryletherketimine. In the invention, the phenolic compound is hydroquinone or 4,4 '-biphenol, specifically, hydroquinone is used as a raw material to finally prepare the polyether ether ketone imine containing the benzene side group, and 4,4' -biphenol is used as a raw material to finally prepare the biphenyl polyether ether ketone imine containing the benzene side group. In the present invention, the molar ratio of the N-phenyl (4, 4' -difluorodiphenyl) ketimine to the phenolic compound is preferably (1.5 to 1): 1, more preferably (1.2 to 1): 1. in the present invention, the catalyst preferably includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide, and the molar ratio of the 4,4' -biphenol to the catalyst is preferably 1: (1.1 to 1.5), more preferably 1: (1.1 to 1.4), more preferably 1: (1.1-1.3). In the present invention, the organic solvent preferably includes one or more of diphenyl sulfone, sulfolane, dimethyl sulfoxide and N, N-dimethylacetamide; the water-carrying agent preferably comprises one or more of benzene, toluene and xylene; the volume ratio of the water-carrying agent to the organic solvent is preferably (0.1-0.7): 1, more preferably (0.4 to 0.7): 1; the specific amount of the water-carrying agent and the organic solvent is preferably 6 to 25wt%, and more preferably 10 to 25wt%, based on 5 to 30wt% of the solid content of the system in which the polymerization reaction is carried out. In the invention, the polymerization reaction preferably comprises a water removal treatment, and the temperature of the water removal treatment is preferably 120-160 ℃, and more preferably 130-140 ℃; the time for the water removal treatment is preferably 1 to 5 hours, and more preferably 2 to 3 hours; the water removal treatment is preferably carried out in a protective atmosphere. In the present invention, the polymerization temperature is preferably 170 to 210 ℃, more preferably 180 to 190 ℃; the time is preferably 6 to 48 hours, and more preferably 8 to 12 hours; the polymerization reaction is preferably carried out in a protective atmosphere; the substitution reaction is preferably carried out under stirring conditions.
In the present invention, it is preferable that the polymerization reaction further comprises: discharging the obtained product system into methanol, and sequentially washing and drying the obtained solid material after solid-liquid separation to obtain the polyaryletherketimine. The solid-liquid separation mode is not particularly limited in the invention, and the solid-liquid separation mode can be a mode known by persons skilled in the art, such as filtration; the washing is preferably carried out by water washing and ethanol washing in sequence, and the times of the water washing and the ethanol washing are independent and preferably 2-5 times; the drying is preferably vacuum drying.
The method for preparing the high thermal conductivity electromagnetic shielding polyarylether composite fiber of the invention is explained in detail below.
Mixing polyaryletherketone imine, filler and an organic solvent to obtain spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material. In the present invention, the carbon nanotube material preferably has a length of 5 to 15 μm, and an aspect ratio of (35 to 250): 1; the carbon nano tube material can be an unfunctionalized carbon nano tube or a functionalized carbon nano tube; the functionalized carbon nanotube preferably comprises one or more of a hydroxyl carbon nanotube, a carboxyl carbon nanotube and an amino carbon nanotube; the carbon nanotube material is preferably a single-walled carbon nanotube material or a multi-walled carbon nanotube material. In the present invention, the thickness (i.e., longitudinal dimension) of the graphene nanoplatelets is preferably 1 to 20nm, and the diameter (i.e., transverse dimension) of the graphene nanoplatelets is preferably 1 to 20 μm; the graphene nanosheet material can be an unfunctionalized graphene nanosheet or a functionalized graphene nanosheet, and the functionalized graphene nanosheet is preferably one or more of an amino graphene nanosheet, a carboxyl graphene nanosheet and a hydroxyl graphene nanosheet; the preparation method of the amino graphene nanoplatelets is described in detail later.
