CN112094602A - Epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive and preparation method thereof - Google Patents
Epoxy resin-based carbon nano composite electromagnetic shielding 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
- 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
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive and a preparation method thereof, wherein an excellent carbon nano material is adopted to partially replace a traditional silver powder material, the using amount of silver powder is obviously reduced, a synergistic effect of the carbon nano material and silver nano particles is exerted, an improved flame retardant is added, and the preparation process is optimized, so that a novel epoxy resin-based conductive adhesive material with an electromagnetic shielding function is prepared, and a technical basis is provided for the application of the epoxy resin-based conductive adhesive material in the field of electronic information.
Description
Technical Field
The invention relates to the technical field of materials, in particular to epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive and a preparation method thereof.
Background
Epoxy resins (Epoxyresins) are a general term for compounds which contain two or more epoxy groups in one molecule and which form a three-dimensional crosslinked network-like cured product in the presence of a suitable chemical agent. There are many types of epoxy resins, and their molecular weights fall within a range of oligomers, sometimes referred to as epoxy oligomers, to distinguish the cured epoxy resins. The epoxy resin and the curing agent can form three-dimensional reticular thermosetting plastic after reaction. The resin is usually used in a liquid state and is cured at normal temperature or under heating to achieve the purpose of final use. The epoxy resin is used as a liquid resin, has the characteristics of small shrinkage rate in the curing reaction process, and excellent cohesiveness, heat resistance, corrosion resistance, mechanical property and electrical property of a cured product, and is a variety with larger application amount in thermosetting resin. At present, the epoxy resin is widely applied to the manufacture of various metal and nonmetal bonding, corrosion-resistant coatings, electrical insulating materials, glass fiber reinforced plastics/composite materials and the like, plays an increasingly important role in aerospace, shipping, electronics, electrical and mechanical manufacturing, chemical corrosion prevention and other industrial fields, becomes an indispensable basic material in various industrial fields, develops towards six directions of high purification, refinement, specialization, serialization, matching and functionalization, and meets the requirements of various industries on different performances of epoxy resin. The application fields of epoxy resins are extremely wide, in the form of direct or indirect use, almost throughout all industrial fields, such as the fields of automobiles, containers, factory equipment, civil engineering and construction, ships, household appliances, and the like as coatings; as adhesives for use in airplanes, automobiles, optical machines, electronic and electric, railway vehicles, civil and architectural applications, and the like; as molding materials for electric appliances, tools, etc.; the fiber reinforced resin matrix composite material is used for airplanes, heavy electric appliances, sports goods and the like.
The epoxy resin has an oxygen index of 19.8 and belongs to the category of flammable materials. Although the flammability of epoxy resins varies greatly due to their composition and structure. For example, the molecular structures and compositions of the two-part type A epoxy resin and the alicyclic epoxy resin are obviously different, and the oxygen index is different due to different O/C ratios of oxygen atoms to carbon atoms in the polymers; the smaller the O/C ratio, the higher the oxygen index. The two-part type A epoxy resin has a higher oxygen index and a lower flammability than the cycloaliphatic epoxy resin, while the novolac epoxy resin has a higher oxygen index than the two-part type A epoxy resin. In conjunction with applications in the field of electronic information, there is a need for flame retardant modification of epoxy resins in view of safety considerations. At present, the commonly used flame retardant is a halogen-containing flame retardant, and the flame retardant performance of the resin is realized mainly through flame retardant elements such as halogen, phosphorus, boron, nitrogen and the like. However, halogen has toxicity and great harm, so how to obtain the novel epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive becomes a problem to be solved urgently.
Disclosure of Invention
The invention provides an epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive and a preparation method thereof, which aim to solve the problem of toxicity caused by flame retardance of halogen in the conventional epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
In a first aspect, the present invention provides a method for preparing an epoxy resin-based carbon nanocomposite electromagnetic shielding conductive adhesive, comprising: taking epoxy resin as a first carrier, diluting the epoxy resin by a diluent, taking a graphene, carbon nano tube and silver powder compound system as a conductive functional filler, and carrying out ball-milling mixing on the diluted epoxy resin and the conductive functional filler to obtain a first mixture; taking a curing agent as a second carrier, taking a compound system of aluminum hydroxide, magnesium hydroxide and red phosphorus as a flame retardant, and carrying out ball milling and mixing on the curing agent and the flame retardant to obtain a second mixture; and curing the second mixture through the second mixture to obtain the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
Optionally, the mass ratio of the epoxy resin, the curing agent, the diluent, the conductive functional filler and the flame retardant is 100: 20-50: 5-25: 12-60: 30 to 100.
