WO2020147020A1 - 三层结构树脂基复合材料及其应用 - Google Patents

三层结构树脂基复合材料及其应用 Download PDF

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Publication number
WO2020147020A1
WO2020147020A1 PCT/CN2019/071833 CN2019071833W WO2020147020A1 WO 2020147020 A1 WO2020147020 A1 WO 2020147020A1 CN 2019071833 W CN2019071833 W CN 2019071833W WO 2020147020 A1 WO2020147020 A1 WO 2020147020A1
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Prior art keywords
composite material
resin
prepolymer
barium titanate
layer structure
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PCT/CN2019/071833
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English (en)
French (fr)
Inventor
顾嫒娟
赵丹
梁国正
袁莉
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Suzhou University
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Suzhou University
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Priority to US17/423,257 priority Critical patent/US11987014B2/en
Priority to PCT/CN2019/071833 priority patent/WO2020147020A1/zh
Publication of WO2020147020A1 publication Critical patent/WO2020147020A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B29C70/62—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler being oriented during moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/242—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
    • B29K2105/167—Nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines

Definitions

  • the invention relates to a resin-based composite material with high energy storage density, high dielectric constant (>1000, 100Hz) and low dielectric loss ( ⁇ 0.6, 100Hz) and its application, in particular to a three-layer structure resin-based composite material Composite materials and their applications belong to the technical field of dielectric functional composite materials.
  • Dielectric capacitors do not involve electrochemical reactions during charging and discharging, and are generally solid, do not undergo morphological changes, and have a high operating temperature, which is beneficial to ensure the stable operation and service reliability of pulsed power equipment and electronic power systems.
  • High-performance dielectric energy storage materials are the core materials of dielectric capacitors. Among them, high-permittivity polymer-based composite materials have the advantages of light weight, easy processing, and adjustable dielectric properties, and are recognized as high-performance dielectric capacitors. The most promising candidate material.
  • the energy storage density ( U e ) of a linear dielectric is proportional to the dielectric constant ( ⁇ r ) and the square of the breakdown strength ( E b ) of the dielectric.
  • polymer matrix composite materials generally cannot have both high dielectric constant and high breakdown strength.
  • the dielectric constant is still less than 100, and there are many structural defects and low breakdown strength.
  • the seepage phenomenon is used to obtain a high dielectric constant, but its dielectric properties are very sensitive to the content of the conductor, and the dielectric loss is high (>1, @100Hz), which is prone to breakdown and medium
  • the electric constant is also lower than 350.
  • the oriented carbon nanotube bundle composed of many single carbon nanotubes interacting in a certain direction has excellent mechanical properties, electrical conductivity and dispersibility. Compared with other one-dimensional materials, it can improve nanocomposite more effectively The dielectric properties of the material.
  • the dielectric constant (265, @100Hz) of the prepared polymer matrix composites still needs to be further improved; at the same time, the oriented carbon nanotube bundles/resin composites also have relatively high dielectric loss.
  • the purpose of the present invention is to provide a new type of resin-based composite material with high energy storage density, low dielectric loss and high dielectric constant, and the establishment of the preparation process is controllable and easy, and the production cycle is short. , A preparation method suitable for large-scale applications.
  • a three-layer structure resin-based composite material includes the following steps:
  • the invention also discloses a preparation method of the three-layer structure resin-based composite material, which comprises the following steps:
  • the amount of oriented carbon nanotube bundles is 0.1-2% of the mass of the curable resin system, preferably 0.3-1%; the first prepolymer and the second prepolymer are equal in amount, which can be Equal volume can also be equal mass.
  • the three-layer resin-based composite material prepared in this way has a well-balanced structure, which is conducive to the development of anisotropic properties; in step (2), the amount of polydopamine-coated barium titanate nanofibers is curable resin
  • the quality of the system is 10-40%, preferably 15-25%.
  • the addition amount of the inorganic material of the present invention is far lower than the prior art, but it is not obvious that the technical effect of achieving a breakdown strength of 4.92 is achieved.