In the present invention, the mass fraction of the graphene nanosheet material in the filler is preferably 10 to 70%, more preferably 10 to 50%, and even more preferably 15 to 50%; the mass of the filler is preferably 1-30% of the total mass of the filler and the polyaryletherketone imine, and specifically can be 1%, 6%, 12%, 18%, 24% or 30%. In the invention, the organic solvent preferably comprises one or more of tetrahydrofuran, dichloromethane, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and specifically may be a mixed solvent of N-methylpyrrolidone and tetrahydrofuran, or a mixed solvent of N-methylpyrrolidone and dichloromethane, or a mixed solvent of N, N-dimethylacetamide and tetrahydrofuran; the volume ratio of the N-methylpyrrolidone to the tetrahydrofuran in the mixed solvent of the N-methylpyrrolidone and the tetrahydrofuran is preferably (4-5): the volume ratio of the N-methylpyrrolidone to the dichloromethane in the mixed solvent of the N-methylpyrrolidone and the dichloromethane is preferably (2-3): the volume ratio of the N, N-dimethylacetamide to the dichloromethane in the mixed solvent of the N, N-dimethylacetamide and the dichloromethane is preferably (4-5): and 3, the volume ratio of the N, N-dimethylacetamide to the tetrahydrofuran in the mixed solvent of the N, N-dimethylacetamide and the tetrahydrofuran is preferably (4-5): 2; the amount of the organic solvent is based on the total content of the polyaryletherketone imine and the filler in the spinning solution being 7 to 20wt%, more preferably 10 to 16wt%, further preferably 11 to 14wt%, and further preferably 12 to 13wt%. Mixing polyaryletherketone imine, a filler and an organic solvent, and preferably sequentially carrying out stirring treatment and ultrasonic oscillation to obtain a spinning solution; the stirring is preferably magnetic stirring, and the stirring time is preferably 3-120 min, and more preferably 60min; the time of the ultrasonic oscillation is preferably 10 to 60min, and more preferably 30min.
After the spinning solution is obtained, the spinning solution is subjected to electrostatic spinning to obtain the polyarylether composite fiber. In the present invention, the method of electrospinning the spinning solution preferably comprises: and (3) placing the spinning solution into an injector, placing the injector containing the spinning solution into a propeller, then carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber. In the present invention, the conditions of the electrospinning include: the propelling speed of the propeller is preferably 0.01-0.20 mL/min, more preferably 0.05-0.15 mL/min, further preferably 0.06-0.09 mL/min, and further preferably 0.07-0.08 mL/min; during the propelling, the propelling speed of the propeller is preferably kept constant; the distance between the needle point of the syringe and the collecting plate is preferably 5-20 cm, more preferably 8-18 cm, further preferably 13-17 cm, and further preferably 15-16 cm; the voltage is preferably 5 to 25kV, more preferably 10 to 17kV, and further preferably 15 to 16kV. In the invention, in the electrostatic spinning process, the ambient temperature is preferably 20-25 ℃, and more preferably 23 ℃; the relative humidity of air is preferably 10 to 40%, more preferably 25 to 30%. In an embodiment of the invention, the pusher is preferably an automatic pusher; the automatic thruster is preferably an automatic thruster conventional in the art.
After the electrostatic spinning, the present invention preferably dries the resulting material to substantially remove the solvent; the drying temperature is preferably 100-120 ℃, and more preferably 110-120 ℃; the time is preferably 6 to 48 hours, and more preferably 15 to 24 hours; the drying is preferably vacuum drying.
The invention provides a high-thermal-conductivity electromagnetic shielding polyarylether composite fiber prepared by the preparation method in the technical scheme, which comprises a polyarylether matrix and a filler which is oriented, arranged and dispersed in the polyarylether matrix. In the invention, the diameter of the polyarylether composite fiber is preferably 100-900 nm. In the invention, the polyarylether composite fiber is wholly in a film shape, and the thickness of the film is preferably 50-200 μm. In the present invention, the content of the filler in the polyarylether composite fiber is preferably 1 to 30wt%, and specifically may be 1wt%, 6wt%, 12wt%, 18wt%, 24wt% or 30wt%. The invention can make the filler oriented and arranged based on the electrostatic spinning technology, thereby better playing the advantage of the heat-conducting property of the filler, constructing a good heat-conducting network under the condition of lower filling amount, and improving the heat-radiating efficiency and the heat-conducting enhancement effect; meanwhile, the electromagnetic wave shielding structure is beneficial to enhancing the reflection and absorption loss of electromagnetic waves, thereby improving the shielding efficiency.