Optionally, the mass ratio of the graphene, the carbon nanotubes and the silver powder is 1-5: 1-5: 10 to 50;
the mass ratio of the aluminum hydroxide to the magnesium hydroxide to the red phosphorus is 10-50: 10-50: 0 to 5.
Optionally, the graphene is lamellar graphene, and the thickness of the graphene is 5-50 nm, and the width of the graphene is 10-50 microns.
Optionally, the carbon nanotube is a multi-walled carbon nanotube, the outer diameter of the carbon nanotube is 10-50 nm, and the length of the carbon nanotube is 10-100 μm.
Optionally, the silver powder is spherical, flake or linear, the amount of the spherical silver powder is 50 parts at most, the amount of the linear silver powder is 10 parts at least, and the size of one dimension of the silver powder is 1-4 μm.
Optionally, the ball milling revolution speed of ball milling and mixing the diluted epoxy resin and the conductive functional filler is 100-.
Optionally, the curing agent and the flame retardant are subjected to ball milling and mixing, wherein the ball milling revolution speed is 100-.
Optionally, curing the second mixture by the second mixture comprises: and solidifying the second mixture through the second mixture, wherein the mass ratio of the first mixture to the second mixture is 10: 2-5, and the curing time is 10-60 min.
In a second aspect, the invention provides an epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive, which is prepared by any one of the methods.
The invention has the following beneficial effects:
the invention adopts excellent carbon nano material to partially replace the traditional silver powder material, obviously reduces the consumption of silver powder, and prepares the novel epoxy resin-based conductive adhesive material with electromagnetic shielding function by exerting the synergistic effect of the carbon nano material and the silver nano particles, adding the improved flame retardant and optimizing the preparation process.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing an epoxy resin-based carbon nanocomposite electromagnetic shielding conductive adhesive according to a first embodiment of the present invention;
fig. 2 is a schematic flow chart of another method for preparing an epoxy resin-based carbon nanocomposite electromagnetic shielding conductive adhesive according to a first embodiment of the present invention;
FIG. 3a is a diagram illustrating the effect of a first embodiment of the present invention on the physical application of a conductive agent;
fig. 3b is a diagram illustrating an actual application effect of another mixture ratio of the conductive agent according to the first embodiment of the present invention.
Detailed Description
The embodiment of the invention aims at the problem that the existing epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive adopts halogen as a flame retardant to introduce toxin, and provides a method for preparing the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive. The present invention will be described in further detail below with reference to the drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The first embodiment of the invention provides a method for preparing epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive, and referring to fig. 1, the method comprises the following steps:
s101, preparing a first mixture and a second mixture;
specifically, in the embodiment of the invention, epoxy resin is used as a first carrier, the epoxy resin is diluted by a diluent, a graphene, carbon nano tube and silver powder compound system is used as a conductive functional filler, and the diluted epoxy resin and the conductive functional filler are subjected to ball milling and mixing to obtain a first mixture; taking a curing agent as a second carrier, taking a compound system of aluminum hydroxide, magnesium hydroxide and red phosphorus as a flame retardant, and carrying out ball milling and mixing on the curing agent and the flame retardant to obtain a second mixture;
s102, curing the second mixture through the second mixture to obtain the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
In other words, the embodiment of the invention adopts the excellent carbon nano material to partially replace the traditional silver powder material, the consumption of the silver powder is obviously reduced, the novel epoxy resin-based conductive adhesive material with the electromagnetic shielding function is prepared by exerting the synergistic effect of the carbon nano material and the silver nano particles, adding the improved flame retardant and optimizing the preparation process, and the technical basis is provided for the application of the epoxy resin-based conductive adhesive material in the field of electronic information.
