CN114369337A - Preparation method of graphene-based epoxy resin heat-conducting composite material - Google Patents
Preparation method of graphene-based epoxy resin heat-conducting composite material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229920001577 copolymer Polymers 0.000 claims description 8
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
Abstract
The invention discloses a preparation method of a graphene-based epoxy resin heat-conducting composite material, which comprises the following specific steps: (1) preparing pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA; (2) preparing HBPE @ Py @ PGMA functionalized graphene dispersion liquid; (3) mixing the HBPE @ Py @ PGMA functionalized graphene dispersion liquid, epoxy resin and a chloroform solvent, and stirring at room temperature for 1-3 hours to uniformly mix the solution; then adding a curing agent, and stirring for 0.5-1.5 hours at room temperature; (4) carrying out vacuum filtration on the mixed solution obtained in the step (3) in a vacuum oven at room temperature to remove bubbles; (5) and (3) pouring the mixed solution obtained in the step (4) into a polytetrafluoroethylene mold, pre-curing for 0.5-1h at 40-60 ℃, and curing for 6-10h at 60-80 ℃ in a constant-temperature air-blowing drying oven to obtain the graphene-based epoxy resin heat-conducting composite material. The method has simple process and short preparation period, and the prepared composite material has good heat-conducting property.
Description
Technical Field
The invention discloses a preparation method of a graphene-based epoxy resin heat-conducting composite material.
Background
In the field of microelectronics, with the miniaturization of the volume of components, heat conduction materials are required to have the characteristics of small volume and high heat conduction. The polymer heat-conducting composite material can well solve the problem that the device can still keep normal heat dissipation in different working environments.
Epoxy resin (EP) is an oligomer obtained by polymerizing molecules containing 2 or more epoxy groups, has excellent properties such as adhesion, corrosion resistance and insulation, and is widely used in adhesives, paints, electrical insulating materials and composite materials. (functionalization of the nano carbon tubes and application thereof in composite materials [ J ] new materials and new sciences 2016, 42(1):1-3.) has also been widely used in electronics and manufacturing industries. The heat conductivity of the electronic equipment has direct influence on the heat dissipation effect of the electronic equipment. The modification research of the epoxy resin is receiving increasing attention, and the utilization of the high-thermal-conductivity filler to improve the thermal conductivity of the composite material is a mature scheme at present.
Graphene (Graphene) is sp2The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. Due to its excellent thermal, mechanical and electronic properties, graphene has become a new star in the field of material science, and has very good thermal conductivity. The thermal conductivity coefficient of pure defect-free single-layer graphene is as high as 5300W/mK, which is more than ten times that of copper and is the highest carbon material so far. Ultrasonic-assisted liquid phase stripping of graphene is an effective method for large-scale preparation of low-defect and few-layer graphene. In addition, the graphene prepared by the liquid phase stripping method is relatively simple to prepare, and a complicated transfer process is not needed.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene-based epoxy resin heat-conducting composite material, which is simple in process and short in preparation period, and the prepared composite material has good heat-conducting property.
The preparation method is characterized by researching on the aspects of a composite material preparation process, filler appearance, distribution state, interface design and the like, the composite material takes epoxy resin as a matrix and modified graphene as filler, firstly, the graphene is subjected to non-covalent bond functional modification, and hyperbranched polyethylene copolymer HBPE @ Py @ PGMA which is adsorbed on the surface of the graphene through CH-pi and pi-pi non-covalent bond acting force is used as a stabilizer to prepare the graphene, and then the modified graphene is used as the filler and the epoxy resin is used as the matrix to prepare the graphene-based epoxy resin heat-conducting composite material.
The technical solution adopted by the present invention is specifically explained below.