The invention provides a polyarylether composite material which is obtained by pressing the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber in the technical scheme. In the present invention, the pressing is preferably a melt hot pressing; the temperature of the melting hot pressing is preferably 370-390 ℃, more preferably 375-388 ℃, and further preferably 380-385 ℃; the pressure is preferably 10 to 50MPa, more preferably 25 to 40MPa, and further preferably 30 to 35MPa; the heat preservation and pressure maintaining time is preferably 10 to 30min, and more preferably 15 to 20min. In the present invention, the preheating step is preferably performed before the melt hot pressing, the preheating temperature is preferably the same as the melt hot pressing temperature, and the preheating time is preferably 5 to 30min, and more preferably 10 to 15min. Preferably, the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber is placed in a mold, the mold containing the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber is placed in a hot press for preheating, then pressure is applied, and the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber is subjected to heat preservation and pressure maintaining for melting and hot pressing to obtain the polyarylether composite material. The invention can obtain polyarylether composite materials with different shapes, such as sheets, according to the needs by pressing the high-thermal-conductivity electromagnetic shielding polyarylether composite fibers. The orientation arrangement effect of the carbon nanotube material and the graphene nanosheet material which are mutually bridged can not only improve the overlapping effect between the fillers, promote the formation of a transmission passage or network and give full play to the advantages of high heat conduction and electric conductivity of the fillers, but also reduce the interface thermal resistance between the resin matrix and the fillers and reduce the scattering of phonons; meanwhile, the electromagnetic wave shielding structure is beneficial to enhancing the reflection and absorption loss of electromagnetic waves, thereby improving the shielding efficiency. Therefore, the polyarylether composite material with the orientation arrangement structure provided by the invention has excellent heat conduction and electromagnetic shielding performance.
The invention provides the application of the polyarylether composite material in the technical scheme in the fields of aerospace, automobiles or electronic packaging. The polyarylether composite material can be applied to heat dissipation components of electronic control units and structural control units in the industries of aviation, automobiles and the like so as to reduce energy loss caused by excessive heating and damage the application efficiency and service life of the electronic control units, wherein the structural control units play an important role in controlling power, combustion and waste gas treatment. Moreover, the polyarylether composite material can be applied to electronic interference and communication equipment in detection and fighters in the field of military aviation. In addition, the polyarylether composite material can be applied to a thermal interface material of a 5G chip and a 5G Radio Frequency (RF) module in the field of electronic packaging, the heat dissipation performance of a circuit is improved to improve the service performance of the circuit, and meanwhile, the shielding performance can enable a packaging system to work under a high-frequency condition and ensure that other partitions are not interfered.
In the present invention, the method for preparing an amino graphene nanoplatelet preferably comprises the following steps:
mixing 4,4' -oxydianiline, concentrated acid and sodium nitrite solution, and performing diazotization reaction to obtain a first product system; the concentrated acid is concentrated hydrochloric acid or concentrated sulfuric acid;
mixing the first product system with the graphene nanosheet dispersion liquid, and carrying out grafting reaction to obtain a second product system;
and mixing the second product system with triethylamine, and carrying out neutralization reaction to obtain the amino graphene nanosheet.
