CN115404040A - Preparation method of conductive adhesive - Google Patents
Preparation method of conductive adhesive Download PDFInfo
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- CN115404040A CN115404040A CN202210982387.XA CN202210982387A CN115404040A CN 115404040 A CN115404040 A CN 115404040A CN 202210982387 A CN202210982387 A CN 202210982387A CN 115404040 A CN115404040 A CN 115404040A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Abstract
The invention discloses a preparation method of a conductive adhesive, which comprises the following steps: (1) synthesizing an HBPE @ POSS @ Py polymer; (2) Under the assistance of HBPE @ POSS @ Py polymer, liquid phase stripping is carried out on graphite powder by utilizing ultrasound to obtain stably dispersed graphene dispersion liquid; (3) Mixing the carbon nano tube, the HBPE @ POSS @ Py polymer and the organic solvent A, performing ultrasonic treatment and centrifugation, taking supernatant, performing high-speed centrifugation or vacuum filtration, adding the obtained solid or filter membrane into the organic solvent A, and performing ultrasonic treatment again to obtain a stably dispersed carbon nano tube dispersion liquid; (4) preparing a 107 glue curing agent; (5) Mixing the graphene dispersion liquid, the carbon nano tube dispersion liquid and 107 gum base glue, performing ultrasonic dispersion uniformly, and drying the solvent; and adding 107 adhesive curing agents into the dried mixture, pouring the mixed composite material onto a PET film after stirring, removing bubbles, and heating and curing to form the conductive adhesive. The invention can improve the electric conduction and heat conduction performance of the conductive adhesive and can also improve the bonding performance of the conductive adhesive.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a preparation method of a conductive adhesive.
Background
With the rapid development of 5G technology in recent years and the rapid development of electronic devices, various electronic device products are gradually developed toward high integration, small size, portability and multiple functions. The problems of connection, packaging and the like of electronic devices are increasingly highlighted, and the defects of the traditional materials are increasingly noticed. The polymer adhesive is widely concerned about with the advantages of low cost, simple process, low curing temperature, strong creep resistance, low pollution and the like, but most of the traditional resin adhesives at present only play a role in bonding, have single function and cannot meet the increasing requirements of electronic equipment on the adhesive. Silicone adhesives have attracted attention because of their excellent thermal stability, weatherability, electrical insulation and chemical resistance. The development of advanced information technologies such as 5G and the like, and new-generation information technologies represented by mobile internet, cloud computing, big data, artificial intelligence, internet of things and the like are deeply integrated with various aspects of society, and the promotion effect of related technologies on the development of economic society is increasingly remarkable.
At present, the conductive adhesive is generally compounded by conductive filler, a polymer matrix and some additives. Metals such as silver and copper are commonly used as conductive fillers because of their high electrical conductivity. However, the use of metal fillers is often limited due to negative effects, such as easy silver powder sedimentation during long-term storage, uneven distribution resulting in affected electrical properties, and thus new fillers are highly needed for preparing conductive adhesives.
In a word, in order to ensure that the conductive adhesive works normally in the using process, a high polymer material with high conductivity and certain bonding strength is urgently needed, and the problem of how to improve the conductivity of the high polymer material needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a conductive adhesive, which aims to solve the problem that the application field of the existing conductive adhesive is limited.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of the conductive adhesive comprises the following steps:
(1) Synthesis of hbpe @ poss @ py: preparing a polymerization system consisting of polyhedral oligomeric silsesquioxane (POSS) shown in a formula I, a pyrene-containing monomer shown in a formula II, an alpha-diimine palladium catalyst and an anhydrous organic solvent, carrying out polymerization reaction in an anhydrous and oxygen-free ethylene atmosphere, and after the reaction is finished, carrying out separation and purification to obtain an HBPE @ POSS @ Py polymer; the structural formulas of the POSS monomer and the pyrene-containing monomer are respectively shown as formula I and formula II:
wherein R is isobutyl;
(2) Mixing graphite powder, HBPE @ POSS @ Py polymer and an organic solvent A, carrying out ultrasonic treatment on the obtained mixture after sealing to obtain an initial graphene dispersion liquid B, and further carrying out low-speed centrifugation and standing treatment to obtain a graphene dispersion liquid C containing excessive HBPE @ POSS @ Py polymer; carrying out high-speed centrifugation or vacuum filtration on the obtained graphene dispersion liquid C to remove excessive HBPE @ POSS @ Py polymer, collecting solid or a filter membrane, and dispersing the solid or the filter membrane into the organic solvent A again by ultrasonic to obtain a stably dispersed graphene dispersion liquid;
(3) Mixing carbon nanotube powder, HBPE @ POSS @ Py polymer and an organic solvent A, carrying out ultrasonic treatment on the obtained mixture after sealing to obtain an initial dispersion liquid D of the carbon nanotube, and further carrying out low-speed centrifugation and standing treatment to obtain a carbon nanotube dispersion liquid E containing excessive HBPE @ POSS @ Py polymer; carrying out high-speed centrifugation or vacuum filtration on the obtained carbon nanotube dispersion liquid E to remove the contained excessive HBPE @ POSS @ Py polymer, collecting the solid or filtering membrane, and dispersing the solid or filtering membrane into the organic solvent A again by ultrasound to obtain the stably dispersed carbon nanotube dispersion liquid;
(4) Uniformly mixing ethyl orthosilicate and dibutyltin dilaurate in a mass ratio of 2-4:1 to prepare a 107-gel curing agent;
(5) Mixing the graphene dispersion liquid, the carbon nano tube dispersion liquid and 107 gum base glue, uniformly dispersing by using ultrasonic waves, and drying the solvent in a drying oven at the temperature of 60-120 ℃; adding the 107 glue curing agent prepared in the step (4) into the dried mixture, placing the mixture into an ice water bath, stirring for 10-30 min, pouring the mixed composite material on a PET film, placing the PET film in a normal-temperature vacuum oven for 10-20 min to remove bubbles, and then transferring the PET film into a blast oven at the temperature of 30-80 ℃ for 6-12 h to cure to form a conductive adhesive;
mixing the graphene dispersion liquid and the carbon nanotube dispersion liquid according to the mass ratio of the graphene to the carbon nanotubes of 0.2-5:1; the mass ratio of the 107 gum base to the 107 gum curing agent is 5-20; the total mass fraction of the graphene and the multi-walled carbon nano-tubes is 3-15% based on 100% of the total mass of the 107 gum and the 107 gum curing agent.
