CN112961635B - Graphene-doped epoxy resin conductive adhesive and preparation method thereof - Google Patents
Graphene-doped epoxy resin conductive adhesive and preparation method thereof Download PDFInfo
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- 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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Abstract
The invention discloses a graphene-doped epoxy resin conductive adhesive and a preparation method thereof, and particularly relates to the technical field of epoxy resin conductive adhesives. The invention can improve the safety and stability of the epoxy resin conductive adhesive, so that the conductive adhesive can be used for a long time at different temperatures and under different strong acid and strong alkali environments to keep normal adhesion connection performance and conductivity; the carbon black and the epoxy resin are respectively subjected to various ultrasonic dispersion modification treatments by adopting the nano silver particle-loaded reduced graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire and the silicon dioxide magnetic microsphere, so that various performances of the carbon black and the epoxy resin can be effectively improved, and the heat resistance, the stability and the acid and alkali resistance of the epoxy resin conductive adhesive can be effectively enhanced.
Description
Technical Field
The invention relates to the technical field of epoxy resin conductive adhesives, in particular to a graphene-doped epoxy resin conductive adhesive and a preparation method thereof.
Background
The conductive adhesive is an adhesive which has certain conductivity after being cured or dried. It can connect multiple conductive materials together to form an electrical path between the connected materials. In the electronics industry, conductive adhesives have become an indispensable new material. The variety of the conductive adhesive is various, and the conductive adhesive can be divided into a general conductive adhesive and a special conductive adhesive from the application angle. The conductive adhesive mainly comprises a resin matrix, conductive particles, a dispersing additive, an auxiliary agent and the like. The matrix mainly comprises epoxy resin, acrylate resin, polyvinyl chloride and the like. The resin matrix of the filler-type conductive adhesive can be, in principle, a resin matrix of various types of adhesive, and commonly used thermosetting adhesives such as epoxy resin, organic silicon resin, polyimide resin, phenolic resin, polyurethane, acrylic resin and the like are generally used. The adhesives form a molecular skeleton structure of the conductive adhesive after curing, guarantee mechanical properties and bonding properties, and enable conductive filler particles to form channels. Epoxy resin-based conductive adhesives dominate because epoxy resins can be cured at room temperature or below 150 ℃ and have rich formulation designability. Epoxy resin has excellent performances of corrosion resistance, electrical insulation, adhesion and the like, but the performances of crack propagation resistance, heat resistance, wear resistance and the like are still required to be improved. Graphene is a honeycomb structure formed by hybridization of a single layer of carbon atoms through SP2 and orderly extending and stacking, and has excellent mechanical strength, specific surface area, electric/thermal conductivity, friction coefficient and the like. In order to make up for the defects of the epoxy resin and fully exert the excellent performance of the graphene, the graphene can be used as a filler to be mixed with the epoxy resin, so that the composite material with excellent comprehensive performance is obtained.
The existing graphene-doped epoxy resin conductive adhesive has poor aging resistance, is very easy to damage when working at high temperature and high acid-base degree for a long time, and reduces the adhesion connection performance and the conductivity.
Disclosure of Invention
In order to overcome the above defects in the prior art, embodiments of the present invention provide a graphene-doped epoxy resin conductive adhesive and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the graphene-doped epoxy resin conductive adhesive comprises the following components in percentage by weight: 29.0-37.0% of carbon black, 1.95-2.95% of nano-silver particle-loaded reduced graphene, 1.95-2.95% of carbon nano tube fibers, 1.95-2.95% of copper-nickel alloy nanowires, 1.95-2.95% of silicon dioxide magnetic microspheres, 7.50-9.50% of a curing agent, 16.0-18.0% of an active diluent, 1.10-1.90% of a coupling agent, and the balance of epoxy resin;
further, the paint comprises the following components in percentage by weight: 29.0% of carbon black, 1.95% of nano-silver particle-loaded reduced graphene, 1.95% of carbon nanotube fibers, 1.95% of copper-nickel alloy nanowires, 1.95% of silica magnetic microspheres, 7.50% of a curing agent, 16.0% of an active diluent, 1.10% of a coupling agent and the balance of epoxy resin.