  • the curable resin system includes resin or resin and curing agent; the curable resin system includes resin or resin and curing agent; the curable resin system and the curable resin system may be the same or different.
  • the present invention In order to distinguish between two terms, it means that the resin system can be cured under certain conditions (heating, light, microwave, etc.), reaching a degree of curing of nearly 100%.
  • the resin system can be a single resin, a combination of several resins, or a combination of resin and corresponding curing agent.
  • the resin includes bismaleimide resin, cyanate ester resin, epoxy resin, and polyimide.
  • One or more of the resins, and the curing agent is conventionally selected according to the type of resin. Under the preparation method of the present invention, the technical effects of high storage density, low dielectric loss and high dielectric constant can be obtained; the so-called resin, curing agent of the present invention Agent is a conventional term in the art.
  • the preparation method of the polydopamine-coated barium titanate nanofiber includes the following steps:
  • the barium salt is barium acetate
  • the titanate compound is tetrabutyl titanate
  • the solvent is acetic acid
  • the viscosity modifier is polyvinylpyrrolidone
  • the electrospinning parameter is 1.7kV/cm
  • the calcination is at 10° Calcined at 700°C for 3h at a heating rate of C/min and an air atmosphere
  • the lye is an aqueous sodium hydroxide solution
  • the reaction is a shaking reaction at room temperature for 24h.
  • the molar ratio of barium salt to titanate compound is 1
  • the mass ratio of dopamine hydrochloride, tris hydrochloride, water, and barium titanate nanofiber is 0.2:0.1:100:2.
  • the thickness of the barium titanate nanofiber pre-cured sheet is 50-1000 ⁇ m, preferably 150-300 ⁇ m; the barium titanate nanofiber prepolymer is formed into a film by the coating method.
  • the three-layer structure resin-based composite material prepared in this way can guarantee a high dielectric constant to the greatest extent, maintain a high dielectric constant even slightly increased, and significantly improve the breakdown strength.
  • the curing degree of the oriented carbon nanotube bundle pre-cured sheet is 30%-60%; the curing degree of the barium titanate nanofiber pre-cured sheet is 30%-60%.
  • the degree of curing is a conventional term in the field. Pre-curing the raw materials can increase the dispersibility of inorganic components (carbon nanotube bundles, barium titanate nanofibers) at low viscosity and avoid excessive fluidity during the final curing process. The problem of instability of the three-layer structure, while limiting the degree of pre-polymerization curing can also improve the curing effect between layers.
  • the first prepolymer in step (1), is pre-cured by microwave intermittent curing; in step (3), the first prepolymer is cured by microwave intermittent curing.
  • the microwave intermittent curing time is 10-30s each time, and the intermittent time is 5-15s.
  • the present invention does not use conventional thermal curing methods in the field of resin curing, but uses microwave intermittent curing, that is, microwave curing for a period of time, pause for a period of time, and then microwave curing-pause, continuous cycle, the total curing time is determined according to the resin system, so that The obtained three-layer structure resin-based composite material has a curing degree exceeding 97%.
  • the invention also discloses the application of the above-mentioned three-layer structure resin-based composite material in the preparation of the dielectric functional composite material.
  • the preparation method of the three-layer structure resin-based composite material disclosed in the present invention specifically includes the following steps: by mass,
  • prepolymer A 100 parts of the microwave curable resin system with 0.1 ⁇ 2 parts of oriented carbon nanotube bundles, and prepolymerize to obtain prepolymer A;
  • the aligned carbon nanotube bundle may be unsurface-treated or surface-treated.
  • the preparation method of polydopamine-coated barium titanate nanofibers of the present invention includes the following steps:
  • 1Mix a mole of 1 part of barium acetate and 1 part of tetrabutyl titanate in 10 parts of acetic acid and mix uniformly, add an appropriate amount of polyvinylpyrrolidone to adjust the viscosity to form a stable precursor solution F; take the precursor solution F, Electrospinning under 1.7kV/cm, the end of electrostatic spinning, drying at 40°C for 4h to obtain as-spun composite nanofiber G; put as-spun composite nanofiber G in a muffle furnace under air atmosphere , The temperature is raised to 700°C at a heating rate of 10°C/min, and the temperature is kept and calcined for 3 hours. After natural cooling, barium titanate nanofibers are obtained, which is recorded as BTnf.