The alpha-diimine palladium catalyst in step (1) of the present invention is preferably one of the following: the catalyst comprises an acetonitrile alpha-diimine palladium catalyst 1 and a six-membered ring alpha-diimine palladium catalyst 2 containing a carbomethoxy group, wherein the structural formulas of the two are as follows:
wherein
The above two alpha-diimine palladium 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.,1995,117,6414；
[2]Johnson L.K.,Mecking S.,Brookhart M.J.Am.Chem.Soc.,1996,118,267.[0028]。
in step (1) of the present invention, the ethylene may be technical grade ethylene or polymer grade ethylene with a purity of 99.95% or more, preferably polymer grade ethylene.
Preferably, in step (1), the anhydrous organic solvent is selected from one of the following: anhydrous dichloromethane, trichloromethane or chlorobenzene, preferably anhydrous dichloromethane.
Preferably, in the step (1), in the polymerization system, the molar ratio of the polyhedral oligomeric silsesquioxane (POSS) to the pyrene-containing monomer is 0.5-2: 1, the initial concentration of the cage-type Polysilsesquioxane (POSS) is 0.1-1 mol/L; the initial concentration of the alpha-diimine palladium catalyst is 5-15 mg/mL.
Preferably, in step (1), the polymerization reaction temperature is room temperature (more preferably 25 to 35 ℃); the ethylene pressure during the polymerization is preferably 1 to 1.5atm; the polymerization reaction time is 12-48 h.
Preferably, in the step (1), the separation and purification after the polymerization reaction is completed is performed according to the following steps: (a) Removing the solvent, dissolving the obtained polymerization product in toluene, adding a small amount of hydrogen peroxide and hydrochloric acid, fully stirring at room temperature to dissolve palladium particles, adding methanol to precipitate out the polymerization product, and removing the supernatant to obtain the polymerization product; repeating the process for 3-4 times; (b) Dissolving the obtained polymerization product in THF, adding methanol to precipitate the polymerization product, removing supernatant to obtain polymerization product, and repeating the process for 3-4 times; (c) The obtained product is vacuumized at room temperature and is dried for 24 to 96 hours at the temperature of between 40 and 80 ℃ in vacuum, and the final polymerization product is obtained.
In the invention, the graphite powder can adopt one of the following sources: natural phosphorus flake graphite or expanded graphite, preferably natural phosphorus flake graphite. The carbon nano-tube is a multi-wall carbon nano-tube.
The organic solvent A in steps (2) and (3) of the present invention may be one of the following analytically pure or chemically pure solvents: chloroform, THF, acetone, dichloromethane, preferably chloroform.
In the step (2), the feeding ratio of the graphite powder to the organic solvent A is 2-200 mg/mL, preferably 5-15mg/mL; the feeding mass ratio of HBPE @ POSS @ Py to graphite powder is 0.1-2:1, preferably 0.1-1:1.
In the step (3), the feeding ratio of the carbon nano tube to the organic solvent A is 0.25-2.5 mg/mL, and the feeding mass ratio of HBPE @ POSS @ Py to the carbon nano tube is 0.8-16.
In the steps (2) and (3), continuously performing ultrasonic treatment on the obtained mixture for 12-72 hours under the conditions that the ultrasonic power is 20-100W and the constant temperature is 15-35 ℃ to obtain graphene initial dispersion liquid B or carbon nano tube initial dispersion liquid D; and centrifuging the graphene initial dispersion liquid B or the carbon nano tube initial dispersion liquid D for 15-60 min at room temperature (preferably 15-35 ℃) and 2000-8000 rpm, standing for 10-20 min, and collecting the centrifugal supernatant liquid to obtain the graphene dispersion liquid C or the carbon nano tube dispersion liquid E containing excessive HBPE @ POSS @ Py polymer.
In steps (2) and (3) of the present invention, the obtained graphene dispersion C or carbon nanotube dispersion E may be subjected to high speed centrifugation to remove the excess hbpe @ poss @ py polymer contained therein, wherein the high speed centrifugation is preferably performed at room temperature (preferably 15 to 35 ℃) and 30000 to 50000rpm, and the centrifugation time is preferably 25 to 60min. In order to sufficiently remove excessive HBPE @ POSS @ Py contained in the graphene dispersion liquid C or the carbon nanotube dispersion liquid E, the bottom precipitate obtained by high-speed centrifugation can be subjected to ultrasonic washing again by using the organic solvent A, and then subjected to high-speed centrifugation again; the "ultrasonic washing-high speed centrifugation" step may be repeated as many times as necessary.
In the steps (2) and (3), the graphene dispersion liquid C or the carbon nano tube dispersion liquid E can be subjected to vacuum filtration by using a microporous filtration membrane to remove excessive HBPE @ POSS @ Py contained in the graphene dispersion liquid C or the carbon nano tube dispersion liquid E, the obtained filtration membrane is added with the organic solvent A to perform ultrasonic dispersion again (room temperature (preferably 15-35 ℃), 0.5-24 h and 40-100W of power), and the vacuum filtration-ultrasonic process can be repeated for multiple times as required to finally obtain the graphene dispersion liquid or the carbon nano tube dispersion liquid. The preferable average pore diameter of the micro-porous filtering membrane is 0.1-0.2 μm, and the material is one of polytetrafluoroethylene, polyvinylidene fluoride or alumina.
