WO2021135375A1 - Graphene ab adhesive and preparation method therefor - Google Patents

Graphene ab adhesive and preparation method therefor Download PDF

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Publication number
WO2021135375A1
WO2021135375A1 PCT/CN2020/114650 CN2020114650W WO2021135375A1 WO 2021135375 A1 WO2021135375 A1 WO 2021135375A1 CN 2020114650 W CN2020114650 W CN 2020114650W WO 2021135375 A1 WO2021135375 A1 WO 2021135375A1
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Prior art keywords
graphene
glue
epoxy resin
ether
glycidyl ether
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PCT/CN2020/114650
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French (fr)
Chinese (zh)
Inventor
蒋路谣
华永军
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苏州桐力光电股份有限公司
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Publication of WO2021135375A1 publication Critical patent/WO2021135375A1/en

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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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the technical field of adhesive materials, and relates to a graphene AB glue and a preparation method thereof.
  • the epoxy resin molecular chain contains epoxy groups and epoxy ring structures.
  • the unique three-membered ring structure can be cross-linked with acid-base curing agents to form a three-way network structure and a thermosetting material with a body-shaped molecular structure.
  • Epoxy groups, hydroxyl groups, ether bonds and ester bonds and other polar groups make epoxy resin thermosetting materials have high mechanical properties, excellent adhesion properties, low curing shrinkage and stable electrical properties, which can meet various special performance and process properties The current requirements of other thermosetting materials cannot match it.
  • Epoxy AB glue is an adhesive made of epoxy resin as the main body. Its chemical resistance, physical resistance and process ease of operation make it widely used in the sealing and protection of high and low voltage electrical appliances, motors and electronic components.
  • functionalized epoxy resin adhesives are mainly composed of matrix resin and functionalized fillers, namely functionalized metals and metal oxides.
  • the functionalized fillers are combined through the coating and bonding effect of the matrix resin to form a closed circuit. Or conduction to give the epoxy material the electronic and electrified function, and realize the functional connection of sensitive components.
  • Traditional metal and metal oxide electronic and electrical functions are single, with limited effects, and are easy to chemically react with acidic and alkaline curing agents in epoxy thermosetting materials, and the stability and reliability of electronic and electrical performance are seriously affected.
  • a large number of functionalized metals and metal oxides occupy a huge volume and weight ratio in epoxy resins, which are easy to migrate, settle and delaminate, resulting in a substantial increase in viscosity of epoxy thermosetting materials before curing, poor process operability, and poor operability after curing.
  • the force and functionality gradually disappear with time, and the reliability is seriously affected. Therefore, how to optimize and reduce the filling amount of functionalized fillers to improve the electronic and electrification performance of epoxy thermosetting materials and broaden its application range has become one of the important topics in the field of epoxy materials research.
  • Graphene is a honeycomb hexagonal lattice two-dimensional carbon nano-plane monoatomic layer material formed by carbon atoms in SP 2 hybrid mode. It is the basic structural unit of all carbon crystals except diamond. Graphene has excellent mechanical, electrical and thermal properties, and is of special significance to the basic research of materials science. It enables some physical effects that can only be demonstrated theoretically before can be verified through experiments, and it is a revolutionary material in the future.
  • Graphene is stable under radiation, does not generate high-energy rays or only low-energy rays, has a small thermal neutron absorption cross-section, and has excellent high-energy ray attenuation and thermal neutron absorption slowing performance, which effectively reduces the radiation energy entering electronic industrial equipment and protects Sensitive components will not be damaged due to huge thermal stress caused by a large amount of heat generated by absorbing radiation energy.
  • the purpose of the present invention is to provide a graphene AB glue and a preparation method.
  • the technical solution provided by the present invention is: a graphene AB glue, the graphene AB glue is composed of component A and component B mixed in a mass ratio of 1-2:1 :
  • the raw material formula of component A includes the following mass percentages of raw materials:
  • the raw material formula of component B includes the following mass percentages of raw materials:
  • the bisphenol type glycidyl ether epoxy resin is diphenol methane glycidyl ether, diphenol propane glycidyl ether, hydrogenated diphenol propane glycidyl ether, and methylol diphenol propane At least one of glycidyl ethers.
  • the polyphenol type glycidyl ether epoxy resin is at least one of ortho-cresol formaldehyde polyglycidyl ether, resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether.
  • the heterocyclic mixed epoxy resin is triglycidyl isocyanurate, glycidyl cyanurate, 1,3-diglycidyl hydantoin and 1-glycidyl-3 -At least one of glycidyloxymethyl-5,5-dimethylhydantoin.
  • the reactive diluent is propylene oxide butyl ether, propylene oxide phenyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether and resorcinol At least one of diglycidyl ethers.
  • the toughening agent is at least one of carboxyl-terminated liquid nitrile rubber, polyvinyl butyral, polyphenylene ether ketone, chlorosulfonated polyethylene, polyvinyl acetate, and powdered polyvinyl alcohol .
  • the carbon interface treatment agent is at least one of hydrocarbyl boric acid, carborane, borate and diborane.
  • the reactive organosilicon modifier is a compound conforming to the following general structural formula:
  • Y represents an epoxy group, an amino group, a methyl propionyloxy group or a mercapto group
  • R represents an alkyl group or an aryl group
  • X represents a methoxy group, an ethoxy group or a chloro group.
  • the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; the graphene loose packing density is 0.01-0.2 g/cm Within 3 , the tap density is 0.05 ⁇ 0.2g/cm 3 .
  • the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
  • the curing agent is polyamide, polyetheramine, polythiol, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride. At least one of.
  • the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, triphenylphosphine, bicyclic amidine, benzyldimethylamine, triisopropanol titanate At least one of tertiary amine ester and triethanolamine.
  • the inactive diluent is at least one of ethyl acetate, dibutyl phthalate, cyclohexanone and styrene.
  • the technical solution provided by the present invention is: a method for preparing graphene AB glue: It is characterized in that it includes the following steps:
  • Step 1 Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
  • Step 2 Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
  • Step 3 Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 1 to 2: 1 to form the graphene AB glue.
  • the negative pressure condition is that the vacuum degree is -0.08 ⁇ -0.1MPa.
  • the graphene AB glue and graphene-based electromagnetic and thermal shielding epoxy material uses the excellent electronic and thermal effects of graphene to not only achieve the performance of simultaneous electromagnetic and thermal shielding, but also The weight ratio and volume ratio are properly controlled, so that the components work together to achieve excellent mechanical strength and reliable stability.
  • the conductivity of the graphene AB glue is 10 3 ⁇ 10 4 S/m
  • the electromagnetic shielding efficiency is 45 ⁇ 50dB at 10KHz
  • the thermal conductivity is 2.0 ⁇ 2.5W/(m ⁇ K), and it is hot at 14.5°C
  • the sub-capture cross-section is 0.01 ⁇ 0.1mbar
  • the thrust of aluminum/aluminum is 15 ⁇ 20Kg
  • the thrust of PC/PC is 8 ⁇ 10Kg
  • after 168 hours of reliability test of “high temperature and high humidity” the loss rate of electromagnetic and thermal shielding effectiveness is within 5%
  • the loss rate of mechanical strength is within 15%.
  • Example 1 A graphene AB glue and preparation method
  • a graphene AB glue characterized in that it includes the following components and mass percentages:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the bisphenol-type glycidyl ether epoxy resin is diphenol-based methane glycidyl ether, the viscosity is 4000 mPa ⁇ s at 25° C., and the epoxy equivalent is 170 g/eq).
  • the polyphenol type glycidyl ether epoxy resin is a mixture of o-cresol formaldehyde polyglycidyl ether and resorcinol formaldehyde polyglycidyl ether in a mass ratio of 1:1; the viscosity at 25°C is 5000 mpa ⁇ s, Epoxy equivalent is 200g/eq.
  • the heterocyclic mixed epoxy resin is triglycidyl isocyanurate with an epoxy equivalent of 100 g/eq).
  • the reactive diluent is a mixture of propylene oxide butyl ether and propylene oxide phenyl ether in a mass ratio of 1:5; the epoxy equivalent is controlled within the range of 200 g/eq.
  • the toughening agent is a mixture of polyvinyl butyral and polyphenylene ether ketone in a mass ratio of 2:1.
  • the carbon interface treatment agent is a mixture of hydrocarbyl boric acid, carborane, and boric acid ester in a mass ratio of 1:1.2:1.