In other words, the embodiment of the invention adopts the carbon nano composite conductive functional auxiliary agent and the halogen-free composite flame retardant to respectively treat the epoxy resin and the curing agent, and synchronously prepares the liquid mixed component containing the specific functional component, optimizes the reaction process condition and process rule, obtains the optimal process and parameter condition, mainly solves the problems of light weight, conductivity, flame retardance and the like of the epoxy resin-based conductive adhesive used in the electronic information field, and prepares the epoxy resin-based carbon nano composite conductive adhesive material with the electromagnetic shielding function.
In specific implementation, the mass ratio of the epoxy resin, the curing agent, the diluent, the conductive functional filler and the flame retardant in the embodiment of the invention is 100: 20-50: 5-25: 12-60: 30-100, wherein the mass ratio of the graphene to the carbon nano tube to the silver powder is 1-5: 1-5: 10 to 50; the mass ratio of the aluminum hydroxide to the magnesium hydroxide to the red phosphorus is 10-50: 10-50: 0 to 5.
In addition, the graphene is a lamellar graphene, the thickness of the graphene is 5-50 nm, and the width of the graphene is 10-50 microns. The carbon nano tube is a multi-wall carbon nano tube, the outer diameter of the carbon nano tube is 10-50 nm, and the length of the carbon nano tube is 10-100 mu m. The silver powder is spherical, flaky or linear, the using amount of the spherical silver powder is 50 parts at most, the using amount of the linear silver powder is 10 parts at least, and the size of one dimension of the silver powder is 1-4 mu m.
Compared with a metal-based epoxy adhesive prepared by a traditional method, the epoxy resin-based carbon nano composite electromagnetic shielding conductive agent developed by the embodiment of the invention mainly adopts a carbon nano material with a high specific surface area, and the lamellar graphene and the carbon nano tube are selected to be overlapped for use to replace a large amount of silver powder in the traditional metal-based epoxy adhesive, wherein the using amount of the silver powder in the traditional conductive adhesive is 200-300 parts, while the using amount of the carbon nano material in the embodiment of the invention is remarkably reduced to 10-50 parts, instead of the lamellar graphene and the multi-walled carbon nano tube, although the mass part of the carbon nano material is small, the carbon nano material belongs to a nano material, is in a lamellar shape and a fibrous shape and has a large volume ratio, and the lamellar structure, the fibrous structure and the silver particles play a good synergistic effect, so that a three-dimensional conductive network in an epoxy resin matrix forms perfect electric connection, and the weight is obviously reduced, and the light-weight LED lamp has the obvious characteristic of light weight. In addition, considering the application in the field of electronic information, the requirement on flame retardance is high, so that the flame-retardant epoxy resin carbon nano composite electromagnetic shielding conductive adhesive is prepared by adopting the synergistic effect of the halogen-free flame retardant, namely aluminum hydroxide, magnesium hydroxide and red phosphorus, so that the product has remarkable light weight, electromagnetic shielding and flame retardant properties, and is beneficial to popularization and application in the field of electronic information and other related fields.
The epoxy resin-based carbon nano composite electromagnetic shielding conductive agent developed by the embodiment of the invention not only considers the electric connection performance of the existing conductive adhesive, but also focuses on solving the problem of electromagnetic radiation interference in the field of electronic information, namely solving the problem of electromagnetic wave radiation, and the invention has better electromagnetic wave shielding efficiency in the frequency range of 300 MHz-18 GHz, the electromagnetic wave shielding efficiency of the invention is controllable in the range of 20 dB-50 dB, and the shielding efficiency of specific frequency points is as follows: 300MHz/28dB, 450MHz/35dB, 1GHz/45dB, 6GHz/49dB, 10GHz/50dB, 18GHz/40 dB.
Specifically, in the embodiment of the invention, a liquid epoxy resin A component and a curing agent B component are used as carriers, a graphene, carbon nanotube and silver powder compound system is used as a conductive functional filler, an aluminum hydroxide, magnesium hydroxide and red phosphorus compound system is used as a flame retardant, and a first mixture and a second mixture are prepared in a grouping and dispersing manner to obtain the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive, as shown in fig. 2, the method specifically comprises the following steps:
(1) weighing the epoxy resin A, the curing agent B and various functional/auxiliary additives:
sequentially weighing the epoxy resin A, the curing agent B, the conductive functional filler, the flame retardant, other auxiliary additives and the like.