The method mixes 4,4' -oxydianiline, concentrated acid and sodium nitrite solution to carry out diazotization reaction, thereby obtaining a first product system. In the invention, the concentrated acid is concentrated hydrochloric acid or concentrated sulfuric acid; the concentration of the concentrated sulfuric acid is preferably 11.8-13 mol/L, more preferably 12-12.5 mol/L, and the concentration of the concentrated sulfuric acid is preferably 9-12 mol/L, more preferably 9.5-11 mol/L; the molar ratio of the concentrated acid to 4,4' -oxydianiline is preferably (1.5-5): 1, more preferably (2 to 4): 1, more preferably (2.5 to 3): 1, wherein the amount of concentrated hydrochloric acid is calculated as HCl and the amount of concentrated sulfuric acid is calculated as H 2 SO 4 And (6) counting. In the present invention, the molar ratio of the 4,4' -oxydianiline to the sodium nitrite in the sodium nitrite solution is preferably 1: (2 to 7), more preferably 1: (2 to 5), more preferably 1: (2.5-3); the concentration of the sodium nitrite solution is preferably 1 to 1.5mol/L, and more preferably 1.1 to 1.3mol/L. In the present invention, 4' -oxydianiline, a concentrated acid and a sodium nitrite solution are mixed, preferably 4,4' -oxydianiline is added to the concentrated acid, the resulting 4,4' -oxydianiline solution is cooled to 3-5 ℃, and then the sodium nitrite solution is added dropwise under stirring. In the present invention, the temperature of the diazotization reaction is preferably 0 to 15 ℃, more preferably 5 to 12 ℃, and further preferably 8 to 10 ℃; the time is preferably 30 to 60min, and more preferably 30 to 45min; the diazotisation reaction is preferably carried out under stirring conditions. In the invention, in the process of the nitridization reaction, the amino group of the 4,4' -oxydianiline generates diazonium salt and amine salt respectively to obtain a brown biphenyl ether solution containing the diazonium salt and the amine salt, namely a first product system.
After the first product system is obtained, the first product system is mixed with the graphene nanosheet dispersion liquid for grafting reaction, and a second product system is obtained. In the present invention, the molar ratio of the 4,4' -oxydianiline to the graphene nanoplatelets in the graphene nanoplatelet dispersion is preferably (1 to 3): 1, more preferably (1.25 to 2.5): 1, more preferably (1.5 to 2): 1. in the present invention, the concentration of the graphene nanoplatelet dispersion is preferably 1 to 5mg/mL, more preferably 1.5 to 4mg/mL, and even more preferably 2 to 3mg/mL; the solvent of the graphene nanosheet dispersion is preferably an organic solvent and water, and the volume ratio of the organic solvent to the water is preferably (1-5): 1, more preferably (2 to 3.5): 1; the organic solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. In the present invention, the thickness (i.e., longitudinal dimension) of the graphene nanoplatelets is preferably 1 to 20nm, and the diameter (i.e., transverse dimension) of the nanoplatelets is preferably 1 to 20 μm. According to the invention, the graphene nanosheet is dispersed in a mixture of an organic solvent and water under ultrasonic conditions preferably to obtain a graphene nanosheet dispersion liquid. In the present invention, the first product system is mixed with the graphene nanoplatelet dispersion, preferably the first product system is added to the graphene nanoplatelet dispersion. In the present invention, the temperature of the grafting reaction is preferably 60 to 90 ℃, more preferably 70 to 85 ℃, and further preferably 75 to 80 ℃; the time is preferably 5 to 20 hours, more preferably 10 to 16 hours, and still more preferably 12 to 14 hours. In the grafting reaction process, diazonium salt contained in a first product system generates free radicals after electron denitrification, and then generates addition reaction with carbon-carbon double bonds on graphene nanosheets to generate new carbon-carbon single bonds which are connected through the covalent bonds.
After a second product system is obtained, the second product system is mixed with triethylamine, and neutralization reaction is carried out to obtain the amino graphene nanosheet. In the present invention, the molar ratio of the 4,4' -oxydianiline to triethylamine is preferably 1: (1 to 3), more preferably 1: (1.5 to 2.5), more preferably 1: (2-2.3). In the present invention, the second product system is mixed with triethylamine, preferably triethylamine is added to the second product system. In the present invention, the temperature of the neutralization reaction is preferably 30 to 60 ℃, more preferably 40 to 50 ℃; the time is preferably 30 to 90min, and more preferably 40 to 60min; the neutralization reaction is preferably carried out under stirring conditions. In the neutralization reaction process, the aromatic salt compound on the graphene nanosheet obtained after the grafting reaction (namely, the ammonium salt generated in the azide reaction process) is neutralized by triethylamine and converted into aromatic amine.