The invention provides a preparation method of a graphene-based epoxy resin heat-conducting composite material, which comprises the following specific steps:
(1) preparing pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA; the copolymer consists of an HBPE core containing pyrene end groups (Py) and a Poly Glycidyl Methacrylate (PGMA) side chain;
(2) taking pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA as a stripping stability and functional assistant, ultrasonically stripping natural flaky graphite in an organic solvent, and removing un-stripped natural flaky graphite and excessive pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA through centrifugation to obtain HBPE @ Py @ PGMA functionalized Graphene (GNs) dispersion liquid, wherein the HBPE @ Py @ PGMA is adsorbed on the surface of graphene through CH-pi and pi-pi non-covalent bond acting forces to prevent the GNs from agglomerating; the size of the graphene is mainly distributed between 100nm and 600 nm;
(3) mixing the HBPE @ Py @ PGMA functionalized graphene dispersion liquid, epoxy resin and a chloroform solvent, and stirring at room temperature for 1-3 hours to uniformly mix the solution; adding curing agent, and stirring for 0.5-1.5 hours at room temperature to uniformly mix the solution;
(4) carrying out vacuum filtration on the mixed solution obtained in the step (3) in a vacuum oven at room temperature to remove bubbles;
(5) pouring the mixed solution obtained in the step (4) into a Polytetrafluoroethylene (PTFE) mold, pre-curing for 0.5-1h at 40-60 ℃, and curing for 6-10h at 60-80 ℃ in a constant-temperature air-blast drying oven to obtain the graphene-based epoxy resin composite material;
in the graphene-based epoxy resin heat-conducting composite material, the mass content of graphene is 1.0-4.0%.
Preferably, in the graphene-based epoxy resin heat-conducting composite material, the mass content of graphene is 1.0-4.0%, more preferably 3.0-4.0%, and the composite material has good heat-conducting property. In the step (1) of the invention, the pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA can be prepared by referring to a method reported in a literature. The invention specifically recommends that the pyrenyl hyperbranched polyethylene terpolymer is prepared according to the following steps:
(a) under certain ethylene pressure, Pd-diimine is used as a catalyst, and a pyrene-containing monomer shown as a formula (I), ethylene and 2- (2-bromoisobutyroyloxy) ethyl acrylate (BIEA) are synthesized into HBPE @ Py @ Br through a one-step chain walking mechanism;
(b) HBPE @ Py @ Br is taken as a macroinitiator, GMA is taken as a monomer, bipyridine or PMDETA is taken as an ATRP reaction ligand, CuBr is taken as a catalyst, and the pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA is synthesized through the reaction of Atom Transfer Radical Polymerization (ATRP) in cyclohexanone solvent.
Preferably, the Pd-diimine catalyst is one of the following: the catalyst comprises an acetonitrile Pd-diimine catalyst 1 and a hexatomic ring Pd-diimine catalyst 2 containing a carbomethoxy, wherein the structural formulas of the two are as follows:
both of the above Pd-diimine catalysts can be synthesized in the laboratory with reference to the following documents:
[1]Johnson L.K.,Killian C.M.,Brookhart M.J.Am.Chem.Soc.,1995,117,6114；
[2]Johnson L.K.,Mecking S.,Brookhart M.J.Am.Chem.Soc.,1996,118,267.
preferably, in the step (a), the polymerization reaction is carried out under the conditions of 25 to 30 ℃ and 1 to 1.5atm of ethylene pressure for 12 to 24 hours with stirring, and more preferably under the conditions of 25 ℃ and 1atm of ethylene pressure for 24 hours with stirring.
Preferably, in the step (a), the initial concentrations of the pyrene-containing monomer, 2- (2-bromoisobutyroyloxy) ethyl acrylate (BIEA for short) and Pd-diimine in the polymerization reaction system are (0.10-0.30g/ml), (0.10-0.30g/ml) and (25-50 mg/ml).
Preferably, in the step (b), the feeding molar ratio of HBPE @ Py @ Br, GMA, bipyridine or PMDETA, CuBr is 1 (100) -200: 2:1, wherein the mole number of HBPE @ Py @ Br is counted by the mole number of Br contained in the HBPE @ Py @ Br.
Preferably, in the step (b), the polymerization temperature is 30 to 35 ℃ and the polymerization time is 0.5 to 24 hours, more preferably, the polymerization temperature is 30 ℃ and the polymerization time is 4 hours.