Further, the paint comprises the following components in percentage by weight: 37.0% of carbon black, 2.95% of nano-silver particle-loaded reduced graphene, 2.95% of carbon nanotube fibers, 2.95% of copper-nickel alloy nanowires, 2.95% of silica magnetic microspheres, 9.50% of a curing agent, 18.0% of an active diluent, 1.90% of a coupling agent and the balance of epoxy resin.
Further, the paint comprises the following components in percentage by weight: 33.0% of carbon black, 2.45% of nano-silver particle-loaded reduced graphene, 2.45% of carbon nanotube fibers, 2.45% of copper-nickel alloy nanowires, 2.45% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent and the balance of epoxy resin.
Further, the curing agent is a polyamine curing agent, the coupling agent is a titanate coupling agent, and the silica magnetic microspheres are core-shell silica magnetic microspheres.
The invention also provides a preparation method of the graphene-doped epoxy resin conductive adhesive, which comprises the following specific preparation steps:
the method comprises the following steps: weighing carbon black, nano silver particle-loaded reduced graphene, carbon nanotube fibers, copper-nickel alloy nanowires, silica magnetic microspheres, a curing agent, an active diluent, a coupling agent and epoxy resin according to the weight percentage;
step two: carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified carbon black A; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of carbon nanotube fiber in the first step to obtain modified carbon black B; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of copper-nickel alloy nanowires in the first step to obtain modified carbon black C; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified carbon black D;
step three: performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified epoxy resin a; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of carbon nanotube fiber in the first step to obtain modified epoxy resin b; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of the epoxy resin and one third part by weight of the copper-nickel alloy nanowires in the step one to obtain modified epoxy resin c; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified epoxy resin d;
step four: carrying out ultrasonic oscillation dispersion treatment on the carbon black, the reduced graphene loaded with the nano silver particles, the carbon nano tube fibers, the copper-nickel alloy nanowires, the silicon dioxide magnetic microspheres and the epoxy resin which are remained in the step one to obtain a modified base material E;
step five: uniformly mixing the modified carbon black A, the modified carbon black B, the modified carbon black C and the modified carbon black D which are prepared in the step two to obtain composite modified carbon black;
step six: performing ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin a prepared in the third step to obtain a modified base material F; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin b prepared in the third step to obtain a modified base material G; performing ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin c prepared in the third step to obtain a modified base material H; performing ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin d prepared in the third step to obtain a modified base material I;
step seven: and (3) mixing the modified base material E prepared in the fourth step with the modified base material F, the modified base material G, the modified base material H, the modified base material I and the reactive diluent prepared in the sixth step, heating to 50-60 ℃, stirring for 1-2 hours, continuously adding a coupling agent and a curing agent, heating to 63-67 ℃, and ultrasonically oscillating for 2-3 hours to obtain the graphene-doped epoxy resin conductive adhesive.
Further, when the ultrasonic oscillation dispersion treatment is performed in the second step and the third step, the ultrasonic oscillation frequency is 1.6 MHz.
Further, when the ultrasonic oscillation dispersion treatment is performed in the sixth and seventh steps, the ultrasonic oscillation frequency is 1.5 MHz.
Further, in the sixth step and the seventh step, the raw material is subjected to intermittent ultrasonic oscillation dispersion treatment, wherein the ultrasonic oscillation treatment is performed once every 10min and is performed for 20min every time.
Further, in the sixth step and the seventh step, the raw material is subjected to intermittent ultrasonic oscillation dispersion treatment, wherein the ultrasonic oscillation treatment is performed once every 10min, and each ultrasonic oscillation treatment is performed for 10 min.