  • the reactive organosilicon modifier conforms to the general structural formula YRSiX 3 : wherein Y is an epoxy group; R is an alkyl group; X is a methoxy group.
  • the graphene is a single-layer graphene, the bulk density of the graphene is controlled within 0.01 g/cm 3 , and the tap density is within 0.01 g/cm 3.
  • the carbon nanotubes are single-walled carbon nanotubes, the diameter of the carbon nanotubes is controlled within 1 to 5 nanometers, and the length is controlled within 0.1 to 5 microns.
  • the curing agent is polyamide, with an amine value of 350 mgKOH/g, an active hydrogen equivalent of 150 g/eq, and a viscosity of 50,000 mPa.S at 25°C.
  • the curing accelerator is a mixture of triphenylphosphine and bicyclic amidine in a mass ratio of 1:1.
  • the inactive diluent is a mixture of ethyl acetate and dibutyl phthalate in a mass ratio of 1:1.
  • the preparation method of graphene AB glue includes the following steps:
  • the low speed is 15r/min
  • the high speed is 50r/min
  • the dispersing disc speed is 1000r/min
  • the negative pressure condition is that the vacuum degree is -0.09MPa.
  • Embodiment 2 A graphene AB glue and its preparation method
  • the bisphenol-type glycidyl ether epoxy resin is a mixture composed of diphenol-based propane glycidyl ether and hydrogenated diphenol-based propane glycidyl ether in a mass ratio of 1:1.5.
  • Diphenol-based propane glycidyl ether has a viscosity of 8000mpa ⁇ s at 25°C and an epoxy equivalent of 170g/eq)
  • hydrogenated diphenol-based propane glycidyl ether has a viscosity of 10,000mpa ⁇ s at 25°C and an epoxy equivalent of 500g/eq).
  • the polyphenol-type glycidyl ether epoxy resin is o-cresol formaldehyde polyglycidyl ether, resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether in a mass ratio of 1:1:1:2
  • the heterocyclic mixed epoxy resin is 1,3-diglycidyl hydantoin and 1-glycidyl-3-glycidyloxymethyl-5,5-dimethyl hydantoin according to 1:1 The mass ratio constitutes a mixture.
  • the epoxy equivalent of 1,3-diglycidylhydantoin is 500.
  • the epoxy equivalent of 1-glycidyl-3-glycidyloxymethyl-5,5-dimethylhydantoin is 500.
  • the reactive diluent is propylene oxide butyl ether; the epoxy equivalent is controlled in the range of 200 g/eq.
  • the toughening agent is a mixture of carboxyl-terminated liquid nitrile rubber and polyvinyl butyral in a mass ratio of 3:1.
  • the carbon interface treatment agent is hydrocarbyl boric acid.
  • the reactive organosilicon modifier conforms to the general structural formula YRSiX 3 : wherein Y is an amino group; R is an aryl group; X is a chloro group.
  • the graphene is a mixture of single-layer graphene and double-layer graphene according to a mass ratio of 1:1.
  • the bulk density of the graphene is controlled within 0.2g/cm 3 and the tap density is 0.2g/cm 3 Within.
  • the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:1.
  • the diameter of the carbon nanotubes is controlled within 1 to 5 nanometers, and the length is controlled within 0.1 to 5 microns. .
  • the curing agent is polyether amine with an amine value of 200 mgKOH/g and an active hydrogen equivalent of 50 g/eq.
  • the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.
  • the inactive diluent is a mixture of ethyl acetate and dibutyl phthalate in a mass ratio of 1:1.
  • Embodiment 3 A graphene AB glue and its preparation method
  • a graphene AB glue is composed of component A and component B mixed in a mass ratio of 1.5:1:
  • the raw material formula of component A includes the following mass percentages of raw materials:
  • the raw material formula of component B includes the following mass percentages of raw materials:
  • a preferred embodiment is: a mixture of the diphenol-based methane glycidyl ether, the diphenol-based propane glycidyl ether, and the hydrogenated diphenol-based propane glycidyl ether in a mass ratio of 1:3:1.
  • the polyphenol-type glycidyl ether epoxy resin is a mixture composed of resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether in a mass ratio of 1:2.
  • heterocyclic mixed epoxy resin is 1,3-diglycidyl hydantoin.
  • a preferred embodiment is: the reactive diluent is propylene oxide phenyl ether.
  • a preferred embodiment is that the toughening agent is chlorosulfonated polyethylene.
  • a preferred embodiment is that the carbon interface treatment agent is carborane.
  • the reactive organosilicon modifier is a compound conforming to the following general structural formula:
  • Y represents methyl propionyloxy
  • R represents alkyl
  • X represents ethoxy
  • the graphene is a single-layer graphene; the graphene has a loose packing density of 0.01 g/cm 3 or less, and a tap density of 0.05 g/cm 3 .
  • the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
  • a preferred embodiment is that the curing agent is polythiol.
  • a preferred embodiment is that the curing speed-increasing agent is benzyldimethylamine.
  • the inactive diluent is dibutyl phthalate.
  • a method for preparing graphene AB glue including the following steps:
  • Step 1 Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
  • Step 2 Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
  • Step 3 Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 1:1 to form the graphene AB glue.
  • a preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.08 MPa.
  • Embodiment 4 A graphene AB glue and preparation method
  • a graphene AB glue is composed of component A and component B mixed in a mass ratio of 1-2:1:
  • the raw material formula of component A includes the following mass percentages of raw materials:
  • the raw material formula of component B includes the following mass percentages of raw materials:
  • a preferred embodiment is that the bisphenol type glycidyl ether epoxy resin is diphenol propane glycidyl ether.
  • polyphenol type glycidyl ether epoxy resin is resorcinol formaldehyde polyglycidyl ether.
  • heterocyclic mixed epoxy resin is glycidyl cyanurate.
  • the reactive diluent is ethylene glycol diglycidyl ether.
  • the toughening agent is a mixture of polyvinyl acetate and powdered polyvinyl alcohol in a mass ratio of 1:1.
  • the carbon interface treatment agent is hydrocarbyl boric acid, carborane powder polyvinyl alcohol.
  • the reactive organosilicon modifier is a compound conforming to the following general structural formula:
  • Y represents a mercapto group
  • R represents an alkyl group
  • X represents a methoxy group
  • the graphene is a multilayer graphene; the graphene loose packing density is within 0.08 g/cm 3 , and the tap density is 0.15 g/cm 3 .
  • the carbon nanotubes are multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
  • the curing agent is methyltetrahydrophthalic anhydride.
  • a preferred embodiment is that the curing speed-increasing agent is bicyclic amidine.
  • a preferred embodiment is that the inactive diluent is ethyl acetate.
  • the technical solution provided by the present invention is: a method for preparing graphene AB glue: It is characterized in that it includes the following steps:
  • Step 1 Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
  • Step 2 Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
  • Step 3 Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 2:1 to form the graphene AB glue.
  • a preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.1 MPa.
  • Embodiment 5 A graphene AB glue and its preparation method
  • a preferred embodiment is that the bisphenol type glycidyl ether epoxy resin is hydroxymethyl diphenol propane glycidyl ether.
  • polyphenol type glycidyl ether epoxy resin is ortho-cresol formaldehyde polyglycidyl ether.
  • the heterocyclic mixed epoxy resin is 1-glycidyl-3-glycidyloxymethyl-5,5-dimethylhydantoin.
  • the reactive diluent is a mixture of propylene oxide phenyl ether and ethylene glycol diglycidyl ether in a mass ratio of 1:1.
  • a preferred embodiment is that the toughening agent is chlorosulfonated polyethylene.
  • a preferred embodiment is that the carbon interface treatment agent is diborane.
  • the reactive organosilicon modifier is a compound conforming to the following general structural formula:
  • the graphene is a few-layer graphene; the graphene has a loose packing density of 0.15 g/cm 3 or less, and a tap density of 0.15 g/cm 3 .
  • the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:1, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1- 5 microns.
  • the curing agent is a mixture of methylhexahydrophthalic anhydride and methylnadic anhydride in a mass ratio of 1:1.
  • the curing speed-increasing agent is a mixture of triisopropanol titanate tertiary amine ester and triethanolamine in a mass ratio of 1:1.
  • the inactive diluent is dibutyl phthalate.