In the step (2) of the present invention, the preparation of the hyperbranched polyethylene copolymer HBPE @ Py @ PGMA functionalized graphene dispersion can be performed according to a method reported in a literature. The invention specifically recommends that step (2) is carried out as follows: pouring a certain amount of natural flaky graphite into a reaction vessel filled with an organic solvent solution of HBPE @ Py @ PGMA polymer, and sealing; and (3) placing the sealed reaction container into an ultrasonic pool, performing ultrasonic treatment at room temperature for 24-60 hours (preferably 48 hours), wherein the ultrasonic power can be selected from 180-320W (preferably 240W), taking out the mixed solution after the ultrasonic treatment, placing the mixed solution into a centrifuge tube, centrifuging the mixed solution, wherein the rotating speed can be controlled at 3000-5000rpm (preferably 4500rpm), and the centrifuging time is 10-50min, wherein the centrifuging process mainly comprises the steps of removing blocky non-stripped natural flaky graphite, performing vacuum filtration (preferably with the aperture of a filter membrane of 200nm) on the graphene dispersion liquid containing the excessive pyrenyl terpolymer obtained by centrifuging to remove the contained excessive copolymer, performing ultrasonic treatment again to disperse the copolymer into an organic solvent, repeating the operation of vacuum filtration-ultrasonic treatment for more than 3 times, drying the dispersion liquid to constant weight, and dispersing the dispersion liquid into the organic solvent to obtain the HBPE @ Py @ PGMA functionalized graphene dispersion liquid. Preferably, the feeding mass ratio of the HBPE @ Py @ PGMA to the natural flaky graphite is 1: 8; the adding amount of the flaky graphite is 8mg/ml based on the metering concentration of the solvent chloroform. Preferably, the organic solvent is chloroform, dichloromethane, tetrahydrofuran or toluene.
In the invention, the epoxy resin is preferably bisphenol A type resin E-51, the curing agent is preferably E593 type curing agent, and the mass ratio of the epoxy resin to the curing agent is 100: 25-28.
In the present invention, the room temperature is preferably 25 to 30 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method, the pyrene-functionalized hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA is subjected to liquid phase stripping in a common organic solvent chloroform to obtain the graphene nanosheet, and meanwhile, the interaction between the hyperbranched structure and the surface of the nanosheet enables a target polymer to be adsorbed on the surface of the nanosheet, so that the surface modification filler is played, and the filler is good in dispersibility in a polymer matrix and strong in interface interaction.
(2) According to the graphene epoxy resin composite material, the graphene nano filler has good compatibility in an epoxy resin matrix through the hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA which is adhered to the surface of graphene and contains the HBPE core with the pyrene end group (Py) and the side chain of the Poly Glycidyl Methacrylate (PGMA), and the graphene epoxy resin composite material prepared by the method has high thermal conductivity.
Drawings
Fig. 1 is a flow chart illustrating a typical preparation process of a graphene-based epoxy resin composite according to the present invention;
fig. 2 is a cross-section SEM of the graphene-based epoxy resin thermal conductive composite material with graphene content prepared in example 1, with a 2 μm scale;
FIG. 3 is a graph of thermal conductivity curves of graphene epoxy resin thermal conductive composites of different graphene contents prepared in examples 1-5;
fig. 4 shows the efficiency of enhancing the thermal conductivity of the graphene epoxy resin thermal conductive composite materials with different graphene contents prepared in examples 1 to 5.
Detailed Description
The invention is further illustrated but not limited by the following examples.