After the neutralization reaction, the solid-liquid separation is preferably carried out on the obtained product system, and the obtained solid material is sequentially washed and dried to obtain the amino graphene nanosheet. In the invention, the solid-liquid separation mode is preferably filtration, and more preferably filtration by using a vacuum pump; the washing preferably comprises organic solvent washing and water washing which are sequentially carried out, and the selectable types of the organic solvent are preferably the same as the solvent in the graphene nanosheet dispersion liquid, and are not described herein again. The invention has no special limitation on the drying, and can realize full drying of the materials.
FIG. 1 is a schematic view of the preparation process of the polyarylether composite material of the present invention, and the technical solution of the present invention will be clearly and completely described with reference to FIG. 1 and the examples 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Some of the raw material sources and index parameters used in the following examples and comparative examples are as follows:
the carbon nano tube is an unfunctionalized multi-wall carbon nano tube, the length is 5-15 mu m, the length-diameter ratio is (35-250): 1.
the carboxyl graphene nano-sheet has the sheet diameter of 1-20 mu m and the thickness of 1-20 nm and is purchased from Kelaman reagent Co.
The graphene oxide nano-sheet has the sheet diameter of 1-20 microns and the thickness of 1-20 nm, and is purchased from Kaifyi New Material Co.
The radius size of the amino graphene nano sheet is 1-20 mu m, the thickness is 1-20 nm, and the preparation method comprises the following steps: mixing 4,4 '-oxydianiline (0.3 mmol) and concentrated sulfuric acid (9 mol/L,0.072 mL) to obtain a4, 4' -oxydianiline solution; cooling the 4,4' -oxydianiline solution to 3-5 ℃, then dropwise adding the solution into a sodium nitrite aqueous solution (1.3 mol/L, the amount of sodium nitrite is 0.9 mmol) under the stirring condition, and continuously stirring for 45min under the condition of 15 ℃ after the addition is finished to obtain a brown diphenyl ether solution containing azide salt and amine salt; mixing graphene nanosheets (0.125 mmol, the size of the flake diameter is 1-20 microns, and the thickness is 1-20 nm) and N, N-dimethylacetamide with water under an ultrasonic condition to obtain a graphene nanosheet dispersion liquid with the concentration of 2.5mg/mL, wherein the volume ratio of the N, N-dimethylacetamide to the water is 2; adding the diphenyl ether solution into the graphene nanosheet dispersion liquid, and heating to 75 ℃ to react for 14h; and adding triethylamine (0.65 mmol) into the obtained product system after the reaction is finished, stirring and reacting for 60min at 40 ℃, filtering the obtained product system through a vacuum pump to obtain a crude product, then washing with N, N-dimethylacetamide and water in sequence, and drying to obtain the amino graphene nanosheet.
Example 1
Adding 4,4' -difluorobenzophenone (0.1 mol), aniline (0.15 mol), toluene (80 mL) and a molecular sieve (the dosage is 50 g) into a three-neck flask with a mechanical stirring device, a Dean-Stark water separator and a condenser pipe, heating to reflux under the condition of nitrogen protection, and stirring for reaction for 24 hours; cooling the obtained product system to room temperature, filtering to remove the molecular sieve, evaporating the filtrate to remove the solvent, and recrystallizing the obtained crude product in methanol to obtain yellow crystal N-phenyl (4, 4' -difluorodiphenyl) ketimine; adding the N-phenyl (4, 4 '-difluorodiphenyl) ketimine (20 mmol), 4' -biphenol (20 mmol), anhydrous potassium carbonate (3.04g, 22mmol), toluene (20 mL) and sulfolane (30 mL) into a three-neck flask with a mechanical stirring device, a Dean-Stark water separator and a condensation tube, heating to 140 ℃ under the protection of nitrogen to remove water azeotropically for 3h, then heating to 190 ℃, and keeping the temperature and stirring for reaction for 12h; discharging the obtained product system into methanol, filtering, washing the obtained filter cake with water and ethanol for several times respectively, and then carrying out vacuum drying to obtain the biphenyl polyetheretherketone imine containing the benzene side groups.