Weighing 100 parts (mass ratio) of an epoxy resin A component, wherein the epoxy resin A is E-51 epoxy resin, E-44 epoxy resin or modified epoxy resin and the like;
weighing 10-50 parts of a component B of a curing agent, wherein the curing agent B is polyamine and organic acid anhydride, the polyamine is Diethylenetriamine (DETA) in aliphatic amine, triethylenetetramine or tetraethylenepentamine and denaturants of several kinds of polybasic aliphatic amine, or N-aminoethyl piperazine (N-AEP) in alicyclic amine, the organic acid anhydride curing agent is phthalic anhydride, trimellitic anhydride (TMA) in aromatic acid anhydride, ethylene glycol of trimellitic anhydride, glyceride or Maleic Anhydride (MA) in alicyclic acid anhydride, Tung Oil Anhydride (TOA) or alkylene dibutyrate, and the specific selection of the curing agent B is determined according to the type of epoxy resin A and the specific application performance and process requirements of the electromagnetic shielding conductive adhesive;
weighing 1-5 parts of graphene and/or 1-5 parts of carbon nanotubes and 10-50 parts of silver powder, wherein the graphene used in the invention is lamellar graphene, the thickness of the graphene is within the range of 5-50 nm, the width of the graphene is within the range of 10-50 micrometers (mum), the carbon nanotubes are multi-walled carbon nanotubes, the outer diameter of the carbon nanotubes is 10-50 nm, the length of the carbon nanotubes is within the range of 10-100μm, the silver powder is in the form of spheres, sheets or wires, the using amount of the spheres is at most 50 parts, the using amount of the wires is at least 10 parts, and one dimension of the size of the silver powder is 1-5μm;
weighing 10-50 parts of aluminum hydroxide, 10-50 parts of magnesium hydroxide and 0-5 parts of red phosphorus;
other auxiliary aids comprise a curing accelerator, a diluent, a toughening agent and the like, wherein the curing accelerator is Benzyldimethylamine (BDMA), 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), diethylaminopropylamine, zinc/nickel/cobalt acetylacetonate, tin octoate or the like, and the curing agent B is selected according to the polyamine or the organic acid anhydride, and the use amount of the curing agent B is 0-10 parts; the diluent is benzyl alcohol, benzene, toluene, alcohol, ketone or n-Butyl Glycidyl Ether (BGE), Glycidyl Methacrylate (GMA) and the like, and the weight is 5-25 parts; the toughening agent used in the invention is an epoxy toughening agent, which is a cardanol epoxy compound, polypropylene glycol diglycidyl ether or linoleic acid dimer diglycidyl ester, and the like, and the weight of the toughening agent is 0-30 parts.
(2) Mixing of epoxy resin a with conductive fillers and diluents etc.:
100 parts of epoxy resin and 5-25 parts of diluent weighed in the step (1), according to the type of the epoxy resin A, 0-30 parts of toughening agent is selectively added, 12-60 parts of conductive filler is obtained by compounding lamellar graphene, multi-walled carbon nano-tubes and silver powder, the mixture is mixed together and placed in a resin ball ink tank for stirring and mixing, grinding balls mainly comprise grinding balls with the diameters of phi 6mm and phi 10mm, wherein the number of the phi 6mm balls is 100-500, the phi 10mm balls is 20-100, the revolution speed is controlled at 100-500 r/min according to the capacity adjustment quantity, the time is 15-120 min, an epoxy resin A combined system C is obtained, and the epoxy resin A is placed in a No. 1 container.
(3) Mixing of curing agent B with flame retardant and accelerator, etc.:
placing 20-50 parts of curing agent B weighed in the step (1) and 30-100 parts of a flame retardant aluminum hydroxide, magnesium hydroxide and red phosphorus compound system in a spherical ink tank, stirring and mixing, wherein grinding balls mainly comprise grinding balls with diameters phi 6mm and phi 10mm, the number of the phi 6mm balls is 100-400, the phi 10mm balls is 20-80, the number is adjusted according to the capacity, the revolution speed is set to be 100-300 r/min, the time is 15-60 min, and a compound system D of the curing agent B is obtained and is filled in a No. 2 container.
(4) According to the requirement of the dosage, taking 10 parts of the C system in the No. 1 container (2) and 2-5 parts of the D system in the No. 2 container (3), stirring and mixing uniformly, and directly using.