  • the pre-polymerization process, pre-curing process, and curing process of the present invention depend on the resin system used, and the degree of pre-polymerization is not particularly limited, and the curing degree of pre-curing is controlled to be 30%-60%, and the curing degree of curing is >97%.
  • the present invention has the following beneficial effects:
  • the present invention uses oriented carbon nanotube bundles and barium titanate nanofibers as functional bodies to design a novel three-layer structure resin-based composite material, which has both high energy storage density and high dielectric constant (>1000, @ 100Hz) and low dielectric loss ( ⁇ 0.6, @100Hz).
  • oriented carbon nanotube bundles are used as conductors and cured by microwave curing, so that the formed dielectric layer has a unique high dielectric constant.
  • the unique tube bundle structure enables more microcapacitance structures to be formed inside the composite material to achieve a higher dielectric constant.
  • the curing time required for microwave curing is short, and the functional body can be well dispersed in the resin.
  • the magnetic susceptibility and polarizability in the direction parallel to the axis of the aligned carbon nanotube bundle are different from the magnetic susceptibility and polarizability in the direction perpendicular to the axis of the aligned carbon nanotube bundle, and thus along the electromagnetic field direction Orientation, that is, the functional body is oriented in a certain direction in the resin matrix, so the obtained carbon nanotube bundle resin-based material layer produces higher electric polarization and has a high dielectric constant.
  • Barium titanate has excellent dielectric energy storage properties, among which the barium titanate nanofibers arranged in parallel can achieve high breakdown strength at low addition levels.
  • the invention uses the resin composite material in which the barium titanate nanofibers are arranged in parallel as the high breakdown strength layer to ensure that the three-layer composite material has high breakdown strength.
  • the barium titanate layer has a low dielectric constant, while the carbon nanotube bundle layer has a high dielectric constant.
  • the difference in dielectric constant between the two layers increases, and the low dielectric constant layer will bear more
  • the high local electric field relieves the electric field intensity of the high dielectric constant layer and prevents the material from being completely broken down; and due to the local electric field redistribution, the three-layer structure composite material has a higher dielectric constant.
  • the barium titanate layer exists between the two carbon nanotube bundle layers, which can significantly limit the transfer of internal charges in the material, thereby effectively reducing the dielectric loss.
  • the three-layer structure resin-based composite material provided by the present invention has a controllable preparation process, is easy to scale production, and has a short cycle, and is suitable for large-scale applications; because the three-layer structure composite material has both high dielectric constant and high breakdown strength , Thereby giving the three-layer structure composite material excellent energy storage density.
  • Fig. 1 is a scanning electron microscope (SEM) photograph of a three-layer resin-based composite material provided in Example 1 of the present invention in X, Y, and Z directions.
  • Example 2 is a scanning electron micrograph of the barium titanate nanofiber/epoxy resin composite material and the layer-to-layer interface of the three-layer composite material in the three-layer structure resin-based composite material provided in Example 1 of the present invention.
  • Example 3 is a scanning electron micrograph of the interface between the three-layer structure resin-based composite material layer and the layer provided in Example 1 of the present invention.
  • Figure 4 is a three-layer structure resin-based composite material provided by Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy composite material provided by Comparative Example 1, and a barium titanate nanofiber/epoxy resin composite material provided by Comparative Example 2
  • Figure 5 is a three-layer resin matrix composite material provided in Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy resin composite material provided in Comparative Example 1, and a barium titanate nanofiber/epoxy resin composite material provided in Comparative Example 2
  • Fig. 6 is a three-layer resin-based composite material provided in Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy composite material provided in Comparative Example 1, and a barium titanate nanofiber/epoxy resin composite material provided in Comparative Example 2
  • Fig. 7 is a three-layer structure resin-based composite material provided in Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy resin composite material provided in Comparative Example 1, and an oriented carbon nanotube bundle/barium titanate nanofiber/ The breakdown strength of the epoxy resin composite material and the double-layer structure composite material ([ACB/EP] 2 ) provided by Comparative Example 4.