Abstract

A graphene AB adhesive and a preparation method therefor. The graphene AB adhesive comprises the following components according to the percentage by weight: a component A: 30%-60% of bisphenol-type glycidyl ether epoxy resin, 10%-30% of polyphenol-type glycidyl ether epoxy resin, 1%-10% of heterocyclic mixed epoxy resin, 1%-10% of a reactive diluent, 1-10% of a toughening agent, 5%-30% of graphene, 1%-10% of carbon nanotubes, 0.1%-2% of a carbon interface treating agent, and 0.01%-1% of a reactive organic silicon modifier; and a component B: 30%-50% of a curing agent, 1%-10% of a curing accelerator, 1%-10% of an inactive diluent, 5%-30% of graphene, 1%-10% of carbon nanotubes, 0.1%-2% of a carbon interface treating agent, and 0.01%-1% of a reactive organic silicon modifier. According to the graphene AB adhesive, the excellent electronic effect, heat effect and other physical properties of graphene are utilized, the electromagnetic and heat simultaneous shielding performance is achieved, the weight ratio and the volume ratio are properly controlled, the components achieve a synergistic effect, and excellent mechanical strength and reliable stability are achieved.

Description

一种石墨烯AB胶及其制备方法Graphene AB glue and preparation method thereof 技术领域Technical field
本发明属于胶粘材料技术领域，涉及一种石墨烯AB胶及其制备方法。The invention belongs to the technical field of adhesive materials, and relates to a graphene AB glue and a preparation method thereof.
背景技术Background technique
环氧树脂分子链上含有环氧基团和环氧基环状结构，独特的三元环结构可与酸碱性固化剂交联反应成三向网状结构和体型分子结构的热固性材料。环氧基、羟基、醚键和酯键等极性基团致使环氧树脂热固性材料机械性能高、附着性能优异、固化收缩率小和电气性能稳定等，能满足各种特殊使用性能和工艺性能的要求，当前其他热固性材料无法与之匹敌。环氧AB胶以环氧树脂为主体制成的胶粘剂，耐化学性能、耐物理性能和工艺易操作性能使它广泛应用于高低压电器、电机和电子元器件等密封和保护。The epoxy resin molecular chain contains epoxy groups and epoxy ring structures. The unique three-membered ring structure can be cross-linked with acid-base curing agents to form a three-way network structure and a thermosetting material with a body-shaped molecular structure. Epoxy groups, hydroxyl groups, ether bonds and ester bonds and other polar groups make epoxy resin thermosetting materials have high mechanical properties, excellent adhesion properties, low curing shrinkage and stable electrical properties, which can meet various special performance and process properties The current requirements of other thermosetting materials cannot match it. Epoxy AB glue is an adhesive made of epoxy resin as the main body. Its chemical resistance, physical resistance and process ease of operation make it widely used in the sealing and protection of high and low voltage electrical appliances, motors and electronic components.
随着电子元器件小型化和微型化以及印制板高密度化和高度集中化等迅速发展，电子封装材料对电气化程度、抗疲劳性、线分辨率和操作工艺等性能的要求越来越突出。常用的功能化环氧树脂粘合剂以基体树脂和功能化填料即功能化金属和金属氧化物等为主要组成成分，通过基体树脂的包覆粘结作用把功能化填料结合在一起，形成闭路或导通，以赋予环氧材料电子电气化功能，实现敏感元器件的功能化连接。传统金属和金属氧化物电子电气功能化单一，作用有限，且易与环氧热固性材料中酸性和碱性固化剂发生化学反应，电子电气化性能稳定可靠性受到严重影响。大量的功能化金属和金属氧化物在环氧树脂中占据庞大体积比和重量比，易迁移、沉降和分层，导致环氧热固性材料固化前粘度大幅度上升，工艺可操作性差，固化后又硬又脆，柔性和抗疲劳性严重降低，机械性能降低，与基材粘结力变差，且填充大量功能化金属和金属氧化物的热固性材料作业时稳定性差，在湿热等特殊环境中，作用力和功能性随时间延长逐渐消失，可靠性受到严重影响。所以如何优化降低功能化填料填量以提高环氧热固性材料的电子电气化性能和拓宽其应用范围成为环氧材料研究领域的重要课题之一。With the rapid development of miniaturization and miniaturization of electronic components and high-density and high-centralization of printed boards, electronic packaging materials have increasingly prominent requirements for electrification, fatigue resistance, line resolution, and operating technology. . Commonly used functionalized epoxy resin adhesives are mainly composed of matrix resin and functionalized fillers, namely functionalized metals and metal oxides. The functionalized fillers are combined through the coating and bonding effect of the matrix resin to form a closed circuit. Or conduction to give the epoxy material the electronic and electrified function, and realize the functional connection of sensitive components. Traditional metal and metal oxide electronic and electrical functions are single, with limited effects, and are easy to chemically react with acidic and alkaline curing agents in epoxy thermosetting materials, and the stability and reliability of electronic and electrical performance are seriously affected. A large number of functionalized metals and metal oxides occupy a huge volume and weight ratio in epoxy resins, which are easy to migrate, settle and delaminate, resulting in a substantial increase in viscosity of epoxy thermosetting materials before curing, poor process operability, and poor operability after curing. Hard and brittle, severely reduced flexibility and fatigue resistance, reduced mechanical properties, poor adhesion to the substrate, and poor stability during operation of thermosetting materials filled with a large amount of functionalized metals and metal oxides. In special environments such as damp heat, The force and functionality gradually disappear with time, and the reliability is seriously affected. Therefore, how to optimize and reduce the filling amount of functionalized fillers to improve the electronic and electrification performance of epoxy thermosetting materials and broaden its application range has become one of the important topics in the field of epoxy materials research.
石墨烯是一种由碳原子以SP 2杂化方式形成的蜂窝状六角型晶格二维碳纳米平面单原子层材料，是除金刚石外所有碳晶体的基本结构单元。石墨烯具有优异的力学、电学和热学特性，对材料学基础研究有着特殊意义，它使得一些此前只能在理论上进行论证的物理效应可以通过实验进行验证，是一种未来革命性的材料。石墨烯在辐射下稳定，不产生高能量射线或只产生低能量射线， 热中子吸收截面小，优异的高能量射线衰减和热中子吸收慢化性能有效减弱辐射能量进入电子工业设备，保护敏感元件不致因吸收辐射能量产生大量热量引起巨大的热应力而损坏。不仅如此，石墨烯中的载流子遵循一种特殊的量子隧道效应，即使在碰到杂质时也不会产生背反射，超高的载流子迁移率和超强的局域导电性导致电磁感应在石墨烯上产生反向电磁场和涡流，减弱和抵消干扰电磁波的作用，达到最佳的电磁屏蔽效果。将石墨烯加入环氧树脂中，线分辨率高，适用于精细的引线间距和高密度组装，符合微电子产品轻量化、微型化的发展需求。石墨烯填充环氧热固性材料，不与其中的酸性和碱性固化剂发生化学反应，体积比和重量比适宜得当，各组分协同作用，致使环氧热固化材料具有良好的耐热性和抗疲劳性，与各种基材粘结牢固，剥离力强大，电子电气化性能异常稳定。 Graphene is a honeycomb hexagonal lattice two-dimensional carbon nano-plane monoatomic layer material formed by carbon atoms in SP 2 hybrid mode. It is the basic structural unit of all carbon crystals except diamond. Graphene has excellent mechanical, electrical and thermal properties, and is of special significance to the basic research of materials science. It enables some physical effects that can only be demonstrated theoretically before can be verified through experiments, and it is a revolutionary material in the future. Graphene is stable under radiation, does not generate high-energy rays or only low-energy rays, has a small thermal neutron absorption cross-section, and has excellent high-energy ray attenuation and thermal neutron absorption slowing performance, which effectively reduces the radiation energy entering electronic industrial equipment and protects Sensitive components will not be damaged due to huge thermal stress caused by a large amount of heat generated by absorbing radiation energy. Not only that, the carriers in graphene follow a special quantum tunneling effect, even when it encounters impurities, there will be no back reflection, ultra-high carrier mobility and ultra-strong local conductivity lead to electricity Magnetic induction produces reverse electromagnetic fields and eddy currents on the graphene to weaken and offset the effect of interference electromagnetic waves to achieve the best electromagnetic shielding effect. Adding graphene to epoxy resin has high line resolution, is suitable for fine lead pitch and high-density assembly, and meets the development needs of lightweight and miniaturization of microelectronic products. Graphene-filled epoxy thermosetting material does not chemically react with the acidic and alkaline curing agents in it. The volume ratio and weight ratio are appropriate. The synergistic effects of each component make the epoxy thermosetting material have good heat resistance and resistance. Fatigue, strong adhesion to various substrates, strong peeling force, and exceptionally stable electronic and electrification performance.