(5) And (3) curing and compounding the epoxy resin system C and the curing agent system D at the temperature of between room temperature and 120 ℃, wherein the curing time is different according to the temperature, and the curing is completed within 10 to 60min, so that the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive is obtained.
Fig. 3 is a diagram illustrating the actual application effect of different conductive agent ratios according to the first embodiment of the present invention, and it can be seen from fig. 3a and 3b that the final color of the whole coating is different after curing through the addition ratio of different conductive agents, but is mainly black or slightly light black.
The process according to the invention will be explained and illustrated in detail below by means of four specific examples:
(1) weighing the component A of the epoxy resin, E-51 and 100 parts (100 g) by mass, and standing for later use;
(2) weighing the curing agent B component, DETA and 15 parts, and standing for later use;
(3) weighing 20 parts of acetone and a diluent, placing the mixture into the epoxy resin A in the step (1), and stirring and mixing the mixture;
(4) weighing a conductive filler system, 3 parts of lamellar graphene, 1 part of multi-walled carbon nanotube and 30 parts of silver powder, sequentially adding the conductive filler system, the lamellar graphene, the multi-walled carbon nanotube and the silver powder into the epoxy resin A obtained in the step (3), and primarily stirring and mixing;
(5) weighing a flame retardant compound system, 50 parts of aluminum hydroxide, 10 parts of magnesium hydroxide and 2 parts of red phosphorus, adding into the curing agent B in the step (2), and carrying out preliminary stirring and mixing;
(6) respectively placing 300 particles and 20 particles of grinding beads with the diameter phi of 6mm and the diameter phi of 10mm in a resin ball milling tank;
(7) transferring the epoxy resin A mixed solution mixed with the diluent in the step (3) and the conductive filler system in the step (4) into a resin ball milling tank, controlling the rotating speed at 300r/min for 30min, and carrying out ball milling treatment to obtain a mixed system C;
(8) transferring and filling the mixed system C in the step (7) into a No. 1 container;
(9) transferring the curing agent B mixed with the flame retardant compound system in the step (6) into a resin ball milling tank in the step (6), and carrying out ball milling treatment at the rotating speed of 300r/min for 30min to obtain a mixed system D;
(10) transferring and filling the mixed system D in the step (9) into a No. 2 container;
(11) and (3) taking out 10 parts of the mixed system C from the No. 1 container in the step (8), taking out 2 parts of the mixed system D in the step (9), uniformly stirring and mixing, coating the mixture on a use occasion, and curing and drying at room temperature or heating to 30-40 ℃ for accelerated drying and curing.
And obtaining the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
Example two
(1) Weighing 100 parts (100 g) of epoxy resin A and E-44, and standing for later use;
(2) weighing 40 parts of curing agent B and TMA, and standing for later use;
(3) weighing a diluent, namely 20 parts of BGE, putting the BGE into the epoxy resin A in the step (1), and stirring and mixing;
(4) weighing a curing accelerator, namely DMP-30, 10 parts, putting the mixture into the curing agent B in the step (2), and uniformly stirring;
(5) weighing a conductive filler system, 3 parts of lamellar graphene, 1 part of multi-walled carbon nanotube and 50 parts of silver powder, sequentially adding the conductive filler system, the lamellar graphene, the multi-walled carbon nanotube and the silver powder into the epoxy resin A obtained in the step (3), and primarily stirring and mixing;
(6) weighing 20 parts of a flexibilizer and a cardanol epoxy compound, and placing the cardanol epoxy compound in the curing agent B system in the step (2);
(7) weighing a flame retardant compound system, 50 parts of aluminum hydroxide and 30 parts of magnesium hydroxide, adding into the curing agent B in the step (2), and carrying out preliminary stirring and mixing;
(8) placing 400 particles and 50 particles of grinding beads with the diameter phi of 6mm and the diameter phi of 10mm in a resin ball milling tank respectively;
(8) transferring the epoxy resin A mixed solution mixed with the diluent in the step (3) and the conductive filler system in the step (5) into a resin ball milling tank, controlling the rotating speed at 500r/min for 30min, and carrying out ball milling treatment to obtain a mixed system C;
(9) transferring and filling the mixed system C in the step (8) into a No. 1 container;
(10) transferring the curing agent B mixed with the toughening agent in the step (6) and the flame retardant compound system in the step (7) into a resin ball milling tank in the step (8), and carrying out ball milling treatment at the rotating speed of 300r/min for 30min to obtain a mixed system D;
(11) transferring and filling the mixed system D in the step (10) into a No. 2 container;
(12) and (3) taking out 10 parts of the mixed system C from the No. 1 container in the step (9), taking out 5 parts of the mixed system D in the step (10), uniformly stirring and mixing, coating the mixture on a use occasion, and heating to 50-60 ℃ for drying and curing.