  • Figure 8 is a three-layer structure resin-based composite material provided in Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy resin composite material provided in Comparative Example 1, and an oriented carbon nanotube bundle/barium titanate nanofiber/ The energy storage density of the epoxy resin composite material and the double-layer structure composite material ([ACB/EP] 2 ) provided in Comparative Example 4.
  • the first prepolymer and the second prepolymer take the first prepolymer and pour it into the preheated mold, and then put the mold in a microwave oven, and irradiate it for 5 cycles (the irradiation process for each cycle is It is medium heat, heating for 30s, and cooling for 10s), and after natural cooling, the oriented carbon nanotube/epoxy cured resin composite pre-cured sheet B with a curing degree of 60% is obtained.
  • barium titanate nanofibers are obtained, which are denoted as BTnf.
  • Figure 1 is a scanning electron microscope photograph of oriented carbon nanotube bundles distributed in an epoxy resin matrix in a BEB three-layer resin-based composite material provided in Example 1 of the present invention, where X, Y, and Z in the figure represent respectively Scanning electron microscope images in X, Y, and Z directions. It can be seen that the distribution of oriented carbon nanotube bundles in the epoxy resin is not random, but is evenly dispersed and arranged regularly, and is more inclined to be arranged along the Z direction.
  • FIG 2 is a scanning electron micrograph of the distribution of barium titanate nanofibers in epoxy resin in the B-E-B three-layer resin-based composite material provided in Example 1 of the present invention. Barium titanate nanofibers are evenly dispersed, but their arrangement tends to be aligned in the horizontal direction.
  • FIG 3 is a scanning electron micrograph of the interface between the layers of the B-E-B three-layer resin-based composite material provided in Example 1 of the present invention. It can be seen that the interlayer bonding is good, and there are no defects such as voids.
  • the curing degree is 60 % Oriented carbon nanotube/epoxy cured resin composite material precured sheet B.
  • FIG 4 is the three-layer resin-based composite material BEB composite material provided by Example 1 of the present invention, the oriented carbon nanotube bundle/epoxy resin composite material (ACB/EP) provided by Comparative Example 1, and Comparative Example 2 Barium titanate nanofiber/epoxy resin (BTnf/EP) composite material, the oriented carbon nanotube bundle/barium titanate nanofiber/epoxy resin (ACB/BTnf/EP) composite material provided by Comparative Example 3 and Comparative Example 4 The conductivity-frequency curve of the provided double-layer structure composite material ([ACB/EP] 2 ).
  • the ACB/EP composite material provided by Comparative Example 1 reaches 10 -7 , 10 -11 , 10 -9 , 10 -9 , and 10 -10 orders of magnitude (@1Hz), respectively.
  • the electrical conductivity of the BEB composite material provided in Example 1 is the lowest. This is because the presence of the polydopamine-coated barium titanate nanofiber/epoxy resin composite material layer has an obstructive effect on the conductive path inside the composite material and reduces the composite material. Leakage of materials.
  • FIG. 5 is the three-layer resin-based composite BEB composite material provided in Example 1 of the present invention, the oriented carbon nanotube bundle/epoxy resin composite material (ACB/EP) provided in Comparative Example 1, and Comparative Example 2 Barium titanate nanofiber/epoxy resin (BTnf/EP) composite material, the oriented carbon nanotube bundle/barium titanate nanofiber/epoxy resin (ACB/BTnf/EP) composite material provided by Comparative Example 3 and Comparative Example 4
  • the dielectric constant-frequency curve of the provided double-layer structure composite material [ACB/EP] 2 ). It can be seen that the BEB composite material provided in Example 1 has the highest dielectric constant.
  • the ACB/EP composite material provided by Comparative Example 1 At 100 Hz, the ACB/EP composite material provided by Comparative Example 1, the BTnf/EP composite material provided by Comparative Example 2, the ACB/BTnf/EP composite material provided by Comparative Example 3, and the double-layer structure composite material provided by Comparative Example 4 ( [ACB/EP] 2 )
  • the dielectric constants of the BEB composite material provided in Example 1 are 797.6, 21.1, 350.4, 828, 1080.9, respectively.