发明内容Summary of the invention
本发明的目的在于提供一种石墨烯AB胶及制备方法。The purpose of the present invention is to provide a graphene AB glue and a preparation method.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种石墨烯AB胶，所述石墨烯AB胶由组份A和组份B按照1-2:1的质量比例混合后构成：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a graphene AB glue, the graphene AB glue is composed of component A and component B mixed in a mass ratio of 1-2:1 :
所述组分A的原料配方包括下列质量百分比的原料：The raw material formula of component A includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000001
Figure PCTCN2020114650-appb-000001
所述组分B的原料配方包括下列质量百分比的原料：The raw material formula of component B includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000002
Figure PCTCN2020114650-appb-000002
Figure PCTCN2020114650-appb-000003
Figure PCTCN2020114650-appb-000003
优选的技术方案为：所述双酚型缩水甘油醚环氧树脂为二酚基甲烷缩水甘油醚、二酚基丙烷缩水甘油醚、氢化二酚基丙烷缩水甘油醚、羟甲基二酚基丙烷缩水甘油醚中的至少一种。The preferred technical solution is: the bisphenol type glycidyl ether epoxy resin is diphenol methane glycidyl ether, diphenol propane glycidyl ether, hydrogenated diphenol propane glycidyl ether, and methylol diphenol propane At least one of glycidyl ethers.
优选的技术方案为：所述多酚型缩水甘油醚环氧树脂为邻甲酚甲醛多缩水甘油醚、间苯二酚甲醛多缩水甘油醚和线性苯酚甲醛多缩水甘油醚中的至少一种。The preferred technical solution is that the polyphenol type glycidyl ether epoxy resin is at least one of ortho-cresol formaldehyde polyglycidyl ether, resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether.
优选的技术方案为：所述杂环混合型环氧树脂为异氰尿酸三缩水甘油酯、三聚氰酸缩水甘油醚、1,3-二缩水甘油基海因和1-缩水甘油基-3-缩水甘油氧合甲基-5,5-二甲基海因中的至少一种。The preferred technical solution is: the heterocyclic mixed epoxy resin is triglycidyl isocyanurate, glycidyl cyanurate, 1,3-diglycidyl hydantoin and 1-glycidyl-3 -At least one of glycidyloxymethyl-5,5-dimethylhydantoin.
优选的技术方案为：所述活性稀释剂为环氧丙烷丁基醚、环氧丙烷苯基醚、乙二醇二缩水甘油醚、1，4-丁二醇二缩水甘油醚和间苯二酚二缩水甘油醚中的至少一种。The preferred technical solution is: the reactive diluent is propylene oxide butyl ether, propylene oxide phenyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether and resorcinol At least one of diglycidyl ethers.
优选的技术方案为：所述增韧剂为端羧基液体丁腈橡胶、聚乙烯醇缩丁醛、聚苯醚酮、氯磺化聚乙烯、聚醋酸乙烯和粉末聚乙烯醇中的至少一种。The preferred technical solution is: the toughening agent is at least one of carboxyl-terminated liquid nitrile rubber, polyvinyl butyral, polyphenylene ether ketone, chlorosulfonated polyethylene, polyvinyl acetate, and powdered polyvinyl alcohol .
优选的技术方案为：所述碳界面处理剂为烃基硼酸、碳硼烷、硼酸酯和乙硼烷中的至少一种。The preferred technical solution is that the carbon interface treatment agent is at least one of hydrocarbyl boric acid, carborane, borate and diborane.
优选的技术方案为：所述反应型有机硅改质剂为符合下列结构通式的化合物：The preferred technical solution is: the reactive organosilicon modifier is a compound conforming to the following general structural formula:
YRSiX 3 YRSiX 3
其中Y代表环氧基、氨基、甲基丙乙烯酰氧基或巯基；R代表烷基或芳基；X代表甲氧基、乙氧基或氯基。Wherein Y represents an epoxy group, an amino group, a methyl propionyloxy group or a mercapto group; R represents an alkyl group or an aryl group; X represents a methoxy group, an ethoxy group or a chloro group.
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯、少层石墨烯和多层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.2g/cm 3以内，振实密度为0.05～0.2g/cm 3。 The preferred technical solution is: the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; the graphene loose packing density is 0.01-0.2 g/cm Within 3 , the tap density is 0.05～0.2g/cm 3 .
优选的技术方案为：所述碳纳米管为单壁碳纳米管和多壁碳纳米管中的一种或两种，所述碳纳米管直径为1-5纳米，长度为0.1-5微米。The preferred technical solution is that the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
优选的技术方案为：所述的固化剂为聚酰胺、聚醚胺、聚硫醇、、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐和甲基纳迪克酸酐中的至少一种。The preferred technical solution is: the curing agent is polyamide, polyetheramine, polythiol, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride. At least one of.
优选的技术方案为：所述固化增速剂为2，4，6-三(二甲胺基甲基)苯酚、三 苯基膦、双环脒、苄基二甲胺、钛酸三异丙醇叔胺酯和三乙醇胺中的至少一种。The preferred technical solution is: the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, triphenylphosphine, bicyclic amidine, benzyldimethylamine, triisopropanol titanate At least one of tertiary amine ester and triethanolamine.
优选的技术方案为：所述非活性稀释剂为乙酸乙酯、邻苯二甲酸二丁酯、环己酮和苯乙烯中的至少一种。The preferred technical solution is: the inactive diluent is at least one of ethyl acetate, dibutyl phthalate, cyclohexanone and styrene.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯AB胶的方法：其特征在于：包括下列步骤：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a method for preparing graphene AB glue: It is characterized in that it includes the following steps:
步骤1：向反应釜A中依次加入双酚型缩水甘油醚环氧树脂、多酚型缩水甘油醚环氧树脂、杂环混合型环氧树脂、活性稀释剂、增韧剂、碳界面处理剂和反应型有机硅改质剂，搅拌均匀；再向反应釜A中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压条件下搅拌和分散至均匀无气泡，得到胶样A；Step 1: Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
步骤2：向反应釜B中加入固化剂、固化增速剂、非活性稀释剂、碳界面处理剂、反应型有机硅改质剂、搅拌均匀；再向反应釜B中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压和循环水冷却条件下，搅拌至均匀无气泡，得到胶样B；Step 2: Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
步骤3：分别取出胶样A和胶样B，按照1～2:1的重量比混合均匀，即制成石墨烯AB胶。Step 3: Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 1 to 2: 1 to form the graphene AB glue.
优选的技术方案为：负压条件为真空度为-0.08～-0.1MPa。The preferred technical solution is: the negative pressure condition is that the vacuum degree is -0.08～-0.1MPa.
由于上述技术方案运用，本发明与现有技术相比具有的优点是：Due to the application of the above technical solutions, the advantages of the present invention compared with the prior art are:
本发明与现有技术相比，该石墨烯AB胶及石墨烯基电磁和热屏蔽环氧材料利用石墨烯优异的电子效应和热效应等物理性质，不仅达到了电磁和热同时屏蔽的性能，而且重量比和体积比控制适当，使各组分协同作用，达到了优秀的力学强度和可靠稳定性。通过测试，该石墨烯AB胶的电导率在10 3～10 4S/m，在10KHz处电磁屏蔽效能45～50dB；导热率2.0～2.5W/(m·K)，在14.5℃时热中子俘获截面0.01～0.1mbar；铝/铝推力15～20Kg,PC/PC推力8～10Kg；经过168个小时的‘高温高湿’可靠性测试，电磁和热屏蔽效能损耗率在5％以内，力学强度损耗率在15％以内。 Compared with the prior art, the graphene AB glue and graphene-based electromagnetic and thermal shielding epoxy material uses the excellent electronic and thermal effects of graphene to not only achieve the performance of simultaneous electromagnetic and thermal shielding, but also The weight ratio and volume ratio are properly controlled, so that the components work together to achieve excellent mechanical strength and reliable stability. Through the test, the conductivity of the graphene AB glue is 10 3 ～10 4 S/m, the electromagnetic shielding efficiency is 45～50dB at 10KHz; the thermal conductivity is 2.0～2.5W/(m·K), and it is hot at 14.5℃ The sub-capture cross-section is 0.01～0.1mbar; the thrust of aluminum/aluminum is 15～20Kg, and the thrust of PC/PC is 8～10Kg; after 168 hours of reliability test of “high temperature and high humidity”, the loss rate of electromagnetic and thermal shielding effectiveness is within 5%, The loss rate of mechanical strength is within 15%.