Adding 5g of benzene-side-group-containing biphenyl polyether ether ketone imine and a filler (specifically, 0.224g of carbon nano tube and 0.096g of amino graphene nano sheet) into a flask containing N-methyl pyrrolidone and tetrahydrofuran (the volume ratio of the N-methyl pyrrolidone to the tetrahydrofuran is 5); extracting the spinning solution by using an injector, then placing the injector in an automatic propeller, carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber with the filler having an oriented arrangement structure; the electrostatic spinning conditions include: the ambient temperature is 23 ℃, and the relative air humidity is 30%; the propulsion speed of the propeller was 0.09mL/min, the distance between the tip of the syringe and the collection plate was 20cm, and the voltage was 15kV (high voltage power supply).
And transferring the polyarylether composite fiber into a vacuum oven at 120 ℃ for vacuum drying for 24h to fully remove the solvent, putting the dried polyarylether composite fiber into a mould, preheating the mould containing the polyarylether composite fiber in a hot press at 385 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 50MPa for carrying out melt hot pressing to obtain the polyarylether composite material, wherein the filler content is 6wt%.
Example 2
The procedure of example 1 was followed to prepare a biphenyl type polyetheretherketone imine containing phenyl side groups.
Adding 5g of benzene-containing side group-containing biphenyl polyether ether ketone imine and a filler (specifically, 0.48g of carbon nano tube and 0.20g of carboxyl graphene nano sheet) into a flask containing N-methyl pyrrolidone and tetrahydrofuran (the volume ratio of the N-methyl pyrrolidone to the tetrahydrofuran is 4); adopting an injector to extract the spinning solution, then placing the injector in an automatic propeller, and carrying out electrostatic spinning under the propelling of the propeller and the action of a high-voltage power supply, wherein the electrostatic spinning conditions comprise that: the ambient temperature is 23 ℃, the air relative humidity is 30%, the propelling speed of the propeller is 0.08mL/min, the distance between the needle point of the injector and the collecting plate is 18cm, the voltage is 16kV (provided by a high-voltage power supply), and finally the polyarylether composite fiber with the filler having the oriented arrangement structure is collected on the collecting plate.
And transferring the polyarylether composite fiber into a vacuum oven at 120 ℃ for vacuum drying for 24h to fully remove the solvent, putting the dried polyarylether composite fiber into a mould, preheating the mould containing the polyarylether composite fiber in a hot press at 385 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 40MPa for carrying out melt hot pressing to obtain the polyarylether composite material, wherein the filler content is 12wt%.
Example 3
The procedure of example 1 was followed to prepare a biphenyl type polyetheretherketone imine containing phenyl side groups.
Adding 5g of biphenyl polyetheretherketone imine containing lateral groups and a filler (specifically, 0.77g of carbon nanotubes and 0.33g of graphene oxide nanosheets) into a flask containing N-methylpyrrolidone and dichloromethane (the volume ratio of the N-methylpyrrolidone to the dichloromethane is 3); extracting the spinning solution by using an injector, then placing the injector in an automatic propeller, carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber with the filler having an oriented arrangement structure; the electrostatic spinning conditions include: the ambient temperature is 23 ℃, and the relative air humidity is 30%; the propulsion speed of the propeller is 0.07mL/min, the distance between the needle point of the syringe and the collecting plate is 16cm, and the voltage is 17kV (provided by a high-voltage power supply).
And transferring the polyarylether composite fiber into a vacuum oven at 120 ℃ for vacuum drying for 24h to fully remove the solvent, putting the dried polyarylether composite fiber into a mould, preheating the mould containing the polyarylether composite fiber in a hot press at 380 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 35MPa for carrying out melt hot pressing to obtain the polyarylether composite material, wherein the filler content is 18wt%.