In the step (5) of the present invention, the graphene dispersion liquid and the carbon nanotube dispersion liquid are preferably mixed in a mass ratio of graphene to carbon nanotubes of 0.5 to 2:1, and more preferably in a mass ratio of 1:1.
In step (5) of the present invention, the mass ratio of the 107 gum base to the 107 gum curing agent is preferably 5 to 15, more preferably 10.
In the step (5) of the invention, the total mass fraction of the graphene and the multi-wall carbon nano tubes is 3-5% based on 100% of the total mass of the 107 glue base and the 107 glue curing agent, and then the conductive adhesive with better bonding performance can be obtained.
In the step (5), the graphene dispersion liquid, the carbon nano tube dispersion liquid and 107 gum base glue are mixed and uniformly dispersed by ultrasonic, and the mixed liquid is placed in an oven at 60-80 ℃ to dry the solvent; and (3) adding the 107 glue curing agent prepared in the step (4) into the dried mixture, placing the mixture into an ice water bath, stirring for 15-25 min, pouring the mixed composite material onto PET, placing the PET in a normal-temperature vacuum oven for 10-15 min to remove bubbles, and then transferring the PET into a blast oven at the temperature of 60-80 ℃ for 6-10 h to cure to form the conductive adhesive.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) The conductive filler selected by the conductive adhesive provided by the invention is a carbon-based filler, the graphene and the carbon nano tube have very high conductivity, and can be uniformly dispersed in a polymer matrix by a solution blending method after being dispersed by HBPE @ POSS @ Py.
(2) The conductive adhesive provided by the invention takes functionalized graphene and multi-walled carbon nanotubes as fillers, exerts the synergistic conductive effect of the functionalized graphene and the multi-walled carbon nanotubes, and is more favorable for electron transfer.
(3) The invention adopts the functionalized graphene and the multi-walled carbon nanotube as the mixed conductive filler, exerts the synergistic effect of the functionalized graphene and the multi-walled carbon nanotube, can meet the high conductivity required by the conductive adhesive, and simultaneously can improve the heat conductivity of the conductive adhesive and improve the thermal aging problem of the conductive adhesive.
(4) According to the invention, the functionalized graphene and the multi-walled carbon nanotube are used as the mixed conductive filler, so that the conductive and heat-conducting properties of the conductive adhesive can be improved and the bonding property of the conductive adhesive can be improved at the same time under the condition of lower filler content.
(5) The preparation method is simple in preparation process and mild in conditions, and has wide application prospect in the fields of packaging materials and printed circuit boards in the microelectronic industry.
Drawings
FIG. 1 is a schematic diagram of synthesis of HBPE @ POSS @ Py;
FIG. 2 HBPE @ POSS @ Py 1 A HNMR map;
FIG. 3 is an FT-IR diagram of HBPE @ POSS @ Py;
FIG. 4. Schematic representation of HBPE @ POSS @ Py assisted exfoliation of graphene;
FIG. 5 is a schematic diagram of HBPE @ POSS @ Py assisted dispersion of carbon nanotubes;
FIG. 6 is a transmission electron micrograph of graphene;
FIG. 7 is a transmission electron microscope image of carbon nanotubes;
FIG. 8 is a comparative graph of the surface resistance of the composite materials obtained in example 2 and comparative example 1;
FIG. 9 is a comparative plot of the surface resistance of the composites obtained from example 3 and comparative example 2;
FIG. 10 is a comparative plot of the surface resistance of the composites obtained from example 4 and comparative example 3;
FIG. 11 is a comparative plot of the surface resistance of the composites obtained from example 5 and comparative example 4;
FIG. 12 is a graph showing changes in surface resistance of the composite materials obtained in examples 2 to 6 and comparative example 1;
FIG. 13 is a graph comparing thermal conductivities of composite materials obtained in example 7 and comparative example 5;
FIG. 14 is a graph comparing lap shear strengths of composites obtained from examples 8-12 and comparative example 6.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1: synthesis of HBPE @ POSS @ Py
1. Sample preparation
In this embodiment, the hyperbranched polyethylene has a variety of selected types, and illustratively, the hyperbranched polyethylene connected with POSS and connected with pyrene-containing monomer can be obtained by using Pd-diimine catalyst to catalyze ethylene and using a one-step "chain walking" copolymerization mechanism, and the specific preparation process includes the following steps:
(1) A stirring magnet was placed in a 100ml dry double-layer Schlenk bottle, a rubber stopper was plugged, vacuum was applied while the reaction bottle was baked at about 400 ℃ for 3 minutes with an electric heating gun, ethylene was introduced and cooled for 3 minutes, and the ethylene introduction was maintained after repeating 3 times with the pressure set to 1.10 atmospheres (positive pressure protection).
(2) 7.44g (0.008 mol) Acylosobutyl POSS monomer from Hybrid Plastics USA and 1.15g (0.004 mol) pyrene-containing monomer are weighed and poured into a double-layer Schlenk bottle, a rubber stopper is plugged, vacuum is pumped for 3 minutes, ethylene is kept pumped after 3 times of repetition and the pressure is set to be 1.10 atmospheric pressure (positive pressure protection).
(2) 10ml of anhydrous dichloromethane were taken and poured into a double-layer Schlenk flask, the temperature of the waterbath was kept at 25 ℃ and the magnetic stirrer was switched on for stirring.
(3) To a prepared dry brown glass bottle was added Pd-diimine catalyst 1 (200 mg), the brown glass bottle was sealed, vacuum-pumping was repeated 3 times with nitrogen gas, and then 5ml of anhydrous dichloromethane was further injected thereto to prepare a catalyst solution. The solution was taken out and poured into a double-layer Schlenk bottle, and then 3ml and 2ml of anhydrous dichloromethane were taken out and washed twice in a brown glass bottle, and the solution was taken out and poured into a double-layer Schlenk bottle.