具体实施方式Detailed ways
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The following specific examples illustrate the implementation of the present invention. Those familiar with the technology can easily understand the other advantages and effects of the present invention from the content disclosed in this specification.
实施例1：一种石墨烯AB胶及制备方法Example 1: A graphene AB glue and preparation method
一种石墨烯AB胶，其特征在于，包括以下组分及质量百分数：A graphene AB glue, characterized in that it includes the following components and mass percentages:
组分A：Component A:
Figure PCTCN2020114650-appb-000004
Figure PCTCN2020114650-appb-000004
组分B：Component B:
Figure PCTCN2020114650-appb-000005
Figure PCTCN2020114650-appb-000005
所述的双酚型缩水甘油醚环氧树脂为二酚基甲烷缩水甘油醚，25℃时粘度4000mpa·s，环氧当量170g/eq)。The bisphenol-type glycidyl ether epoxy resin is diphenol-based methane glycidyl ether, the viscosity is 4000 mPa·s at 25° C., and the epoxy equivalent is 170 g/eq).
所述的多酚型缩水甘油醚环氧树脂为邻甲酚甲醛多缩水甘油醚、间苯二酚甲醛多缩水甘油醚按照1：1的质量比例构成的混合物；25℃时粘度5000mpa·s，环氧当量200g/eq。The polyphenol type glycidyl ether epoxy resin is a mixture of o-cresol formaldehyde polyglycidyl ether and resorcinol formaldehyde polyglycidyl ether in a mass ratio of 1:1; the viscosity at 25°C is 5000 mpa·s, Epoxy equivalent is 200g/eq.
所述的杂环混合型环氧树脂为异氰尿酸三缩水甘油酯，环氧当量100g/eq)。The heterocyclic mixed epoxy resin is triglycidyl isocyanurate with an epoxy equivalent of 100 g/eq).
所述的活性稀释剂为环氧丙烷丁基醚、环氧丙烷苯基醚按照1：5的质量比例构成的混合物；环氧当量控制在200g/eq范围内。The reactive diluent is a mixture of propylene oxide butyl ether and propylene oxide phenyl ether in a mass ratio of 1:5; the epoxy equivalent is controlled within the range of 200 g/eq.
所述的增韧剂为聚乙烯醇缩丁醛、聚苯醚酮按照2：1的质量比例构成的混合物。The toughening agent is a mixture of polyvinyl butyral and polyphenylene ether ketone in a mass ratio of 2:1.
所述的碳界面处理剂为烃基硼酸、碳硼烷、硼酸酯按照1：1.2：1的质量比例构成的混合物。The carbon interface treatment agent is a mixture of hydrocarbyl boric acid, carborane, and boric acid ester in a mass ratio of 1:1.2:1.
所述的反应型有机硅改质剂符合结构通式为YRSiX 3：其中Y为环氧基；R为烷基；X为甲氧基。 The reactive organosilicon modifier conforms to the general structural formula YRSiX 3 : wherein Y is an epoxy group; R is an alkyl group; X is a methoxy group.
所述的石墨烯为单层石墨烯，上述石墨烯松装密度控制在0.01g/cm 3以内，振实密度为0.01g/cm 3以内。 The graphene is a single-layer graphene, the bulk density of the graphene is controlled within 0.01 g/cm 3 , and the tap density is within 0.01 g/cm 3.
所述的碳纳米管为单壁碳纳米管，上述碳纳米管直径控制在1～5纳米以内，长度控制在0.1～5微米以内。The carbon nanotubes are single-walled carbon nanotubes, the diameter of the carbon nanotubes is controlled within 1 to 5 nanometers, and the length is controlled within 0.1 to 5 microns.
所述的固化剂为聚酰胺，胺值350mgKOH/g，活泼氢当量150g/eq，25℃时粘度50000mPa.S。The curing agent is polyamide, with an amine value of 350 mgKOH/g, an active hydrogen equivalent of 150 g/eq, and a viscosity of 50,000 mPa.S at 25°C.
所述的固化增速剂为三苯基膦、双环脒按照1：1的质量比例构成的混合物。The curing accelerator is a mixture of triphenylphosphine and bicyclic amidine in a mass ratio of 1:1.
所述的非活性稀释剂为乙酸乙酯、邻苯二甲酸二丁酯按照1：1的质量比例构成的混合物。The inactive diluent is a mixture of ethyl acetate and dibutyl phthalate in a mass ratio of 1:1.
石墨烯AB胶的制备方法，包括以下步骤：The preparation method of graphene AB glue includes the following steps:
(1)向反应釜A中依次加入双酚型缩水甘油醚环氧树脂、多酚型缩水甘油醚环氧树脂、杂环混合型环氧树脂、活性稀释剂、增韧剂、碳界面处理剂和反应型有机硅改质剂，低速搅拌，至均匀；再向反应釜中依次加入石墨烯和碳纳米管，低速搅拌，至均匀；最后在负压条件下高速搅拌和分散，至均匀无气泡；(1) Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A With reactive organosilicon modifier, stir at low speed until uniform; then add graphene and carbon nanotubes to the reactor in sequence, stir at low speed until uniform; finally stir and disperse at high speed under negative pressure until uniform without bubbles ；
(2)向反应釜B中加入固化剂；固化增速剂；非活性稀释剂，碳界面处理剂，反应型有机硅改质剂，低速搅拌，至均匀；再向反应釜中依次加入石墨烯和碳纳米管，低速搅拌，至均匀；最后在负压和循环水冷却条件下，低速搅拌，至均匀无气泡；(2) Add curing agent to reactor B; curing accelerator; inactive diluent, carbon interface treatment agent, reactive organosilicon modifier, stir at low speed until uniform; then add graphene to the reactor sequentially And carbon nanotubes, stir at low speed until uniform; finally, under negative pressure and circulating water cooling conditions, stir at low speed until uniform without bubbles;
(3)分别取出胶样AB，按照1.5:1重量比混合均匀，测试固化后性能，达到标准要求后，出料，即制成石墨烯AB胶。石墨烯A胶和石墨烯B胶分别包装，使用时再进行混合。(3) Take out the glue sample AB separately, mix it evenly according to the weight ratio of 1.5:1, test the performance after curing, and discharge the material after reaching the standard requirements, and then make the graphene AB glue. Graphene A glue and graphene B glue are packaged separately, and then mixed before use.
步骤(1)～(4)中所述低速为15r/min，高速为50r/min，分散盘速度为1000r/min；负压条件为真空度为-0.09MPa。In steps (1) to (4), the low speed is 15r/min, the high speed is 50r/min, and the dispersing disc speed is 1000r/min; the negative pressure condition is that the vacuum degree is -0.09MPa.
实施例2：一种石墨烯AB胶及制备方法Embodiment 2: A graphene AB glue and its preparation method
其它实施方式同实施例1，不同之处如下：Other implementations are the same as in Example 1, the differences are as follows:
所述的双酚型缩水甘油醚环氧树脂为二酚基丙烷缩水甘油醚和氢化二酚基丙烷缩水甘油醚按照1：1.5的质量比例构成的混合物。二酚基丙烷缩水甘油醚25℃时粘度8000mpa·s，环氧当量170g/eq)、氢化二酚基丙烷缩水甘油醚25℃时粘度10000mpa·s，环氧当量500g/eq)。The bisphenol-type glycidyl ether epoxy resin is a mixture composed of diphenol-based propane glycidyl ether and hydrogenated diphenol-based propane glycidyl ether in a mass ratio of 1:1.5. Diphenol-based propane glycidyl ether has a viscosity of 8000mpa·s at 25°C and an epoxy equivalent of 170g/eq), and hydrogenated diphenol-based propane glycidyl ether has a viscosity of 10,000mpa·s at 25°C and an epoxy equivalent of 500g/eq).