Example 4
The procedure of example 1 was followed to prepare a biphenyl type polyetheretherketone imine containing phenyl side groups.
Adding 5g of benzene-containing side group biphenyl type polyetheretherketone imine and a filler (specifically, 0.47g of carbon nano tube and 1.11g of carboxyl graphene nano sheet) into a flask containing N, N-dimethylacetamide and dichloromethane (the volume ratio of the N, N-dimethylacetamide to the dichloromethane is 5) and sequentially carrying out magnetic stirring for 1h and ultrasonic oscillation for 30min to obtain a spinning solution containing 11wt% of benzene-containing side group biphenyl type polyetheretherketone imine and the filler; extracting the spinning solution by using an injector, then placing the injector in an automatic propeller, carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber with the filler having an oriented arrangement structure; the electrostatic spinning conditions include: the ambient temperature is 23 ℃, and the relative air humidity is 30%; the propulsion speed of the propeller is 0.06mL/min, the distance between the needle point of the syringe and the collecting plate is 15cm, and the voltage is 16kV (provided by a high-voltage power supply).
And transferring the polyarylether composite fiber into a vacuum oven at 120 ℃ for vacuum drying for 24h to fully remove the solvent, putting the dried polyarylether composite fiber into a mould, preheating the mould containing the polyarylether composite fiber in a hot press at 380 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 30MPa for carrying out melt hot pressing to obtain the polyarylether composite material, wherein the filler content is 24wt%.
Example 5
The procedure of example 1 was followed to prepare a biphenyl type polyetheretherketone imine containing phenyl side groups.
Adding 5g of benzene-side-group-containing biphenyl polyether ether ketone imine and a filler (specifically, 0.64g of carbon nano tube and 1.5g of amino graphene nanosheet) into a flask containing N, N-dimethylacetamide and tetrahydrofuran (the volume ratio of the N, N-dimethylacetamide to the tetrahydrofuran is 5), and sequentially carrying out magnetic stirring for 1h and ultrasonic oscillation for 30min to obtain a spinning solution containing 10wt% of benzene-side-group-containing biphenyl polyether ether ketone imine and the filler; extracting the spinning solution by using an injector, then placing the injector in an automatic propeller, carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber with the filler having an oriented arrangement structure; the electrostatic spinning conditions include: the ambient temperature is 23 ℃, and the relative air humidity is 30%; the propulsion speed of the propeller is 0.05mL/min, the distance between the needle point of the syringe and the collecting plate is 13cm, and the voltage is 15kV (provided by a high-voltage power supply).
And transferring the polyarylether composite fiber into a vacuum oven at 120 ℃ for vacuum drying for 24h to fully remove the solvent, putting the dried polyarylether composite fiber into a mould, preheating the mould containing the polyarylether composite fiber in a hot press at 375 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 25MPa for carrying out melt hot pressing to obtain the polyarylether composite material, wherein the filler content is 30wt%.
Comparative example 1
The biphenyl polyetheretherketone imine containing phenyl side groups was prepared according to the method of example 1.
Adding 5g of phenyl-side-group-containing biphenyl polyetheretherketone imine and a filler (specifically, 0.224g of carbon nanotubes and 0.096g of aminographene nanosheets) into a flask containing N-methylpyrrolidone and tetrahydrofuran (the volume ratio of the N-methylpyrrolidone to the tetrahydrofuran is 5) and carrying out magnetic stirring for 1h and ultrasonic oscillation for 30min in sequence to obtain a mixed dispersion liquid containing 15wt% of the total solid content of the phenyl-side-group-containing biphenyl polyetheretherketone imine and the filler; discharging the materials into water, filtering, washing the obtained filter cake with water and ethanol for several times in sequence, and drying to obtain composite powder;
and putting the mixed powder into a mould, preheating the mould containing the mixed powder in a hot press at 380 ℃ for 15min, and then carrying out heat preservation and pressure maintenance for 15min under the condition that the pressure is 20MPa for carrying out melt hot pressing to obtain the polyarylether composite material.