(4) The reaction flask is sealed, the ethylene pressure is set to be 1atm, and the mixture is obtained by reaction for 48 hours under the condition of room temperature and a magnetic stirrer.
The above mixture separation procedure is as follows:
(1) The resulting reaction was poured into a 100ml beaker and blown dry with a blower.
(2) The resulting product was dissolved in toluene solution until completely dissolved. 1mL of hydrogen peroxide and hydrochloric acid were added thereto, and the mixture was stirred for 4 hours. Adding methanol to precipitate the product, removing the supernatant to obtain the polymerization product again; this process was repeated 3 to 4 times. Dissolving the obtained product in tetrahydrofuran solution until the product is completely dissolved, adding methanol to precipitate the product, removing supernatant to obtain a polymerization product again; this process was repeated 3 to 4 times.
(3) And vacuumizing the obtained product at normal temperature, then placing the product in a vacuum oven to bake for 72h at 60 ℃, and removing the redundant solvent to obtain the purified product HBPE @ POSS @ Py.
2. Characterization and testing
(1) 1 H nuclear magnetic resonance spectroscopy test
HBPE @ POSS @ Py 1 H nuclear magnetic resonance spectrum ( 1 H NMR) was measured by a 500MHz anace model III nuclear magnetic resonance apparatus (Bruker, switzerland) using deuterated chloroform as the solvent and room temperature as the measurement temperature.
(2) Fourier Infrared Spectroscopy
The test instrument is a Nicolet type Fourier infrared spectrometer manufactured by Nicolet corporation in the United states. The test range is 400-4000 cm -1 Resolution of 4cm -1 The number of scans was 32 and the background was air. The sample was prepared by potassium bromide tableting to a concentration of about 0.01mg "mL -1 The polymer of (3) was dropped on potassium bromide and tested after drying thoroughly.
3. Analysis of test results
The HBPE @ POSS @ Py synthesized in example 1 was solid at room temperature and light brown in color. FIG. 2 shows the results of example 1 1 The HNMR spectra confirmed that multiple POSS groups, pyrene-containing groups, had been grafted into HBPE in a ratio of 2.0mol% (i.e., 2.0 POSS groups per 100 ethylene structural units) and 1.8mol% (i.e., 1.8 pyrene-containing groups per 100 ethylene structural units). FIG. 3 shows an infrared analysis chart at 2925cm for example 1 -1 And 2854cm -1 Has obvious stretching vibration peak of saturated hydrocarbon single bond corresponding to vibration peak of methyl, methylene and methine group on the hyperbranched structures of the two. Meanwhile, HBPE @ POSS @ Py is 1750cm -1 And 1110cm -1 Respectively corresponding to the stretching vibration peak of carbon-oxygen double bond and the antisymmetric stretching vibration peak of silicon-oxygen single bondTwo vibration peaks are the characteristic peaks of POSS and are at 3100cm -1 、1600cm -1 、840cm -1 And the absorption vibration characteristic peak of the corresponding benzene ring is shown, which fully indicates that the hyperbranched polymer is grafted with the POSS monomer and the pyrene-containing monomer.
The purified product of the process of this example was used in the examples that follow.
Example 2 and comparative example 1
1. Preparation of samples
(1) Example 2:
the first step is as follows: 640mg of natural graphite flakes having a purity of 99.5% manufactured by Sigma Aldrich, USA, were weighed into a 100ml cylindrical glass bottle.
The second step is that: 320mgHBPE @ POSS @ Py was weighed into a cylindrical glass bottle, rinsed with 10mL chloroform, and then rinsed 2 times with 5mL chloroform.
The third step: 60ml of chloroform is taken out by a liquid transfer gun and poured into a 100ml cylindrical glass bottle, and the bottle is sealed by a raw material belt and a sealing film.
The fourth step: sealing the solution, placing the solution in a numerical control ultrasonic cleaner with 60W ultrasonic power for ultrasonic treatment for 48h (the power of ultrasonic steps involved in the embodiment of the invention is 60W), and introducing circulating cooling water to keep the temperature at 25-35 ℃.
The fifth step: the solution was removed and centrifuged in a desk top high speed centrifuge at room temperature at 4000rpm for 30min. Standing for 15min, collecting upper layer liquid, vacuum filtering with PTFE filter membrane with aperture of 0.1 μm, collecting the filter membrane, adding 20ml chloroform, and ultrasonic treating in an ultrasonic tank for 2 hr, repeating for three times. Finally, the graphene solution uniformly dispersed in chloroform is obtained.
And a sixth step: weighing 80mg of multi-arm carbon nano-tube produced by Zhongke times nano-production and having the purity of more than 95wt% and 320mg of HBPE @ POSS @ Py, and preparing into suspension according to the operations of the first step to the third step. And (3) performing ultrasonic treatment for 24 hours in an ultrasonic numerical control ultrasonic cleaner.
The seventh step: the resulting suspension was centrifuged in a tabletop high speed centrifuge at 4000rpm for 30min. Standing for 15min, collecting upper layer liquid, vacuum filtering with PTFE filter membrane with aperture of 0.1 μm, collecting the filter membrane, adding 20ml chloroform solution, and ultrasonic treating in ultrasonic tank for 2 hr, repeating for three times. Finally obtaining the multi-walled carbon nanotube solution which is evenly dispersed in chloroform.
Eighth step: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, and uniformly mixing in a beaker by a magnetic stirring manner to prepare the 107-gel curing agent.