The invention has the technical effects and advantages that:
1. the graphene-doped epoxy resin conductive adhesive prepared by the raw material formula can effectively improve various performances in the epoxy resin conductive adhesive, and improve the safety and stability of the epoxy resin conductive adhesive, so that the conductive adhesive can be used for a long time at different temperatures and under different strong acid and strong alkali environments to keep normal adhesion connection performance and conductivity; the loaded nano silver particles reduce graphene, and the graphene and the nano silver particles are directly compounded and carried, so that the high temperature resistance and the acid and alkali resistance of the conductive adhesive are ensured;
2. in the process of preparing the graphene-doped epoxy resin conductive adhesive, the carbon black is subjected to various ultrasonic dispersion modification treatments by reducing the graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire and the silicon dioxide magnetic microsphere by adopting the loaded nano silver particles in the second step to obtain various modified carbon blacks, so that various properties of the carbon black can be effectively improved, the heat resistance, the stability and the acid and alkali resistance of the carbon black are improved, and the heat resistance, the stability and the acid and alkali resistance of the epoxy resin conductive adhesive are further improved; in the third step, the epoxy resin is subjected to various ultrasonic dispersion modification treatments by adopting the nano silver particle-loaded reduced graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire and the silicon dioxide magnetic microsphere to obtain various modified epoxy resins, so that various properties of the epoxy resin can be effectively improved, the heat resistance, the stability and the acid and alkali resistance of the epoxy resin are improved, and the heat resistance, the stability and the acid and alkali resistance of the epoxy resin conductive adhesive are further improved; and step five, mixing all the modified carbon black to prepare composite modified carbon black, performing ultrasonic modification treatment on the composite modified carbon black and various modified base materials to obtain various modified base materials in step six, and performing composite modification on the various modified carbon black and various modified epoxy resins to further enhance the heat resistance, stability and acid and alkali resistance of the epoxy resin conductive adhesive.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a graphene-doped epoxy resin conductive adhesive which comprises the following components in percentage by weight: 29.0% of carbon black, 1.95% of nano-silver particle-loaded reduced graphene, 1.95% of carbon nanotube fibers, 1.95% of copper-nickel alloy nanowires, 1.95% of silica magnetic microspheres, 7.50% of curing agent, 16.0% of active diluent, 1.10% of coupling agent and the balance of epoxy resin;
the curing agent is a polyamine curing agent, the coupling agent is a titanate coupling agent, and the silicon dioxide magnetic microspheres are core-shell silicon dioxide magnetic microspheres;
the invention also provides a preparation method of the graphene-doped epoxy resin conductive adhesive, which comprises the following specific preparation steps:
the method comprises the following steps: weighing carbon black, nano silver particle-loaded reduced graphene, carbon nanotube fibers, copper-nickel alloy nanowires, silica magnetic microspheres, a curing agent, an active diluent, a coupling agent and epoxy resin according to the weight percentage;
step two: carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of nano silver particle loaded reduced graphene in the first step to obtain modified carbon black A; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of carbon nanotube fiber in the first step to obtain modified carbon black B; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of copper-nickel alloy nanowires in the first step to obtain modified carbon black C; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified carbon black D;
step three: performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified epoxy resin a; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of carbon nanotube fiber in the first step to obtain modified epoxy resin b; performing ultrasonic oscillation and dispersion treatment on one fifth part by weight of the epoxy resin and one third part by weight of the copper-nickel alloy nanowires in the first step to obtain modified epoxy resin c; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified epoxy resin d;
step four: carrying out ultrasonic oscillation dispersion treatment on the carbon black, the nano silver particle-loaded reduced graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire, the silicon dioxide magnetic microsphere and the epoxy resin which are remained in the step one to obtain a modified base material E;
step five: uniformly mixing the modified carbon black A, the modified carbon black B, the modified carbon black C and the modified carbon black D which are prepared in the step two to obtain composite modified carbon black;
step six: carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin a prepared in the third step to obtain a modified base material F; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin b prepared in the third step to obtain a modified base material G; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin c prepared in the third step to obtain a modified base material H; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin d prepared in the third step to obtain a modified base material I;
step seven: and (3) mixing the modified base material E prepared in the fourth step with the modified base material F, the modified base material G, the modified base material H, the modified base material I and the active diluent prepared in the sixth step, heating to 50-60 ℃, stirring for 1-2 hours, continuously adding a coupling agent and a curing agent, heating to 63-67 ℃, and ultrasonically oscillating for 2-3 hours to obtain the graphene-doped epoxy resin conductive adhesive.