所述的多酚型缩水甘油醚环氧树脂为邻甲酚甲醛多缩水甘油醚、间苯二酚甲醛多缩水甘油醚和线性苯酚甲醛多缩水甘油醚按照1：1：1：2的质量比例构成 的混合物；25℃时粘度8000mpa·s，环氧当量200g/eq。The polyphenol-type glycidyl ether epoxy resin is o-cresol formaldehyde polyglycidyl ether, resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether in a mass ratio of 1:1:1:2 The composition of the mixture; the viscosity at 25°C is 8000mpa·s, and the epoxy equivalent is 200g/eq.
所述的杂环混合型环氧树脂为1,3-二缩水甘油基海因和1-缩水甘油基-3-缩水甘油氧合甲基-5,5-二甲基海因按照1：1的质量比例构成的混合物。1,3-二缩水甘油基海因的环氧当量500。1-缩水甘油基-3-缩水甘油氧合甲基-5,5-二甲基海因的环氧当量500。The heterocyclic mixed epoxy resin is 1,3-diglycidyl hydantoin and 1-glycidyl-3-glycidyloxymethyl-5,5-dimethyl hydantoin according to 1:1 The mass ratio constitutes a mixture. The epoxy equivalent of 1,3-diglycidylhydantoin is 500. The epoxy equivalent of 1-glycidyl-3-glycidyloxymethyl-5,5-dimethylhydantoin is 500.
所述的活性稀释剂为环氧丙烷丁基醚；环氧当量控制在200g/eq范围内。The reactive diluent is propylene oxide butyl ether; the epoxy equivalent is controlled in the range of 200 g/eq.
所述的增韧剂为端羧基液体丁腈橡胶、聚乙烯醇缩丁醛按照3：1的质量比例构成的混合物。The toughening agent is a mixture of carboxyl-terminated liquid nitrile rubber and polyvinyl butyral in a mass ratio of 3:1.
所述的碳界面处理剂为烃基硼酸。The carbon interface treatment agent is hydrocarbyl boric acid.
所述的反应型有机硅改质剂符合结构通式为YRSiX 3：其中Y为氨基；R为芳基；X为氯基。 The reactive organosilicon modifier conforms to the general structural formula YRSiX 3 : wherein Y is an amino group; R is an aryl group; X is a chloro group.
所述的石墨烯为单层石墨烯、双层石墨烯按照1：1的质量比例构成的混合物，上述石墨烯松装密度控制在0.2g/cm 3以内，振实密度为0.2g/cm 3以内。 The graphene is a mixture of single-layer graphene and double-layer graphene according to a mass ratio of 1:1. The bulk density of the graphene is controlled within 0.2g/cm 3 and the tap density is 0.2g/cm 3 Within.
所述的碳纳米管为单壁碳纳米管和多壁碳纳米管按照1：1的质量比例构成的混合物，上述碳纳米管直径控制在1～5纳米以内，长度控制在0.1～5微米以内。The carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:1. The diameter of the carbon nanotubes is controlled within 1 to 5 nanometers, and the length is controlled within 0.1 to 5 microns. .
所述的固化剂为聚醚胺，胺值200mgKOH/g，活泼氢当量50g/eq。The curing agent is polyether amine with an amine value of 200 mgKOH/g and an active hydrogen equivalent of 50 g/eq.
所述的固化增速剂为2，4，6-三(二甲胺基甲基)苯酚。The curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.
所述的非活性稀释剂为乙酸乙酯、邻苯二甲酸二丁酯按照1：1的质量比例构成的混合物。The inactive diluent is a mixture of ethyl acetate and dibutyl phthalate in a mass ratio of 1:1.
实施例3：一种石墨烯AB胶及制备方法Embodiment 3: A graphene AB glue and its preparation method
一种石墨烯AB胶，所述石墨烯AB胶由组份A和组份B按照1。5:1的质量比例混合后构成：A graphene AB glue, the graphene AB glue is composed of component A and component B mixed in a mass ratio of 1.5:1:
所述组分A的原料配方包括下列质量百分比的原料：The raw material formula of component A includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000006
Figure PCTCN2020114650-appb-000006
Figure PCTCN2020114650-appb-000007
Figure PCTCN2020114650-appb-000007
所述组分B的原料配方包括下列质量百分比的原料：The raw material formula of component B includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000008
Figure PCTCN2020114650-appb-000008
优选的实施方式为：所述二酚基甲烷缩水甘油醚、二酚基丙烷缩水甘油醚和氢化二酚基丙烷缩水甘油醚按照1：3：1的质量比例构成的混合物。A preferred embodiment is: a mixture of the diphenol-based methane glycidyl ether, the diphenol-based propane glycidyl ether, and the hydrogenated diphenol-based propane glycidyl ether in a mass ratio of 1:3:1.
优选的实施方式为：所述多酚型缩水甘油醚环氧树脂为间苯二酚甲醛多缩水甘油醚和线性苯酚甲醛多缩水甘油醚按照1：2的质量比例构成的混合物。A preferred embodiment is that the polyphenol-type glycidyl ether epoxy resin is a mixture composed of resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde polyglycidyl ether in a mass ratio of 1:2.
优选的实施方式为：所述杂环混合型环氧树脂为1,3-二缩水甘油基海因。A preferred embodiment is that the heterocyclic mixed epoxy resin is 1,3-diglycidyl hydantoin.
优选的实施方式为：所述活性稀释剂为环氧丙烷苯基醚。A preferred embodiment is: the reactive diluent is propylene oxide phenyl ether.
优选的实施方式为：所述增韧剂为氯磺化聚乙烯。A preferred embodiment is that the toughening agent is chlorosulfonated polyethylene.
优选的实施方式为：所述碳界面处理剂为碳硼烷。A preferred embodiment is that the carbon interface treatment agent is carborane.
优选的实施方式为：所述反应型有机硅改质剂为符合下列结构通式的化合物：A preferred embodiment is: the reactive organosilicon modifier is a compound conforming to the following general structural formula:
YRSiX 3 YRSiX 3
其中Y代表甲基丙乙烯酰氧基；R代表烷基；X代表乙氧基。Wherein Y represents methyl propionyloxy; R represents alkyl; X represents ethoxy.
优选的实施方式为：所述石墨烯为单层石墨烯；所述石墨烯松装密度为0.01g/cm 3以内，振实密度为0.05g/cm 3。 A preferred embodiment is: the graphene is a single-layer graphene; the graphene has a loose packing density of 0.01 g/cm 3 or less, and a tap density of 0.05 g/cm 3 .
优选的实施方式为：所述碳纳米管为单壁碳纳米管和多壁碳纳米管中的一种或两种，所述碳纳米管直径为1-5纳米，长度为0.1-5微米。A preferred embodiment is that the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
优选的实施方式为：所述的固化剂为聚硫醇。A preferred embodiment is that the curing agent is polythiol.
优选的实施方式为：所述固化增速剂为苄基二甲胺。A preferred embodiment is that the curing speed-increasing agent is benzyldimethylamine.
优选的实施方式为：所述非活性稀释剂为邻苯二甲酸二丁酯。A preferred embodiment is: the inactive diluent is dibutyl phthalate.
一种制备石墨烯AB胶的方法：包括下列步骤：A method for preparing graphene AB glue: including the following steps:
步骤1：向反应釜A中依次加入双酚型缩水甘油醚环氧树脂、多酚型缩水甘油醚环氧树脂、杂环混合型环氧树脂、活性稀释剂、增韧剂、碳界面处理剂和反 应型有机硅改质剂，搅拌均匀；再向反应釜A中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压条件下搅拌和分散至均匀无气泡，得到胶样A；Step 1: Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
步骤2：向反应釜B中加入固化剂、固化增速剂、非活性稀释剂、碳界面处理剂、反应型有机硅改质剂、搅拌均匀；再向反应釜B中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压和循环水冷却条件下，搅拌至均匀无气泡，得到胶样B；Step 2: Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
步骤3：分别取出胶样A和胶样B，按照1:1的重量比混合均匀，即制成石墨烯AB胶。Step 3: Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 1:1 to form the graphene AB glue.
优选的实施方式为：负压条件为真空度为-0.08MPa。A preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.08 MPa.