The ninth step: weighing 0.91g of 107 gum base glue produced by Ji Peng silicofluoride materials limited, putting the glue in a small glass bottle, adding 15mg of graphene dispersion liquid (the concentration of graphene in chloroform can be obtained by a differential weight method, specifically, measuring a certain volume of graphene dispersion liquid, drying in a 60 ℃ oven to obtain the total mass of graphene and polymer at the moment, obtaining the content of polymer attached to graphene by a thermogravimetry method to obtain the concentration of graphene) and 15mg of multi-walled carbon nanotube dispersion liquid (the concentration of multi-walled carbon nanotube in chloroform can be obtained by the differential weight method, specifically, measuring a certain volume of multi-walled carbon nanotube dispersion liquid, drying in a 60 ℃ oven to obtain the total mass of multi-walled carbon nanotube and polymer at the moment, obtaining the content of polymer attached to multi-walled carbon nanotube by the thermogravimetry method to obtain the concentration of multi-walled carbon nanotube), uniformly dispersing for 2h by ultrasound, and drying in an 80 ℃ oven to obtain a solvent.
The tenth step: adding 0.09g of 107 glue curing agent into the mixture after drying the solvent, stirring for 20 minutes in an ice-water bath, uniformly coating the mixed composite material on a PET film with the thickness of 25 microns by scraping, placing the PET film in a normal-temperature vacuum oven for 15 minutes to remove bubbles, and then transferring the PET film into a blast oven with the temperature of 60 ℃ for 8 hours to cure, so as to form a 107 glue conductive composite film with the thickness of 200 microns and the total filler mass fraction of graphene/carbon nanotubes of 3wt% (the mass fraction is calculated by taking the total mass of 107 glue base glue and 107 glue curing agent as 100%, the same applies below).
(2) Comparative example 1:
the first step is as follows: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, uniformly mixing in a beaker by a magnetic stirring manner to prepare a 107-gel curing agent;
the second step is that: 0.91g of 107 gum base manufactured by Ji Peng silicofluoride materials ltd was weighed into a glass vial, and 0.09g of 107 gum curing agent was added thereto and stirred in an ice-water bath for 20 minutes.
The third step: and uniformly coating the mixed composite material on a PET film with the thickness of 25 mu m by scraping, placing the PET film in a normal-temperature vacuum oven for 15min to remove bubbles, and then transferring the PET film into a blast oven with the temperature of 60 ℃ for 8h to be cured to form a pure 107 adhesive film.
2. Characterization and testing
(1) TEM analysis of transmission electron microscopy
The test instrument is a JEM-100CX type high-resolution transmission electron microscope produced by FEI company in America.
Preparing a sample: taking 15ml of centrifuged supernatant, taking a proper amount of suspension liquid to drop on the surface of a copper mesh, and testing after the solvent is volatilized to be dry.
(2) High resistance measurement instrument test
The test instrument is a surface resistance tester manufactured by Shanghai faih instruments Ltd.
And (3) placing two metal electrodes on the surface of the adhesive layer at room temperature, selecting different points for testing, measuring for 3 times, and taking the average value.
3. Analysis of test results
By utilizing the idea of the invention, the prepared graphene with uniform distribution and the carbon tube with good dispersion can be directly observed from the TEM images of FIG. 6 and FIG. 7 by taking the obtained HBPE @ POSS @ Py as the stabilizer. As can be seen from the comparison result of the surface resistance test in fig. 8, when the graphene and the multi-walled carbon nanotube are added to the 107 glue, the conductive capability of the adhesive is improved to some extent.
Example 3 and comparative example 2
1. Preparation of samples
(1) Example 3:
a method for preparing a conductive adhesive is provided, which is the same as that in embodiment 2 and will not be described herein again. The difference lies in that: the total mass fraction of graphene and carbon tubes is 8%, wherein the ratio of graphene: the mass ratio of the carbon tubes was 1:1.
(2) Comparative example 2:
the first to fifth steps are the same as those of embodiment 2.
And a sixth step: ethyl orthosilicate and dibutyltin dilaurate are mixed according to the weight ratio of 3:1, and uniformly mixing in a beaker by a magnetic stirring manner to prepare the 107-gel curing agent.
The seventh step: 0.91g of 107 gum base glue produced by Ji Peng silicofluoride materials limited is weighed into a small glass bottle, graphene dispersion liquid with the graphene mass of 80mg is added, the mixture is uniformly dispersed by ultrasonic for 2 hours, and then the mixture is placed into an oven at 80 ℃ to dry a solvent.
Eighth step: and adding 0.09g of 107 glue curing agent into the mixture after the solvent is dried, stirring in an ice-water bath for 20 minutes, uniformly coating the mixed composite material on a PET (polyethylene terephthalate) film with the thickness of 25 micrometers by scraping, placing the PET film in a normal-temperature vacuum oven for 15 minutes to remove bubbles, and then transferring the PET film into a blast oven at 60 ℃ for 8 hours to cure to form a 107 glue conductive composite film with the graphene filler mass fraction of 8 wt%.
2. Characterization and testing
High resistance measurement instrument test
The test apparatus was a surface resistance tester manufactured by Shanghai faih instruments Co., ltd.
Placing two metal electrodes on the surface of the adhesive layer at room temperature, selecting different points for testing, measuring for 3 times, and taking the average value
3. Comparison and analysis of test results
The results of the surface resistance analysis of example 3 and comparative example 2 in fig. 9 show that: under the same adding proportion, the composite material obtained by simultaneously adding the graphene and the carbon nano tube has better conductivity than the composite material obtained by only adding the graphene.
Example 4 and comparative example 3
1. Preparation of samples
(1) Example 4:
a method for preparing a conductive adhesive is provided, which is the same as that in example 2 and will not be described herein. The difference lies in that: the total mass fraction of graphene and carbon tubes is 10%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(2) Comparative example 3:
the first step is as follows: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, and uniformly mixing in a beaker by a magnetic stirring manner to prepare the 107-gel curing agent.