Example 0:
the HBPE @ Py @ PGMA is a pyrenyl hyperbranched polyethylene terpolymer which simultaneously contains HBPE nucleus with pyrene end group (Py) and side chain of Poly Glycidyl Methacrylate (PGMA), and is synthesized in a laboratory, and the specific synthesis steps are as follows:
(1) preparation of HBPE @ Py @ Br:
based on a chain walking mechanism of a Pd-diimine catalyst, ethylene, a pyrene-containing monomer shown in a formula (I) and a BIEA monomer are copolymerized in anhydrous dichloromethane at a polymerization temperature of 25 ℃ for 24 hours. The specific synthesis steps are as follows:
a clean, dry 250mL Schlenk flask was prepared, sealed and evacuated 3 times each under nitrogen, heated to 400 ℃ with a heat gun while evacuating, and evacuated 3 times each under ethylene. Then keeping the constant pressure of ethylene at 0.1MPa, placing the mixture in an oil bath pan at 25 ℃, controlling the reaction temperature at 25 ℃, adding 1.3g of pyrene-containing monomer, vacuumizing and introducing ethylene for 3 times respectively to remove air possibly remained in the bottle. 5mL of anhydrous dichloromethane is added, and magnetic stirring is started to fully dissolve the pyrene-containing monomer. Then 1.2g of BIEA was weighed out and poured into a Schlenk flask. Weighing 500mg of acetonitrile group Pd-diimine catalyst in a 20mL brown bottle which is cleaned and dried, vacuumizing the bottle after sealing the bottle, introducing nitrogen for 3 times respectively, injecting 3mL of anhydrous dichloromethane, fully dissolving the catalyst, extracting the solution and injecting the solution into a Schlenk bottle, finally injecting 2mL of anhydrous dichloromethane into the brown bottle, fully washing the brown bottle to dissolve the residual catalyst, extracting the solution and injecting the solution into the Schlenk bottle. The reaction was stirred for 24h in the dark. After the reaction was completed, the product was transferred to a 100mL beaker and washed thoroughly in a Schlenk flask by adding 5mL of dichloromethane, taking off the residual product. Then the product was purged with cold air to remove the solvent. Adding 50mL of tetrahydrofuran solution, respectively adding 10 drops of concentrated hydrochloric acid and hydrogen peroxide, and stirring for 2 hours to change the solution from yellow-black to yellow and transparent. Blowing the mixture by cold air, dropwise adding a tetrahydrofuran solution under stirring until the product is completely dissolved, dropwise adding a methanol solution until the product is completely precipitated, stirring for 10min and standing for 10 min. And after removing the supernatant, blowing the solvent with cold air, repeatedly dissolving and precipitating for 3 times, finally dissolving and precipitating for 1 time with tetrahydrofuran-acetone, and drying the product in a vacuum oven at 60 ℃ until the weight is constant, wherein the HBPE @ Py @ Br is obtained in a light yellow viscous flow state after about 48 hours.
(2) A clean and strictly dry 100mL Schlenk bottle is taken, in a cyclohexanone solvent, bipyridine is taken as a ligand, CuBr is taken as a catalyst, Glycidyl Methacrylate (GMA) monomer polymerization is initiated, and GMA is taken according to the specific molar ratio: br: and (3) CuBr: 154mmol GMA monomer, 25mL cyclohexanone, 0.770mmol HBPE @ Py @ Br (molar amount of this material based on the molar amount of Br contained therein) and 1.540mmol bipyridine (bpy) were added successively in bpy 200:1:1: 2.
(3) The mixed solution is frozen, vacuumized and unfrozen for three times to ensure the anhydrous and oxygen-free environment in the polymerization process, and then 0.770mmol of CuBr is rapidly added in the nitrogen atmosphere, and the mixture reacts for 4 hours at 30 ℃ after being sealed.
(3) After the reaction is carried out for a preset time, the reaction bottle is immersed into an ice-water bath to terminate the reaction, then the solution is blown to be dry by cold air, THF is added to dissolve the product, then methanol is continuously dripped to precipitate the product, and finally the supernatant is poured out. This step was repeated 3 times to purify the product.
(4) And transferring the product into a centrifuge tube, and drying the centrifuge tube in a vacuum oven at 60 ℃ for 24h to obtain yellowish white solid powder, namely HBPE @ Py @ PGMA.
The HBPE @ Py @ PGMA used in the following examples of the invention were prepared in accordance with the procedure of example 0.
Examples 1 to 5:
the method comprises the following steps: weighing 0.08g of HBPE @ Py @ PGMA into a glass bottle, adding 30mL of chloroform, fully stirring to assist the copolymer HBPE @ Py @ PGMA to dissolve, then adding 0.64g of natural crystalline flake graphite into the glass bottle, finally adding 50mL of chloroform (the mass of the natural crystalline flake graphite in the chloroform is recorded as 8mg/mL), and simultaneously sealing the bottle cap to prepare 12 bottles of graphene dispersion liquid in a large batch.
Step two: and (3) putting the mixed solution treated in the step one into a water bath ultrasonic pool at room temperature for ultrasonic treatment for 48 hours, wherein the ultrasonic power is 240W.