When the ultrasonic oscillation dispersion treatment is performed in the second step and the third step, the ultrasonic oscillation frequency is 1.6 MHz.
When the ultrasonic oscillation dispersion treatment is performed in the sixth step and the seventh step, the ultrasonic oscillation frequency is 1.5MHz, and the raw material is subjected to intermittent ultrasonic oscillation dispersion treatment in the sixth step and the seventh step, wherein the ultrasonic oscillation treatment is performed once every 10min, and each ultrasonic oscillation treatment is performed for 20 min.
Example 2:
different from the embodiment 1, the material comprises the following components in percentage by weight: 37.0% of carbon black, 2.95% of nano-silver particle-loaded reduced graphene, 2.95% of carbon nanotube fibers, 2.95% of copper-nickel alloy nanowires, 2.95% of silica magnetic microspheres, 9.50% of a curing agent, 18.0% of an active diluent, 1.90% of a coupling agent and the balance of epoxy resin.
Example 3:
different from the examples 1-2, the material comprises the following components in percentage by weight: 33.0% of carbon black, 2.45% of nano-silver particle-loaded reduced graphene, 2.45% of carbon nanotube fibers, 2.45% of copper-nickel alloy nanowires, 2.45% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent and the balance of epoxy resin.
Respectively taking the graphene-doped epoxy resin conductive adhesive prepared in the above examples 1-3, the epoxy resin conductive adhesive of the first control group, the epoxy resin conductive adhesive of the second control group, the epoxy resin conductive adhesive of the third control group, the epoxy resin conductive adhesive of the fourth control group and the epoxy resin conductive adhesive of the fifth control group, wherein the epoxy resin conductive adhesive of the first control group is a common epoxy resin conductive adhesive on the market, the epoxy resin conductive adhesive of the second control group is not loaded with nano silver particles to reduce graphene compared with the examples, the epoxy resin conductive adhesive of the third control group has no carbon nanotube fiber compared with the examples, the epoxy resin conductive adhesive of the fourth control group has no copper-nickel alloy nano wire compared with the examples, the epoxy resin conductive adhesive of the fifth control group has no silica magnetic microsphere compared with the examples, and the epoxy resin conductive adhesives prepared in the three examples and the epoxy resin conductive adhesives of the five control groups are respectively tested by eight groups, every 30 samples are taken as a group, and the test results are shown in the table one:
table one:
as can be seen from table one, when the graphene doped epoxy resin conductive adhesive comprises the following raw materials in parts by weight: the weight percentage of the components is as follows: 33.0% of carbon black, 2.45% of nano-silver particle-loaded reduced graphene, 2.45% of carbon nanotube fibers, 2.45% of copper-nickel alloy nanowires, 2.45% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent and the balance of epoxy resin, can effectively improve various properties in the epoxy resin conductive adhesive and improve the safety and stability of the epoxy resin conductive adhesive, so that the conductive adhesive can be used for a long time in different strong acid and strong alkali environments at different temperatures to keep normal adhesion connection performance and conductivity; thus, example 3 is a preferred embodiment of the present invention, and the epoxy resin in the formulation is the main supporting material of the conductive adhesive; carbon black is the main conductive material of the conductive adhesive; the loaded nano silver particles are used for reducing the graphene, the graphene and the nano silver particles are directly combined and carried, the combination effect of the graphene and the nano silver particles is better, the conductivity of the epoxy resin conductive adhesive is further improved, the condition that the combination degree of the graphene and the nano silver particles is damaged by environmental temperature and pH factors is avoided, and the high temperature resistance and the acid and alkali resistance of the conductive adhesive are ensured; the carbon nanotube fiber is a one-dimensional continuous assembly of the carbon nanotube, can be used independently, and can form a two-dimensional film or a three-dimensional woven structure through weaving, the carbon nanotube fiber forms a multiple three-dimensional woven structure in the epoxy resin conductive adhesive to serve as a support, so that the stability of the epoxy resin conductive adhesive can be effectively enhanced, and the high temperature resistance and the acid and alkali resistance of the epoxy resin conductive adhesive are further improved; the copper-nickel alloy nanowire has large specific surface area and high surface activity, the content of the copper-nickel nano particles is rich, the price is low, the graphene can effectively support and fix the metal nano particles to prevent the metal nano particles from agglomerating, a channel is provided for charge transfer by utilizing the high conductivity of the graphene, and the conductivity of the epoxy resin conductive adhesive can be effectively ensured by the synergistic effect of the copper-nickel alloy nanowire and the graphene; the porous structure of the silicon dioxide magnetic microsphere can effectively carry other particles in the raw materials, the combination effect of the raw materials is improved, the stability is good, the core-shell type silicon dioxide magnetic microsphere has complete superparamagnetism, the particle size distribution is uniform, the monodispersity is better, all components in the raw materials can be quickly and fully mixed, and the effect of the raw materials can be fully exerted at all positions of the epoxy resin conductive adhesive.