The second step is that: 0.91g of 107 gum base glue produced by Ji Peng silicofluoride materials limited is weighed into a small glass bottle, 100mg of graphite powder provided by Zhengzhou Hisai chemical products limited and 5mL of chloroform are added, ultrasonic treatment is carried out for 2h to be uniformly dispersed, and then the mixture is placed into an oven at 80 ℃ to dry a solvent.
The third step: and adding 0.09g of 107 glue curing agent into the mixture after the solvent is dried, stirring in an ice-water bath for 20 minutes, uniformly coating the mixed composite material on a PET film with the thickness of 25 microns by scraping, placing the PET film in a normal-temperature vacuum oven for 15 minutes to remove bubbles, and then transferring the PET film into a blast oven with the temperature of 60 ℃ for 8 hours to cure to form a 107 glue conductive composite film with the graphite powder filler mass fraction of 10 wt%.
2. Characterization and testing
High resistance measurement instrument test
The test instrument is a surface resistance tester manufactured by Shanghai faih instruments Ltd.
Placing two metal electrodes on the surface of the adhesive layer at room temperature, selecting different points for testing, measuring for 3 times, and taking the average value
3. Comparison and analysis of test results
The results of the surface resistance analysis of example 4 and comparative example 3 in fig. 10 show that: under the same adding proportion, the composite material obtained by simultaneously adding the graphene and the carbon nano tube has better conductivity than the composite material obtained by only adding the graphite powder.
Example 5, example 6, and comparative example 4
1. Preparation of samples
(1) Example 5:
a method for preparing a conductive adhesive is provided, which is the same as that in embodiment 2 and will not be described herein again. The difference lies in that: the total mass fraction of graphene and carbon tubes is 15%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(2) Example 6:
a method for preparing a conductive adhesive is provided, which is the same as that in example 2 and will not be described herein. The difference lies in that: the total mass fraction of graphene and carbon tubes is 5%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(3) Comparative example 4:
the first step is as follows: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, and uniformly mixing in a beaker by a magnetic stirring manner to prepare the 107-gel curing agent.
The second step is that: 0.91g of 107 gum base glue produced by Ji Peng silicofluoride materials Limited is weighed into a small glass bottle, 150mg of multi-arm carbon nano-tube with the purity of more than 95wt% produced by Zhongke times nano and 5mL of chloroform are added, and the mixture is placed into an oven at 80 ℃ after being evenly dispersed for 2 h.
The third step: and adding 0.09g of 107 glue curing agent into the mixture after the solvent is dried, stirring for 20 minutes in an ice-water bath, uniformly coating the mixed composite material on a PET (polyethylene terephthalate) film with the thickness of 25 micrometers by scraping, placing the PET film in a normal-temperature vacuum oven for 15 minutes to remove bubbles, and then transferring the PET film into a blast oven with the temperature of 60 ℃ for 8 hours to cure to form a 107 glue conductive composite film with the carbon tube filler mass fraction of 15 wt%.
2. Characterization and testing
High resistance measurement instrument test
The test instrument is a surface resistance tester manufactured by Shanghai faih instruments Ltd.
Placing two metal electrodes on the surface of the adhesive layer at room temperature, selecting different points for testing, measuring for 3 times, and taking the average value
3. Comparison and analysis of test results
The results of the surface resistance analysis of example 5 and comparative example 4 in fig. 11 show that: under the same adding proportion, the composite material obtained by simultaneously adding the graphene and the carbon nano tube has better conductivity than the composite material obtained by only adding the multi-arm carbon nano tube which is not subjected to ultrasonic dispersion. From the surface resistance variation trends of examples 2 to 6 and comparative example 1 in fig. 12, the surface resistance of the composite material rapidly decreases with the increase of the conductive filler, but the decrease of the conductive property gradually decreases when the conductive threshold is reached.
Example 7, comparative example 5
1. Preparation of samples
(1) Example 7:
a method for preparing a conductive adhesive is provided, which is the same as that in embodiment 2 and will not be described herein again. Except that in the tenth step the mixed composite was poured into a custom made circular PTFE mould with a diameter of 12.7mm and a depth of 1mm to give a 107 glue composite disc.
(2) Comparative example 5:
the first step is as follows: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, and uniformly mixing in a beaker by a magnetic stirring manner to prepare the 107-gel curing agent.
The second step is that: 0.91g of 107 gum base manufactured by Ji Peng silicofluoride materials ltd was weighed into a glass vial, and 0.09g of 107 gum curing agent was added and stirred in an ice-water bath for 20 minutes.
The third step: and pouring the mixed composite material into a customized circular PTFE (Polytetrafluoroethylene) mold with the diameter of 12.7mm and the depth of 1mm, placing the mold in a normal-temperature vacuum oven for 15min to remove bubbles, and then transferring the mold into a blast oven with the temperature of 60 ℃ for 8h to cure to obtain a 107 glue composite wafer.
2. Characterization and testing
(1) Thermal diffusivity test
The test instrument is an LFA 467 type laser thermal conductivity instrument produced by Germany relaxation resistance. The vertical thermal diffusion coefficient measurement requires that the diameter of a sample is 12.7mm, the thickness is 1-2 mm, and a layer of uniform graphite is sprayed on the surface of the sample before the test. The test selects three data points, and takes the average as the final result.
(2) Differential scanning calorimetry
The test apparatus is a type Q20 differential scanning calorimeter manufactured by TA of America. And (3) testing the specific heat capacity by adopting a sapphire three-wire method, wherein the testing temperature range is from 0 ℃ to 60 ℃, the heating rate is 10 ℃/min, and the testing atmosphere is nitrogen.