Step three: and D, taking out the mixed solution subjected to ultrasonic treatment in the step II, putting the mixed solution into a centrifugal tube, and centrifuging the mixed solution at 4000rpm for 45min to mainly remove the unexfoliated blocky natural crystalline flake graphite. And then taking the supernatant for storage, thus obtaining the dispersion liquid of the Graphene Nano Sheets (GNs).
Step four: taking 400mL of the dispersion in the third step, removing the contained excessive copolymer through vacuum filtration (the aperture of a filter membrane is 200nm), performing ultrasonic treatment again to disperse the excessive copolymer into organic solvent chloroform, repeating the operation for 3 times, measuring 20mL of the collected dispersion, and drying the dispersion in a vacuum oven to constant weight to obtain the productHBPE @ Py @ PGMA functionalized graphene (HBPE @ Py @ PGMA @ - GNs)Respectively occupying HBPE @ Py @ PGMA and graphene by thermogravimetric calculationHBPE @ Py @ PGMA functionalized graphenePercentage by mass. Then adding chloroform (to)HBPE @ Py @ PGMA functionalized grapheneThe mass in the solvent is recorded as 1mg/mL), and ultrasonic dispersion is carried out again for 2h for standby.
Step five: according to the scheme shown in Table 1Quality of HBPE @ Py @ PGMA functionalized grapheneWeighing a certain volume of the graphene dispersion liquid obtained in the third step, weighing 0.4g of bisphenol A type resin E-51, weighing 4ml of chloroform, placing the chloroform and the resin E-51 in a 100ml beaker, and magnetically stirring the mixture for 1 hour at the room temperature of 25 ℃ so as to uniformly mix the epoxy resin and the graphene in a chloroform solvent.
Step six: and then 0.1g of curing agent E593 is added into the graphene epoxy resin mixed solution in the fifth step, and magnetic stirring is carried out for 0.5 hour at the room temperature of 25 ℃ so as to uniformly mix the solution.
Step seven: and (4) carrying out vacuum filtration on the mixed solution obtained in the sixth step for 5 minutes in a vacuum oven at the room temperature of 25 ℃ to remove bubbles.
And step eight, pouring the mixed solution obtained in the step seven into a Polytetrafluoroethylene (PTFE) mould with the diameter of 3cm and the thickness of 1mm, pre-curing for 1 hour at the temperature of 60 ℃, and then curing for 8 hours at the temperature of 80 ℃ in a constant-temperature air-blast drying oven to obtain the cured graphene-based epoxy resin heat-conducting composite material.
TABLE 1
aThe graphene dispersion liquid added in the fifth stepThe mass of HBPE @ Py @ PGMA/GNs;
bthe graphene dispersion liquid added in the fifth stepThe quality of graphene in HBPE @ Py @ PGMA/GNs is determined by The preparation batches are different, so the mass percentage content of graphene in HBPE @ Py @ PGMA/GNs prepared in different examples can exist A difference;
cthe graphene-based epoxy resin heat-conducting composite material comprises graphene in percentage by mass.
Characterization and testing
The thermal diffusivity (α) of the composite was determined by laser flash (LFA 467, Nano-flash, Netzsch). The heat conductivity is calculated by the formula of lambda ═ alpha x CPX ρ where λ is a thermal conductivity in W · m-1·K-1；CPIs specific heat capacity, and has a unit of J.g-1·K-1(ii) a Rho is density in g cm-3(ii) a Alpha is thermal diffusion coefficient and is in mm2·s-1. Determination of C by differential scanning calorimetry (DSC 214, Netzsch)P。
Testing thermal diffusion coefficient: the test instrument is an LFA467 type laser thermal conductivity instrument produced by Germany relaxation resistance. The measured data is that the thermal diffusivity in the thickness direction is measured, the diameter of a sample is required to be 12.7mm, and a layer of uniform graphite is sprayed on the surface of the sample before the test.
Differential scanning calorimetry analysis: the test instrument was a type 214 differential scanning calorimeter manufactured by the company sanchi germany. And (3) testing the specific heat capacity by adopting a sapphire three-wire method, wherein the testing temperature range is from 25 ℃ to 150 ℃, the heating rate is 10 ℃/min, and the testing atmosphere is nitrogen. Heat conductivity coefficient enhancement efficiency (TCE%) calculation formula: TCE ═ [ (λ c- λ e)/λ e ] X100%, where λ c and λ e are the thermal conductivities of the composite and the neat epoxy, respectively.