Example 4
In the above preferred technical solution, the present invention provides a graphene-doped epoxy resin conductive adhesive, which comprises, by weight: 33.0% of carbon black, 2.45% of nano-silver particle-loaded reduced graphene, 2.45% of carbon nano tube fibers, 2.45% of copper-nickel alloy nanowires, 2.45% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent and the balance epoxy resin.
The curing agent is a polyamine curing agent, the coupling agent is a titanate coupling agent, and the silicon dioxide magnetic microspheres are core-shell silicon dioxide magnetic microspheres.
The invention also provides a preparation method of the graphene-doped epoxy resin conductive adhesive, which comprises the following specific preparation steps:
the method comprises the following steps: weighing carbon black, nano silver particle-loaded reduced graphene, carbon nanotube fibers, copper-nickel alloy nanowires, silica magnetic microspheres, a curing agent, an active diluent, a coupling agent and epoxy resin according to the weight percentage;
step two: carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of nano silver particle loaded reduced graphene in the first step to obtain modified carbon black A; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of carbon nanotube fiber in the first step to obtain modified carbon black B; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of copper-nickel alloy nanowires in the first step to obtain modified carbon black C; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified carbon black D;
step three: performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified epoxy resin a; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of carbon nanotube fiber in the first step to obtain modified epoxy resin b; performing ultrasonic oscillation and dispersion treatment on one fifth part by weight of the epoxy resin and one third part by weight of the copper-nickel alloy nanowires in the first step to obtain modified epoxy resin c; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified epoxy resin d;
step four: carrying out ultrasonic oscillation dispersion treatment on the carbon black, the nano silver particle-loaded reduced graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire, the silicon dioxide magnetic microsphere and the epoxy resin which are remained in the step one to obtain a modified base material E;
step five: uniformly mixing the modified carbon black A, the modified carbon black B, the modified carbon black C and the modified carbon black D which are prepared in the step two to obtain composite modified carbon black;
step six: carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin a prepared in the third step to obtain a modified base material F; performing ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin b prepared in the third step to obtain a modified base material G; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin c prepared in the third step to obtain a modified base material H; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin d prepared in the third step to obtain a modified base material I;
step seven: and (3) mixing the modified base material E prepared in the fourth step with the modified base material F, the modified base material G, the modified base material H, the modified base material I and the active diluent prepared in the sixth step, heating to 50-60 ℃, stirring for 1-2 hours, continuously adding a coupling agent and a curing agent, heating to 63-67 ℃, and ultrasonically oscillating for 2-3 hours to obtain the graphene-doped epoxy resin conductive adhesive.
When the ultrasonic oscillation dispersion treatment is performed in the second step and the third step, the ultrasonic oscillation frequency is 1.6 MHz.
When the ultrasonic oscillation dispersion treatment is performed in the sixth and seventh steps, the ultrasonic oscillation frequency is 1.5 MHz.
And in the sixth step and the seventh step, the raw materials are subjected to intermittent ultrasonic oscillation dispersion treatment, wherein the ultrasonic oscillation treatment is carried out once every 10min and 20min every time.