3. Comparison and analysis of test results
By the formula λ (T) = α (T) · Cp (T) ·Rho (T) can be calculated according to the thermal diffusion coefficient, the specific heat capacity and the density of the sample to obtain the thermal conductivity of the sample, and the magnitude of the numerical value of the thermal conductivity reflects the strength of the heat conducting capacity of the sample. Wherein, λ: the thermal conductivity of the sample, W/(m.K); α: thermal diffusivity, m, of the sample 2 S; cp is the specific heat capacity of the sample, J/(kg. K); rho density of the sample, kg/m 3 . Comparing the calculated thermal conductivities, it can be obviously observed from fig. 13 that the vertical thermal conductivity of the adhesive in example 7 is obviously improved compared with that in comparative example 5, which shows that the thermal conductivity of the adhesive in 107 can be effectively improved after the graphene and the carbon nanotubes are added.
Examples 8 to 12 and comparative example 6
1. Preparation of samples
(1) Example 8:
the nine steps of the preparation method are the same as those in the embodiment 2, the tenth step is that 0.09g107 glue curing agent is added into the mixture after the solvent is dried, the mixture is stirred in ice water bath for 20 minutes, a small amount of the mixed composite material is coated on a glass slide (Shenyan brand, the specification is 25.6 multiplied by 76mm, the thickness is 1-1.2 mm), the coating length is 30mm, another glass slide is covered, and the glass slide is placed in a normal-temperature air-blowing oven to be cured for 8 hours, so that a sample for testing the lap joint shear strength is obtained.
(2) Example 9:
a method for preparing a conductive adhesive is provided, which is the same as that in example 8 and will not be described herein. The difference is that the total mass fraction of graphene and carbon tubes is 5%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(3) Example 10:
a method for preparing a conductive adhesive is provided, which is the same as that in example 8 and will not be described herein. The difference is that the total mass fraction of graphene and carbon tubes is 8%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(4) Example 11:
a method for preparing a conductive adhesive is provided, which is the same as that in example 8 and will not be described herein. The difference is that the total mass fraction of graphene and carbon tubes is 10%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(5) Example 12:
a method for preparing a conductive adhesive is provided, which is the same as that in example 8 and will not be described herein. The difference is that the total mass fraction of graphene and carbon tubes is 15%, wherein the mass fraction of graphene: the mass ratio of the carbon tubes was 1:1.
(6) Comparative example 6:
the first step is as follows: ethyl orthosilicate and dibutyltin dilaurate were mixed according to a ratio of 3:1, uniformly mixing in a beaker by a magnetic stirring manner to prepare a 107-gel curing agent;
the second step: 0.91g of 107 gum base manufactured by Ji Peng silicofluoride materials ltd was weighed into a glass vial, and 0.09g of 107 gum curing agent was added thereto and stirred in an ice-water bath for 20 minutes.
The third step: and (3) coating a small amount of the mixed composite material on a glass slide (Shenyan brand, the specification is 25.6 multiplied by 76mm, the thickness is 1-1.2 mm), the coating length is 30mm, covering another glass slide, placing the glass slide in a normal-temperature air-blast oven, and curing for 8 hours to obtain a sample for testing the lap joint shear strength.
2. Characterization and testing
Shear Strength test
High-low temperature double-column testing machine with testing instrument of model Instron5966
At room temperature, a film clamp of 2710-004 type is used for clamping two bonded glass sheets, then a tensile test is carried out, the tensile speed is 5mm/min, the measurement is carried out for 3 times, and an average value is taken.
3. Comparison and analysis of test results
The test results for examples 8-12 and comparative example 6 in FIG. 14 show that: under the addition proportion of 3 percent and 5 percent, the lap shear strength of the composite material obtained by adding the graphene and the carbon nano tubes is more excellent than that of pure 107 glue, which shows that the bonding capability of the 107 glue is improved to a certain extent, the bonding capability is reduced when the filling proportion is continuously increased, but the higher bonding strength is still maintained, and the bonding strength is basically kept stable under the filling proportion of 8 percent to 15 percent.
The above results show that: the uniformly dispersed graphene and carbon nanotube dispersion liquid containing HBPE @ POSS @ Py polymer on the surface can be successfully obtained by utilizing the idea of the invention, and the heat conductivity of the 107 adhesive is improved to a certain extent while the electric conductivity of the adhesive is improved, and the high bonding strength is maintained.
Claims (10)
1. The preparation method of the conductive adhesive is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Synthesis of HBPE @ POSS @ Py: preparing a polymerization system consisting of cage polysilsesquioxane shown as a formula I, pyrene-containing monomer shown as a formula II, alpha-diimine palladium catalyst and an anhydrous organic solvent, performing polymerization reaction in an anhydrous and oxygen-free ethylene atmosphere, and after the reaction is finished, separating and purifying to obtain an HBPE @ POSS @ Py polymer; the structural formulas of the POSS monomer and the pyrene-containing monomer are respectively shown as formula I and formula II:
wherein R is isobutyl;
(2) Mixing graphite powder, HBPE @ POSS @ Py polymer and an organic solvent A, carrying out ultrasonic treatment on the obtained mixture after sealing to obtain graphene initial dispersion liquid B, and further carrying out low-speed centrifugation and standing treatment to obtain graphene dispersion liquid C containing excessive HBPE @ POSS @ Py polymer; carrying out high-speed centrifugation or vacuum filtration on the obtained graphene dispersion liquid C to remove excessive HBPE @ POSS @ Py polymer, collecting solid or a filter membrane, and dispersing the solid or the filter membrane into the organic solvent A again by ultrasonic to obtain graphene dispersion liquid;
(3) Mixing carbon nanotube powder, HBPE @ POSS @ Py polymer and an organic solvent A, carrying out ultrasonic treatment on the obtained mixture after sealing to obtain an initial dispersion liquid D of the carbon nanotube, and further carrying out low-speed centrifugation and standing treatment to obtain a carbon nanotube dispersion liquid E containing excessive HBPE @ POSS @ Py polymer; carrying out high-speed centrifugation or vacuum filtration on the obtained carbon nanotube dispersion liquid E to remove the contained excessive HBPE @ POSS @ Py polymer, collecting the solid or filtering membrane, and dispersing the solid or filtering membrane into the organic solvent A again by ultrasound to obtain the carbon nanotube dispersion liquid;
(4) Uniformly mixing ethyl orthosilicate and dibutyltin dilaurate in a mass ratio of 2-4:1 to prepare a 107-gel curing agent;
(5) Mixing the graphene dispersion liquid, the carbon nano tube dispersion liquid and 107 gum base glue, uniformly dispersing by using ultrasonic waves, and drying the solvent in an oven at the temperature of 60-120 ℃; adding the 107 glue curing agent prepared in the step (4) into the dried mixture, placing the mixture into an ice water bath, stirring for 10-30 min, pouring the mixed composite material on a PET film, placing the PET film in a normal-temperature vacuum oven for 10-20 min to remove bubbles, and then transferring the PET film into a blast oven at the temperature of 30-80 ℃ for 6-12 h to cure to form a conductive adhesive;
mixing the graphene dispersion liquid and the carbon nanotube dispersion liquid according to the mass ratio of the graphene to the carbon nanotubes of 0.2-5:1; the mass ratio of the 107 gum base to the 107 gum curing agent is 5-20; the total mass fraction of the graphene and the multi-walled carbon nanotube is 3-15% by taking the total mass of the 107 glue and the 107 glue curing agent as 100%.