实施例4：一种石墨烯AB胶及制备方法Embodiment 4: A graphene AB glue and preparation method
一种石墨烯AB胶，所述石墨烯AB胶由组份A和组份B按照1-2:1的质量比例混合后构成：A graphene AB glue, the graphene AB glue is composed of component A and component B mixed in a mass ratio of 1-2:1:
所述组分A的原料配方包括下列质量百分比的原料：The raw material formula of component A includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000009
Figure PCTCN2020114650-appb-000009
所述组分B的原料配方包括下列质量百分比的原料：The raw material formula of component B includes the following mass percentages of raw materials:
Figure PCTCN2020114650-appb-000010
Figure PCTCN2020114650-appb-000010
优选的实施方式为：所述双酚型缩水甘油醚环氧树脂为二酚基丙烷缩水甘 油醚。A preferred embodiment is that the bisphenol type glycidyl ether epoxy resin is diphenol propane glycidyl ether.
优选的实施方式为：所述多酚型缩水甘油醚环氧树脂为间苯二酚甲醛多缩水甘油醚。A preferred embodiment is that the polyphenol type glycidyl ether epoxy resin is resorcinol formaldehyde polyglycidyl ether.
优选的实施方式为：所述杂环混合型环氧树脂为三聚氰酸缩水甘油醚。A preferred embodiment is that the heterocyclic mixed epoxy resin is glycidyl cyanurate.
优选的实施方式为：所述活性稀释剂为乙二醇二缩水甘油醚。A preferred embodiment is: the reactive diluent is ethylene glycol diglycidyl ether.
优选的实施方式为：所述增韧剂为聚醋酸乙烯和粉末聚乙烯醇按照1：1的质量比例构成的混合物。A preferred embodiment is: the toughening agent is a mixture of polyvinyl acetate and powdered polyvinyl alcohol in a mass ratio of 1:1.
优选的实施方式为：所述碳界面处理剂为烃基硼酸、碳硼烷粉末聚乙烯醇。A preferred embodiment is: the carbon interface treatment agent is hydrocarbyl boric acid, carborane powder polyvinyl alcohol.
优选的实施方式为：所述反应型有机硅改质剂为符合下列结构通式的化合物：A preferred embodiment is: the reactive organosilicon modifier is a compound conforming to the following general structural formula:
YRSiX 3 YRSiX 3
其中Y代表巯基；R代表烷基；X代表甲氧基。Where Y represents a mercapto group; R represents an alkyl group; X represents a methoxy group.
优选的实施方式为：所述石墨烯为多层石墨烯；所述石墨烯松装密度为0.08g/cm 3以内，振实密度为0.15g/cm 3。 A preferred embodiment is: the graphene is a multilayer graphene; the graphene loose packing density is within 0.08 g/cm 3 , and the tap density is 0.15 g/cm 3 .
优选的实施方式为：所述碳纳米管为多壁碳纳米管，所述碳纳米管直径为1-5纳米，长度为0.1-5微米。In a preferred embodiment, the carbon nanotubes are multi-walled carbon nanotubes, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1-5 micrometers.
优选的实施方式为：所述的固化剂为甲基四氢邻苯二甲酸酐。A preferred embodiment is: the curing agent is methyltetrahydrophthalic anhydride.
优选的实施方式为：所述固化增速剂为双环脒。A preferred embodiment is that the curing speed-increasing agent is bicyclic amidine.
优选的实施方式为：所述非活性稀释剂为乙酸乙酯。A preferred embodiment is that the inactive diluent is ethyl acetate.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯AB胶的方法：其特征在于：包括下列步骤：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a method for preparing graphene AB glue: It is characterized in that it includes the following steps:
步骤1：向反应釜A中依次加入双酚型缩水甘油醚环氧树脂、多酚型缩水甘油醚环氧树脂、杂环混合型环氧树脂、活性稀释剂、增韧剂、碳界面处理剂和反应型有机硅改质剂，搅拌均匀；再向反应釜A中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压条件下搅拌和分散至均匀无气泡，得到胶样A；Step 1: Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
步骤2：向反应釜B中加入固化剂、固化增速剂、非活性稀释剂、碳界面处理剂、反应型有机硅改质剂、搅拌均匀；再向反应釜B中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压和循环水冷却条件下，搅拌至均匀无气泡，得到胶样B；Step 2: Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
步骤3：分别取出胶样A和胶样B，按照2:1的重量比混合均匀，即制成石墨烯AB胶。Step 3: Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 2:1 to form the graphene AB glue.
优选的实施方式为：负压条件为真空度为-0.1MPa。A preferred embodiment is: the negative pressure condition is that the degree of vacuum is -0.1 MPa.
实施例5：一种石墨烯AB胶及制备方法Embodiment 5: A graphene AB glue and its preparation method
其它实施方式同实施例5，不同之处如下：Other implementations are the same as in Example 5, but the differences are as follows:
优选的实施方式为：所述双酚型缩水甘油醚环氧树脂为羟甲基二酚基丙烷缩水甘油醚。A preferred embodiment is that the bisphenol type glycidyl ether epoxy resin is hydroxymethyl diphenol propane glycidyl ether.
优选的实施方式为：所述多酚型缩水甘油醚环氧树脂为邻甲酚甲醛多缩水甘油醚。A preferred embodiment is that the polyphenol type glycidyl ether epoxy resin is ortho-cresol formaldehyde polyglycidyl ether.
优选的实施方式为：所述杂环混合型环氧树脂为1-缩水甘油基-3-缩水甘油氧合甲基-5,5-二甲基海因。A preferred embodiment is: the heterocyclic mixed epoxy resin is 1-glycidyl-3-glycidyloxymethyl-5,5-dimethylhydantoin.
优选的实施方式为：所述活性稀释剂为环氧丙烷苯基醚和乙二醇二缩水甘油醚按照1：1的质量比例构成的混合物。A preferred embodiment is that the reactive diluent is a mixture of propylene oxide phenyl ether and ethylene glycol diglycidyl ether in a mass ratio of 1:1.
优选的实施方式为：所述增韧剂为氯磺化聚乙烯。A preferred embodiment is that the toughening agent is chlorosulfonated polyethylene.
优选的实施方式为：所述碳界面处理剂为乙硼烷。A preferred embodiment is that the carbon interface treatment agent is diborane.
优选的实施方式为：所述反应型有机硅改质剂为符合下列结构通式的化合物：A preferred embodiment is: the reactive organosilicon modifier is a compound conforming to the following general structural formula:
YRSiX 3 YRSiX 3
其中Y代表氨基；R代表烷基；X代表乙氧基。Wherein Y represents amino; R represents alkyl; X represents ethoxy.
优选的实施方式为：所述石墨烯为少层石墨烯；所述石墨烯松装密度为0.15g/cm 3以内，振实密度为0.15g/cm 3。 A preferred embodiment is: the graphene is a few-layer graphene; the graphene has a loose packing density of 0.15 g/cm 3 or less, and a tap density of 0.15 g/cm 3 .
优选的实施方式为：所述碳纳米管为单壁碳纳米管和多壁碳纳米管按照1：1的质量比例构成的混合物，所述碳纳米管直径为1-5纳米，长度为0.1-5微米。A preferred embodiment is that the carbon nanotubes are a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes in a mass ratio of 1:1, and the carbon nanotubes have a diameter of 1-5 nanometers and a length of 0.1- 5 microns.
优选的实施方式为：所述的固化剂为甲基六氢邻苯二甲酸酐和甲基纳迪克酸酐按照1：1的质量比例构成的混合物。A preferred embodiment is: the curing agent is a mixture of methylhexahydrophthalic anhydride and methylnadic anhydride in a mass ratio of 1:1.
优选的实施方式为：所述固化增速剂为钛酸三异丙醇叔胺酯和三乙醇胺按照1：1的质量比例构成的混合物。A preferred embodiment is that: the curing speed-increasing agent is a mixture of triisopropanol titanate tertiary amine ester and triethanolamine in a mass ratio of 1:1.
优选的实施方式为：所述非活性稀释剂为邻苯二甲酸二丁酯。A preferred embodiment is: the inactive diluent is dibutyl phthalate.
以上所述者仅为用以解释本发明之较佳实施例，并非企图具以对本发明做任何形式上之限制，是以，凡有在相同之发明精神下所作有关本发明之任何修饰或变更，皆仍应包括在本发明意图保护之范畴。The above descriptions are only used to explain the preferred embodiments of the present invention, and are not intended to restrict the present invention in any form. Therefore, any modification or alteration related to the present invention is made under the same spirit of the invention. , Should still be included in the scope of the present invention's intended protection.