And obtaining the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
EXAMPLE III
(1) Weighing the component A of the epoxy resin, E-51 and 100 parts (100 g) by mass, and standing for later use;
(2) weighing the curing agent B component, DETA and 20 parts, and standing for later use;
(3) weighing 15 parts of acetone and a diluent, placing the mixture into the epoxy resin A in the step (1), and stirring and mixing the mixture;
(4) weighing a conductive filler system, 2 parts of lamellar graphene, 2 parts of multi-walled carbon nanotubes and 40 parts of silver powder, sequentially adding the conductive filler system, the lamellar graphene, the multi-walled carbon nanotubes and the silver powder into the epoxy resin A obtained in the step (3), and primarily stirring and mixing;
(5) weighing a flame retardant compound system, 50 parts of aluminum hydroxide, 20 parts of magnesium hydroxide and 5 parts of red phosphorus, adding into the curing agent B in the step (2), and carrying out preliminary stirring and mixing;
(6) 250 particles and 15 particles of grinding beads with the diameter phi of 6mm and phi of 10mm are respectively placed in a resin ball milling tank;
(7) transferring the epoxy resin A mixed solution mixed with the diluent in the step (3) and the conductive filler system in the step (4) into a resin ball milling tank, controlling the rotating speed at 200r/min for 50min, and carrying out ball milling treatment to obtain a mixed system C;
(8) transferring and filling the mixed system C in the step (7) into a No. 1 container;
(9) transferring the curing agent B mixed with the flame retardant compound system in the step (6) into a resin ball milling tank in the step (6), and carrying out ball milling treatment at the rotating speed of 200r/min for 50min to obtain a mixed system D;
(10) transferring and filling the mixed system D in the step (9) into a No. 2 container;
(11) the mixed system C10 parts was taken out of Container No. 1 in (8), the mixed system D3 parts was taken out of Container No. 9, and the mixture was stirred and mixed uniformly, applied to the application site, and cured and dried at room temperature.
And obtaining the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
Example four
(1) Weighing a component A of the modified epoxy resin, 4531A and 100 parts (namely 100g) by mass, and standing for later use;
(2) weighing 4531B and 25 parts of curing agent B, and standing for later use;
(3) weighing 10 parts of acetone and a diluent, placing the mixture into the epoxy resin A in the step (1), and stirring and mixing the mixture;
(4) weighing a conductive filler system, 2 parts of lamellar graphene, 3 parts of multi-walled carbon nanotubes and 20 parts of silver powder, sequentially adding the conductive filler system, the lamellar graphene, the multi-walled carbon nanotubes and the silver powder into the epoxy resin A obtained in the step (3), and primarily stirring and mixing;
(5) weighing a flame retardant compound system, 50 parts of aluminum hydroxide, 30 parts of magnesium hydroxide and 2 parts of red phosphorus, adding into the curing agent B in the step (2), and carrying out preliminary stirring and mixing;
(6) 250 particles and 15 particles of grinding beads with the diameter phi of 6mm and phi of 10mm are respectively placed in a resin ball milling tank;
(7) transferring the epoxy resin A mixed solution mixed with the diluent in the step (3) and the conductive filler system in the step (4) into a resin ball milling tank, controlling the rotating speed at 200r/min for 50min, and carrying out ball milling treatment to obtain a mixed system C;
(8) transferring and filling the mixed system C in the step (7) into a No. 1 container;
(9) transferring the curing agent B mixed with the flame retardant compound system in the step (6) into a resin ball milling tank in the step (6), and carrying out ball milling treatment at the rotating speed of 200r/min for 50min to obtain a mixed system D;
(10) transferring and filling the mixed system D in the step (9) into a No. 2 container;
(11) and (3) taking 10 parts of the mixed system C out of the No. 1 container in the step (8), taking 2.5 parts of the mixed system D in the step (9), uniformly stirring and mixing, coating the mixture on a use occasion, and curing and drying for 60min at 40-50 ℃.