2. The method of claim 1, wherein: in the step (1), the alpha-diimine palladium catalyst is selected from one of the following: the catalyst comprises an acetonitrile alpha-diimine palladium catalyst 1 and a six-membered ring alpha-diimine palladium catalyst 2 containing a carbomethoxy group, wherein the structural formulas of the two are as follows:
wherein
The anhydrous grade organic solvent is selected from one of the following: anhydrous dichloromethane, trichloromethane or chlorobenzene;
in the polymerization system, the molar ratio of the cage-type polysilsesquioxane to the pyrene-containing monomer is 0.5-2: 1, the initial concentration of the cage type polysilsesquioxane is 0.1-1 mol/L; the initial concentration of the alpha-diimine palladium catalyst is 5-15mg/mL;
the polymerization reaction temperature is room temperature, the ethylene pressure in the polymerization process is 1-1.5 atm, and the polymerization reaction time is 12-48 h.
3. The method of claim 1, wherein: the organic solvent A in the steps (2) and (3) adopts one of the following analytically pure or chemically pure solvents: chloroform, THF, acetone, dichloromethane.
4. The method of claim 1, wherein: in the step (2), the feeding ratio of the graphite powder to the organic solvent A is 2-200 mg/mL, preferably 5-15mg/mL; the feeding mass ratio of HBPE @ POSS @ Py to graphite powder is 0.1-2:1, preferably 0.1-1:1;
in the step (3), the feeding ratio of the carbon nano tube to the organic solvent A is 0.25-2.5 mg/mL, and the feeding mass ratio of HBPE @ POSS @ Py to the carbon nano tube is 0.8-16.
5. The method of claim 1, wherein: in the steps (2) and (3), continuously performing ultrasonic treatment on the obtained mixture for 12-72 hours under the conditions that the ultrasonic power is 20-100W and the constant temperature is 15-35 ℃ to obtain graphene initial dispersion liquid B or carbon nano tube initial dispersion liquid D; and centrifuging the graphene initial dispersion liquid B or the carbon nano tube initial dispersion liquid D for 15-60 min at room temperature under the condition of 2000-8000 rpm, standing for 10-20 min, and collecting the centrifugal supernatant liquid to obtain the graphene dispersion liquid C or the carbon nano tube dispersion liquid E containing excessive HBPE @ POSS @ Py polymer.
6. The method of claim 1, wherein: in the steps (2) and (3), performing high-speed centrifugation on the obtained graphene dispersion liquid C or carbon nanotube dispersion liquid E to remove excessive HBPE @ POSS @ Py polymer, wherein the high-speed centrifugation condition is recommended to be performed at room temperature and 30000-50000 rpm, and the centrifugation time is 25-60 min; or carrying out vacuum filtration on the graphene dispersion liquid C or the carbon nano tube dispersion liquid E by using a microfiltration membrane so as to remove contained excessive HBPE @ POSS @ Py, adding an organic solvent A into the obtained filter membrane, and carrying out ultrasonic dispersion again to finally obtain the graphene dispersion liquid or the carbon nano tube dispersion liquid.
7. The method of claim 1, wherein: in the step (5), the graphene dispersion liquid and the carbon nanotube dispersion liquid are mixed according to a mass ratio of graphene to carbon nanotubes of 0.5 to 2:1, preferably 1:1.
8. The method of claim 1, wherein: in the step (5), the mass ratio of the 107 gum base to the 107 gum curing agent is 5-15, preferably 10.
9. The method of claim 1, wherein: in the step (5), the total mass fraction of the graphene and the multi-walled carbon nanotubes is 3-5% based on 100% of the total mass of the 107 gum and the 107 gum curing agent.
10. The method of claim 1, wherein: in the step (5), mixing and ultrasonically dispersing the graphene dispersion liquid, the carbon nano tube dispersion liquid and 107 glue base glue uniformly, and drying the solvent in an oven at the temperature of 60-80 ℃; and (3) adding the 107 glue curing agent prepared in the step (4) into the dried mixture, placing the mixture into an ice water bath, stirring for 15-25 min, pouring the mixed composite material onto PET, placing the PET in a normal-temperature vacuum oven for 10-15 min to remove bubbles, and then transferring the PET into a blast oven at the temperature of 60-80 ℃ for 6-10 h to cure to form the conductive adhesive.
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