Characterization and performance testing:
fig. 2 is a scanning electron microscope image of the polyarylether composite fiber prepared in example 1, and it can be seen from fig. 2 that the surface of the polyarylether composite fiber has a certain roughness, which indicates that the filler (i.e., the multiwall carbon nanotube and the amino graphene nanosheet) is arranged along with the polyarylether composite fiber to form a dense network with good lap joint property, which is beneficial to forming a good heat conducting network.
Fig. 3 is a transmission electron microscope image of the polyarylether composite fiber prepared in example 3, and it can be seen from fig. 3 that under the action of a high-voltage electric field, the multiwalled carbon nanotubes are oriented and arranged in the polyarylether composite fiber, which is beneficial to the construction of a dense heat-conducting network, and is further beneficial to the improvement of the heat-conducting enhancement efficiency of the filler on the polyarylether composite material.
FIG. 4 is a graph showing the electromagnetic shielding performance of the polyarylether composite prepared in example 4, and it can be seen from FIG. 4 that when the total filler loading of the polyarylether composite is 24wt% and the thickness of the formed sheet is 140 μm, the polyarylether composite shows 32dB shielding performance at 8.2 GHz.
FIG. 5 is a thermogravimetric analysis of the polyarylether composite prepared in example 5, wherein T is shown in FIG. 5 5 (5% weight loss) at 517 ℃ and T 10 The temperature of (weight loss 10%) is 533 ℃, which shows that the polyarylether composite material provided by the invention has excellent thermal stability.
The thermal conductivity of the polyarylether composites prepared in the examples and comparative examples was measured by flash emission method LFA467 (Germany) and the specific results are shown in Table 1. As shown in Table 1, the polyarylether composite material provided by the invention has excellent thermal conductivity.
TABLE 1 Heat conductivity of polyarylether composites prepared in examples and comparative examples
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 (8)
1. A method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fibers based on an electrostatic spinning technology comprises the following steps:
mixing polyaryletherketone imine, a filler and an organic solvent to obtain a spinning solution; the filler is a carbon nanotube material and a graphene nanosheet material; the polyaryletherketimine is biphenyl polyether ether ketone imine containing benzene side groups; the carbon nanotube material is a multi-wall carbon nanotube material; the graphene nanosheet material is a functionalized graphene nanosheet; the mass of the filler is 1-30% of the total mass of the filler and the polyaryletherketone imine; the mass fraction of graphene nanosheet materials in the filler is 10-50%;
performing electrostatic spinning on the spinning solution to obtain the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber; the total content of the polyaryletherketone imine and the filler in the spinning solution is 7-20 wt%.
2. The method of claim 1, wherein the functionalized graphene nanoplatelets are one or more of amino graphene nanoplatelets, carboxy graphene nanoplatelets, and hydroxy graphene nanoplatelets.
3. The method of claim 1 or 2, wherein the graphene nanoplatelets have a thickness of 1 to 20nm and a sheet diameter size of 1 to 20 μm.
4. The method according to claim 1, wherein the method of electrospinning the spinning dope comprises:
and (3) placing the spinning solution into an injector, placing the injector containing the spinning solution into a propeller, then carrying out electrostatic spinning under the propelling of the propeller and the action of an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber.
5. The method of claim 4, wherein the electrospinning conditions comprise: the propelling speed of the propeller is 0.01-0.20 mL/min, and the distance between the needle point of the syringe and the collecting plate is 5-20 cm; the voltage is 5-25 kV.
6. The high thermal conductivity electromagnetic shielding polyarylether composite fiber prepared by the method of any one of claims 1 to 5, comprises polyaryletherketone imine and filler dispersed in the polyaryletherketone imine in an oriented manner.
7. A polyarylether composite material prepared by pressing the high-thermal-conductivity electromagnetic shielding polyarylether composite fiber disclosed by claim 6.
8. Use of a polyarylether composite according to claim 7 in the field of aerospace, automotive or electronic packaging.
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