Example 5
Unlike example 4, the raw material was subjected to intermittent ultrasonic oscillation dispersion treatment in steps six and seven, and ultrasonic oscillation treatment was performed once every 10 minutes for 10 minutes each time.
Example 6
Different from examples 4-5, the raw materials were subjected to intermittent ultrasonic oscillation dispersion treatment in steps six and seven, and ultrasonic oscillation treatment was performed every 20min for 20 min.
Experiments are respectively carried out on the graphene-doped epoxy resin conductive adhesive prepared in the embodiments 4 to 6, the epoxy resin conductive adhesive of the sixth control group, the epoxy resin conductive adhesive of the seventh control group and the epoxy resin conductive adhesive of the eighth control group, the epoxy resin conductive adhesive of the sixth control group has no operation in the second step compared with the embodiments, the epoxy resin conductive adhesive of the seventh control group has no operation in the third step compared with the embodiments, and the epoxy resin conductive adhesive of the eighth control group has no operation in the sixth step compared with the embodiments; the epoxy resin conductive adhesives prepared in the three examples and the epoxy resin conductive adhesives of the three control groups were tested in six groups, each 30 samples were taken as one group, and the test results are shown in table two:
a second table:
as can be seen from table two, in the process of preparing the graphene-doped epoxy resin conductive adhesive, when the preparation method in the fourth embodiment is the preferred scheme of the present invention, in the second step, the carbon black is subjected to various ultrasonic dispersion modification treatments by using the nano silver particles loaded reduced graphene, the carbon nanotube fibers, the copper-nickel alloy nanowires and the silica magnetic microspheres, so as to obtain various different modified carbon blacks, which can effectively improve various properties of the carbon black, improve heat resistance, stability and acid and alkali resistance of the carbon black, and further improve heat resistance, stability and acid and alkali resistance of the epoxy resin conductive adhesive; in the third step, the loaded nano silver particles are adopted to reduce the graphene, the carbon nano tube fibers, the copper-nickel alloy nanowires and the silicon dioxide magnetic microspheres to respectively carry out various ultrasonic dispersion modification treatments on the epoxy resin, so that various modified epoxy resins are obtained, various performances of the epoxy resins can be effectively improved, the heat resistance, the stability and the acid and alkali resistance of the epoxy resins are improved, and the heat resistance, the stability and the acid and alkali resistance of the epoxy resin conductive adhesive are further improved; and step five, mixing all the modified carbon black to prepare composite modified carbon black, performing ultrasonic modification treatment on the composite modified carbon black and various modified base materials to obtain various modified base materials in step six, and performing composite modification on the various modified carbon black and various modified epoxy resins to further enhance the heat resistance, stability and acid and alkali resistance of the epoxy resin conductive adhesive.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The utility model provides a graphite alkene doping epoxy conducting resin which characterized in that: comprises the following components in percentage by weight: 29.0-37.0% of carbon black, 1.95-2.95% of nano-silver particle-loaded reduced graphene, 1.95-2.95% of carbon nanotube fibers, 1.95-2.95% of copper-nickel alloy nanowires, 1.95-2.95% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent, and the balance of epoxy resin;
the preparation method comprises the following specific steps:
the method comprises the following steps: weighing carbon black, the reduced graphene loaded with the nano silver particles, the carbon nano tube fibers, the copper-nickel alloy nanowires, the silicon dioxide magnetic microspheres, a curing agent, an active diluent, a coupling agent and epoxy resin according to the weight percentage;
step two: carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified carbon black A; performing ultrasonic oscillation and dispersion treatment on one fifth part by weight of carbon black and one third part by weight of carbon nanotube fiber in the first step to obtain modified carbon black B; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of copper-nickel alloy nanowires in the first step to obtain modified carbon black C; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of carbon black and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified carbon black D;