And obtaining the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
Generally speaking, the embodiment of the invention prepares an epoxy resin-based electromagnetic shielding conductive adhesive, wherein a conductive filler system is a carbon nano composite system, namely the conductive adhesive is composed of lamellar graphene, multi-walled carbon nanotubes and silver powder in a certain structural form, and a good three-dimensional conductive network is constructed by virtue of the composite effect of the carbon nano composite system, namely the conductive filler system is formed by filling silver particles in gaps through the lamellar graphene and the lapped fibrous carbon nanotube structures so as to enhance the conductivity of the constructed conductive network; in addition, a halogen-free flame-retardant modification system, namely a compound system of aluminum hydroxide, magnesium hydroxide and red phosphorus, is introduced by combining the electronic information field and the application of electronic and electrical equipment to improve the flame retardant property of the epoxy resin matrix resin and improve the comprehensive use performance of the epoxy resin matrix resin, the introduction of the two typical functional auxiliary agent systems is beneficial to exerting the advantages of the composition and the structural characteristics of each auxiliary agent to form a composite synergistic effect of 1+1 to more than 2, and the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive and the preparation method thereof provided by the invention have important significance for improving the product performance in the rapidly-developed electronic information industry field.
The second embodiment of the invention provides an epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive, which is prepared by adopting the method in any one of the first embodiments of the invention.
The relevant content of the embodiments of the present invention can be understood by referring to the first embodiment of the present invention, and will not be discussed in detail herein.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, and the scope of the invention should not be limited to the embodiments described above.
Claims (10)
1. A method for preparing epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive is characterized by comprising the following steps:
taking epoxy resin as a first carrier, diluting the epoxy resin by a diluent, taking a graphene, carbon nano tube and silver powder compound system as a conductive functional filler, and carrying out ball-milling mixing on the diluted epoxy resin and the conductive functional filler to obtain a first mixture;
taking a curing agent as a second carrier, taking a compound system of aluminum hydroxide, magnesium hydroxide and red phosphorus as a flame retardant, and carrying out ball milling and mixing on the curing agent and the flame retardant to obtain a second mixture;
and curing the second mixture through the second mixture to obtain the epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive.
2. The method of claim 1,
the mass ratio of the epoxy resin, the curing agent, the diluent, the conductive functional filler and the flame retardant is 100: 20-50: 5-25: 12-60: 30 to 100.
3. The method of claim 2,
the mass ratio of the graphene to the carbon nano tube to the silver powder is 1-5: 1-5: 10 to 50;
the mass ratio of the aluminum hydroxide to the magnesium hydroxide to the red phosphorus is 10-50: 10-50: 0 to 5.
4. The method of claim 1,
the graphene is lamellar graphene, the thickness of the graphene is 5-50 nm, and the width of the graphene is 10-50 microns.
5. The method of claim 1,
the carbon nano tube is a multi-wall carbon nano tube, the outer diameter of the carbon nano tube is 10-50 nm, and the length of the carbon nano tube is 10-100 mu m.
6. The method of claim 1,
the silver powder is spherical, flaky or linear, the using amount of the spherical silver powder is 50 parts at most, the using amount of the linear silver powder is 10 parts at least, and the size of one dimension of the silver powder is 1-4 mu m.
7. The method according to any one of claims 1 to 6,
the ball milling revolution speed of ball milling and mixing the diluted epoxy resin and the conductive functional filler is 100-.
8. The method according to any one of claims 1 to 6,
and ball milling and mixing the curing agent and the fire retardant, wherein the ball milling revolution speed is 100-.
9. The method according to any of the claims 1-6, characterized in that solidifying the second mix by means of the second mix comprises:
and solidifying the second mixture through the second mixture, wherein the mass ratio of the first mixture to the second mixture is 10: 2-5, and the curing time is 10-60 min.
10. An epoxy resin-based carbon nano composite electromagnetic shielding conductive adhesive, which is characterized by being prepared by the method of any one of claims 1 to 9.
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| CN113817210A (en) * | 2021-10-21 | 2021-12-21 | 中国电子科技集团公司第三十三研究所 | Carbon nano composite wave-absorbing heat-insulating epoxy foam material and preparation method thereof |
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