Test result comparison and analysis
Fig. 2 (a) is a sectional SEM image of pure epoxy resin, and fig. 2 (b-e) is a sectional SEM of graphene-based epoxy resin thermal conductive composite material with different graphene contents (1.0-4.0 wt%), which shows that GNs are uniformly dispersed in EP, and the distance between adjacent GNs decreases with the increase of filler loading. The fracture surface image clearly shows that the graphene nanosheets are uniformly dispersed in the epoxy matrix, which is probably due to the fact that the hyperbranched polyethylene copolymer HBPE @ Py @ PGMA adsorbed on the surface of the graphene through CH-pi and pi-pi non-covalent bond acting force participates in the epoxy resin through a chemical covalent bond. The curing reaction increases the compatibility of the nanofiller in the organic matrix.
Fig. 3 is a thermal conductivity graph of the graphene epoxy resin thermal conductive composite materials with different graphene contents prepared in examples 1 to 5, and it can be seen from the graph that the thermal conductivity of the graphene/epoxy resin thermal conductive composite film is linearly increased along with the increase of the graphene content, and the thermal conductivity of the pure epoxy resin film is 0.152W · m-1·K-1. When the content of 4 wt% added graphene is that the thermal conductivity coefficient of the graphene epoxy resin thermal conductive composite material is 0.795 W.m-1·K-1. The data fully demonstrate that graphene containing non-covalent polymer surface modification has an obvious heat conduction enhancement effect in epoxy resin heat conduction. Meanwhile, the modification of the epoxy group can promote the dispersion of graphene in epoxy resin, so that a graphene heat-conducting network is formed, and the heat-conducting property is enhanced.
Fig. 4 shows the thermal conductivity enhancement efficiency of the graphene epoxy resin thermal conductive composites with different graphene contents prepared in examples 1 to 5, and it can be seen from the graph that the thermal conductivity enhancement efficiency of the composites gradually increases with the increase of the graphene content, and the increase values of the thermal conductivity enhancement efficiency of the composites with different contents are 75.6% (1 wt%), 101.3% (2 wt%), 239.5% (3 wt%) and 423.0% (4 wt%), respectively.
Table 2 is a specific numerical table of the thermal conductivity of the graphene epoxy resin thermal conductive composite material with different graphene contents.
TABLE 2
Claims (9)
1. A preparation method of a graphene-based epoxy resin heat-conducting composite material comprises the following specific steps:
(1) preparing pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA;
(2) taking pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA as a stripping stability and functional assistant, ultrasonically stripping natural flaky graphite in an organic solvent, and removing un-stripped natural flaky graphite and excessive pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA through centrifugation to obtain HBPE @ Py @ PGMA functional graphene dispersion liquid;
(3) mixing the HBPE @ Py @ PGMA functionalized graphene dispersion liquid, epoxy resin and a chloroform solvent, and stirring at room temperature for 1-3 hours to uniformly mix the solution; adding curing agent, stirring for 0.5-1.5 hours at room temperature to uniformly mix the solution;
(4) carrying out vacuum filtration on the mixed solution obtained in the step (3) in a vacuum oven at room temperature to remove bubbles;
(5) pouring the mixed solution obtained in the step (4) into a polytetrafluoroethylene mold, pre-curing at 40-60 ℃ for 0.5-1h, and curing at 60-80 ℃ for 6-10h in a constant-temperature air-blast drying oven to obtain the graphene-based epoxy resin composite material;
in the graphene-based epoxy resin heat-conducting composite material, the mass content of graphene is 1.0-4.0%.
2. The method of claim 1, wherein: in the graphene-based heat-conducting epoxy resin composite material, the mass content of graphene is 1.0-1.0%, and more preferably 3.0-4.0%.
3. The method of any one of claims 1-2, wherein: in the step (1), the pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA is prepared according to the following steps:
(a) under certain ethylene pressure, Pd-diimine is used as a catalyst, and a pyrene-containing monomer shown as a formula (I), ethylene and 2- (2-bromoisobutyroyloxy) ethyl acrylate are synthesized into HBPE @ Py @ Br through a one-step chain walking mechanism;
(b) HBPE @ Py @ Br is taken as a macroinitiator, GMA is taken as a monomer, bipyridine or PMDETA is taken as an ATRP reaction ligand, CuBr is taken as a catalyst, and the pyrenyl hyperbranched polyethylene terpolymer HBPE @ Py @ PGMA is synthesized through atom transfer radical polymerization in cyclohexanone solvent.