step three: performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of nano silver particle-loaded reduced graphene in the first step to obtain modified epoxy resin a; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of carbon nanotube fiber in the first step to obtain modified epoxy resin b; performing ultrasonic oscillation dispersion treatment on one fifth part by weight of the epoxy resin and one third part by weight of the copper-nickel alloy nanowires in the step one to obtain modified epoxy resin c; carrying out ultrasonic oscillation dispersion treatment on one fifth part by weight of epoxy resin and one third part by weight of silicon dioxide magnetic microspheres in the first step to obtain modified epoxy resin d;
step four: carrying out ultrasonic oscillation dispersion treatment on the carbon black, the nano silver particle-loaded reduced graphene, the carbon nanotube fiber, the copper-nickel alloy nanowire, the silicon dioxide magnetic microsphere and the epoxy resin which are remained in the step one to obtain a modified base material E;
step five: uniformly mixing the modified carbon black A, the modified carbon black B, the modified carbon black C and the modified carbon black D which are prepared in the step two to obtain composite modified carbon black;
step six: carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin a prepared in the third step to obtain a modified base material F; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black prepared in the fifth step and the modified epoxy resin b prepared in the third step to obtain a modified base material G; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin c prepared in the third step to obtain a modified base material H; carrying out ultrasonic oscillation dispersion treatment on one fourth of the composite modified carbon black in part by weight prepared in the fifth step and the modified epoxy resin d prepared in the third step to obtain a modified base material I;
step seven: and (3) mixing the modified base material E prepared in the fourth step with the modified base material F, the modified base material G, the modified base material H, the modified base material I and the active diluent prepared in the sixth step, heating to 50-60 ℃, stirring for 1-2 hours, continuously adding a coupling agent and a curing agent, heating to 63-67 ℃, and ultrasonically oscillating for 2-3 hours to obtain the graphene-doped epoxy resin conductive adhesive.
2. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: comprises the following components in percentage by weight: 29.0% of carbon black, 1.95% of nano-silver particle-loaded reduced graphene, 1.95% of carbon nanotube fibers, 1.95% of copper-nickel alloy nanowires, 1.95% of silica magnetic microspheres, 7.50% of a curing agent, 16.0% of an active diluent, 1.10% of a coupling agent and the balance of epoxy resin.
3. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: comprises the following components in percentage by weight: 37.0% of carbon black, 2.95% of nano-silver particle-loaded reduced graphene, 2.95% of carbon nanotube fibers, 2.95% of copper-nickel alloy nanowires, 2.95% of silica magnetic microspheres, 9.50% of a curing agent, 18.0% of an active diluent, 1.90% of a coupling agent and the balance of epoxy resin.
4. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: comprises the following components in percentage by weight: 33.0% of carbon black, 2.45% of nano-silver particle-loaded reduced graphene, 2.45% of carbon nanotube fibers, 2.45% of copper-nickel alloy nanowires, 2.45% of silicon dioxide magnetic microspheres, 7.50-9.50% of curing agent, 16.0-18.0% of active diluent, 1.10-1.90% of coupling agent and the balance of epoxy resin.
5. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: the curing agent is a polyamine curing agent, the coupling agent is a titanate coupling agent, and the silicon dioxide magnetic microspheres are core-shell silicon dioxide magnetic microspheres.
6. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: when the ultrasonic oscillation dispersion treatment is performed in the second step and the third step, the ultrasonic oscillation frequency is 1.6 MHz.
7. The graphene-doped epoxy resin conductive adhesive according to claim 1, wherein: when the ultrasonic oscillation dispersion treatment is performed in the sixth and seventh steps, the ultrasonic oscillation frequency is 1.5 MHz.
8. The graphene-doped epoxy resin conductive adhesive according to claim 7, wherein: and in the sixth step and the seventh step, the raw materials are subjected to intermittent ultrasonic oscillation dispersion treatment, wherein the ultrasonic oscillation treatment is carried out once every 10min and 20min every time.
9. The graphene-doped epoxy resin conductive adhesive according to claim 7, wherein: and in the sixth step and the seventh step, the raw materials are subjected to intermittent ultrasonic oscillation dispersion treatment, wherein the ultrasonic oscillation treatment is carried out once every 10min, and each ultrasonic oscillation treatment is carried out for 10 min.
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