Claims (15)

  1. 一种石墨烯AB胶，其特征在于：所述石墨烯AB胶由组份A和组份B按照1-2:1的质量比例混合后构成：A graphene AB glue, characterized in that: the graphene AB glue is formed by mixing component A and component B in a mass ratio of 1-2:1:
    所述组分A的原料配方包括下列质量百分比的原料：The raw material formula of component A includes the following mass percentages of raw materials:
    Figure PCTCN2020114650-appb-100001
    Figure PCTCN2020114650-appb-100001
    所述组分B的原料配方包括下列质量百分比的原料：The raw material formula of component B includes the following mass percentages of raw materials:
    Figure PCTCN2020114650-appb-100002
    Figure PCTCN2020114650-appb-100002
  2. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述双酚型缩水甘油醚环氧树脂为二酚基甲烷缩水甘油醚、二酚基丙烷缩水甘油醚、氢化二酚基丙烷缩水甘油醚、羟甲基二酚基丙烷缩水甘油醚中的至少一种。The graphene AB glue according to claim 1, wherein the bisphenol-based glycidyl ether epoxy resin is diphenol-based methane glycidyl ether, diphenol-based propane glycidyl ether, and hydrogenated diphenol-based propane glycidyl ether. At least one of glyceryl ether and hydroxymethyl diphenol propane glycidyl ether.
  3. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述多酚型缩水甘油醚环氧树脂为邻甲酚甲醛多缩水甘油醚、间苯二酚甲醛多缩水甘油醚和线性苯酚甲醛多缩水甘油醚中的至少一种。The graphene AB glue according to claim 1, wherein the polyphenol type glycidyl ether epoxy resin is o-cresol formaldehyde polyglycidyl ether, resorcinol formaldehyde polyglycidyl ether and linear phenol formaldehyde At least one of polyglycidyl ethers.
  4. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述杂环混合型环氧树脂为异氰尿酸三缩水甘油酯、三聚氰酸缩水甘油醚、1,3-二缩水甘油基海因和1-缩水甘油基-3-缩水甘油氧合甲基-5,5-二甲基海因中的至少一种。The graphene AB glue according to claim 1, wherein the heterocyclic mixed epoxy resin is triglycidyl isocyanurate, glycidyl cyanurate, 1,3-diglycidyl At least one of hydantoin and 1-glycidyl-3-glycidyloxymethyl-5,5-dimethylhydantoin.
  5. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述活性稀释剂为环氧丙烷丁基醚、环氧丙烷苯基醚、乙二醇二缩水甘油醚、1，4-丁二醇二缩水甘油醚和间苯二酚二缩水甘油醚中的至少一种。The graphene AB glue according to claim 1, wherein the reactive diluent is propylene oxide butyl ether, propylene oxide phenyl ether, ethylene glycol diglycidyl ether, 1,4-butanedi At least one of alcohol diglycidyl ether and resorcinol diglycidyl ether.
  6. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述增韧剂为端羧基液体丁腈橡胶、聚乙烯醇缩丁醛、聚苯醚酮、氯磺化聚乙烯、聚醋酸乙烯和粉末聚乙烯醇中的至少一种。The graphene AB glue according to claim 1, wherein the toughening agent is carboxyl-terminated liquid nitrile rubber, polyvinyl butyral, polyphenylene ether ketone, chlorosulfonated polyethylene, polyvinyl acetate And at least one of powdered polyvinyl alcohol.
  7. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述碳界面处理剂为烃基硼酸、碳硼烷、硼酸酯和乙硼烷中的至少一种。The graphene AB glue according to claim 1, wherein the carbon interface treatment agent is at least one of hydrocarbyl boric acid, carborane, borate and diborane.
  8. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述反应型有机硅改质剂为符合下列结构通式的化合物：The graphene AB glue according to claim 1, wherein the reactive silicone modifier is a compound conforming to the following general structural formula:
    YRSiX 3 YRSiX 3
    其中Y代表环氧基、氨基、甲基丙乙烯酰氧基或巯基；R代表烷基或芳基；X代表甲氧基、乙氧基或氯基。Wherein Y represents an epoxy group, an amino group, a methyl propionyloxy group or a mercapto group; R represents an alkyl group or an aryl group; X represents a methoxy group, an ethoxy group or a chloro group.
  9. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述石墨烯为单层石墨烯、双层石墨烯、少层石墨烯和多层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.2g/cm 3以内，振实密度为0.05～0.2g/cm 3。 The graphene AB glue according to claim 1, wherein the graphene is at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene; the graphene The bulk density is within 0.01-0.2g/cm 3 , and the tap density is 0.05-0.2g/cm 3 .
  10. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述碳纳米管为单壁碳纳米管和多壁碳纳米管中的一种或两种，所述碳纳米管直径为1-5纳米，长度为0.1-5微米。The graphene AB glue of claim 1, wherein the carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes, and the diameter of the carbon nanotubes is 1- 5 nanometers, the length is 0.1-5 microns.
  11. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述的固化剂为聚酰胺、聚醚胺、聚硫醇、、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐和甲基纳迪克酸酐中的至少一种。The graphene AB glue according to claim 1, wherein the curing agent is polyamide, polyetheramine, polythiol, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and At least one of dicarboxylic anhydride and methylnadic anhydride.
  12. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述固化增速剂为2，4，6-三(二甲胺基甲基)苯酚、三苯基膦、双环脒、苄基二甲胺、钛酸三异丙醇叔胺酯和三乙醇胺中的至少一种。The graphene AB glue according to claim 1, wherein the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol, triphenylphosphine, bicyclic amidine, benzyl At least one of dimethylamine, triisopropanol titanate tertiary amine ester, and triethanolamine.
  13. 根据权利要求1所述的石墨烯AB胶，其特征在于：所述非活性稀释剂为乙酸乙酯、邻苯二甲酸二丁酯、环己酮和苯乙烯中的至少一种。The graphene AB glue according to claim 1, wherein the inactive diluent is at least one of ethyl acetate, dibutyl phthalate, cyclohexanone and styrene.
  14. 一种制备权利要求1-13任一所述的石墨烯AB胶的方法：其特征在于：包括下列步骤：A method for preparing the graphene AB glue according to any one of claims 1-13, characterized in that it comprises the following steps:
    步骤1：向反应釜A中依次加入双酚型缩水甘油醚环氧树脂、多酚型缩水甘油醚环氧树脂、杂环混合型环氧树脂、活性稀释剂、增韧剂、碳界面处理剂和反应型有机硅改质剂，搅拌均匀；再向反应釜A中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压条件下搅拌和分散至均匀无气泡，得到胶样A；Step 1: Add bisphenol type glycidyl ether epoxy resin, polyphenol type glycidyl ether epoxy resin, heterocyclic mixed type epoxy resin, reactive diluent, toughening agent, and carbon interface treatment agent in sequence to reactor A And the reactive organosilicon modifier, stir evenly; then add graphene and carbon nanotubes to reactor A in sequence, and stir evenly; finally stir and disperse under negative pressure until uniform and no bubbles, to obtain gel sample A;
    步骤2：向反应釜B中加入固化剂、固化增速剂、非活性稀释剂、碳界面处理剂、反应型有机硅改质剂、搅拌均匀；再向反应釜B中依次加入石墨烯和碳纳米管，搅拌均匀；最后在负压和循环水冷却条件下，搅拌至均匀无气泡，得到胶样B；Step 2: Add curing agent, curing accelerator, non-reactive diluent, carbon interface treatment agent, reactive silicone modifier to reactor B, and stir well; then add graphene and carbon to reactor B in sequence Nanotubes, stir evenly; finally, under negative pressure and circulating water cooling conditions, stir until uniform and no bubbles, to obtain gel sample B;
    步骤3：分别取出胶样A和胶样B，按照1～2:1的重量比混合均匀，即制成石墨烯AB胶。Step 3: Take out the glue sample A and glue sample B respectively, and mix them evenly according to the weight ratio of 1 to 2: 1 to form the graphene AB glue.
  15. 根据权利要求14所述的方法，其特征在于：负压条件为真空度为-0.08～-0.1MPa。The method according to claim 14, wherein the negative pressure condition is that the degree of vacuum is -0.08 to -0.1 MPa.
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