4. The method of claim 3, wherein: the Pd-diimine catalyst is selected from one of the following: the catalyst comprises an acetonitrile Pd-diimine catalyst 1 and a hexatomic ring Pd-diimine catalyst 2 containing a carbomethoxy, wherein the structural formulas of the two are as follows:
5. the method of claim 4, wherein: in the step (a), in a polymerization reaction system, the initial concentrations of a pyrene-containing monomer, 2- (2-bromoisobutyroyloxy) ethyl acrylate and Pd-diimine are 0.10-0.30g/ml, 0.10-0.30g/ml and 25-50 mg/ml; the polymerization reaction is carried out for 12 to 24 hours under the conditions of 25 to 30 ℃ and the ethylene pressure of 1 to 1.5 atm.
6. The method of claim 4, wherein: in the step (b), the feeding molar ratio of HBPE @ Py @ Br, GMA, bipyridine or PMDETA and CuBr is 1 (100-; the polymerization temperature is 30-35 ℃, and the polymerization time is 0.5-24 hours.
7. The method of claim 3, wherein: the step (2) is implemented as follows: pouring a certain amount of natural flaky graphite into a reaction vessel filled with an organic solvent solution of HBPE @ Py @ PGMA polymer, and sealing; and (2) placing the sealed reaction container into an ultrasonic pool, performing ultrasonic treatment at room temperature for 24-60 hours, wherein the ultrasonic power can be selected from 180-320, taking out the mixed solution after the ultrasonic treatment, placing the mixed solution into a centrifuge tube for centrifugation, controlling the rotation speed to be 3000-5000rpm, and the centrifugation time to be 10-50min, performing vacuum filtration on the graphene dispersion liquid containing the excessive pyrenyl terpolymer obtained by the centrifugation to remove the contained excessive copolymer, performing ultrasonic treatment again to disperse the excessive copolymer into an organic solvent, repeating the vacuum filtration-ultrasonic treatment for more than 3 times, drying the dispersion liquid to constant weight, and dispersing the dispersion liquid into the organic solvent to obtain the HBPE @ Py @ PGMA functionalized graphene dispersion liquid.
8. The method of claim 7, wherein: the organic solvent is chloroform, dichloromethane, tetrahydrofuran or toluene.
9. The method of claim 3, wherein: the epoxy resin is bisphenol A type resin E-51, the curing agent is an E593 type curing agent, and the mass ratio of the epoxy resin to the curing agent is 100: 25-28.
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| CN114854197A (en) * | 2022-04-29 | 2022-08-05 | 浙江元盛塑业股份有限公司 | Method for preparing double-component heat-conducting silicone rubber by taking graphene and multi-walled carbon nanotubes as mixed filler |
| CN114907671A (en) * | 2022-05-07 | 2022-08-16 | 重庆大学 | Fluorinated graphene high-thermal-conductivity insulating composite film material and preparation method and application thereof |
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| CN114736525A (en) * | 2022-04-23 | 2022-07-12 | 广东安拓普聚合物科技有限公司 | Heat-conducting filler applied to high-heat-conducting elastomer |
| CN114736525B (en) * | 2022-04-23 | 2023-01-31 | 广东安拓普聚合物科技有限公司 | Heat-conducting filler applied to high-heat-conducting elastomer |
| CN114854197A (en) * | 2022-04-29 | 2022-08-05 | 浙江元盛塑业股份有限公司 | Method for preparing double-component heat-conducting silicone rubber by taking graphene and multi-walled carbon nanotubes as mixed filler |
| CN114907671A (en) * | 2022-05-07 | 2022-08-16 | 重庆大学 | Fluorinated graphene high-thermal-conductivity insulating composite film material and preparation method and application thereof |
| CN114907671B (en) * | 2022-05-07 | 2023-08-18 | 重庆大学 | Fluorinated graphene high-heat-conductivity insulating composite film material and preparation method and application thereof |
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