  • the dielectric constant value of the BEB composite material provided in Example 1 is the optimal value, which is higher than the value reported so far for the conductor/polymer multilayer composite material containing an insulating layer; the BTnf/EP composite material provided in Comparative Example 2
  • the dielectric constant of the material is the worst value, 21.1 (@100Hz). If barium titanate nanofibers are used directly instead of polydopamine-coated barium titanate nanofibers, the dielectric constant is 16.9 (@100Hz).
  • Barium titanate nanofibers are ceramic functional bodies, and the dielectric constant of the BTnf/EP composite material provided by Comparative Example 2 is the lowest when the addition amount is 20wt%. Compared with the ACB/EP composite material provided by Comparative Example 1, the presence of barium titanate nanofibers in the ACB/BTnf/EP composite material provided by Comparative Example 3 blocks the formation of the conductive network of oriented carbon nanotube bundles, so its medium The dielectric constant is much lower than that of Comparative Example 1.
  • the double-layer structure composite material ([ACB/EP] 2 ) provided by Comparative Example 4 has one more interface layer, which has a stronger interface polarization effect, so the dielectric constant Slightly higher.
  • the BEB composite material provided in Example 1 has a higher dielectric constant, which is due to the existence of two interface layers and space charge polarization.
  • the conductivity of the oriented carbon nanotube bundle/epoxy resin composite layer (layer A) and barium titanate nanofiber/epoxy resin composite layer (layer B) are 10 -7 and 10 -11 (@1Hz), respectively , Their layers will form more charge accumulation than the [ACB/EP] 2 layers, resulting in more significant interface polarization.
  • the dielectric constant of the BEB composite material provided in Example 1 is greatly improved.
  • the difference in the dielectric constant between the oriented carbon nanotube bundle/epoxy composite layer and the barium titanate nanofiber/epoxy composite layer causes the local electric field intensity to redistribute when the composite material is in an electric field, and the dielectric constant
  • the low barium titanate nanofiber/epoxy composite material layer (21.1, @100Hz) is polarized under a higher electric field, and the degree of electrical polarization is higher, so the dielectric constant of the BEB composite material will increase.
  • FIG 6 is a three-layer resin-based composite material BEB composite material provided by Example 1 of the present invention, an oriented carbon nanotube bundle/epoxy resin composite material (ACB/EP) provided by Comparative Example 1, and Comparative Example 2
  • Bnf/EP Barium titanate nanofiber/epoxy resin
  • ACB/BTnf/EP oriented carbon nanotube bundle/barium titanate nanofiber/epoxy resin
  • Comparative Example 3 Provides the dielectric loss-frequency curve of the double-layer structure composite material ([ACB/EP] 2 ). It can be seen that the dielectric loss of the BEB resin-based composite material provided in Example 1 is lower than that of the ACB/EP composite material provided in Comparative Example 1.
  • the BEB composite material provided in Example 1 contains barium titanate nanofibers/epoxy
  • the resin composite material layer has the lowest dielectric loss (0.59, @100Hz), which can significantly limit the transfer of internal charges in the material and play a good role in reducing dielectric loss.
  • FIG 7 is the three-layer resin-based composite material BEB composite material provided in Example 1 of the present invention, the oriented carbon nanotube bundle/epoxy resin composite material (ACB/EP) provided in Comparative Example 1, and Comparative Example 2 Barium titanate nanofiber/epoxy resin (BTnf/EP) composite material, the oriented carbon nanotube bundle/barium titanate nanofiber/epoxy resin (ACB/BTnf/EP) composite material provided by Comparative Example 3 and Comparative Example 4
  • the breakdown path in BEB is long. , Due to the existence of the intermediate interface layer, the breakdown path is extended.
  • the barium titanate nanofiber/epoxy resin composite material layer with a small dielectric constant can withstand a higher electric field than the oriented carbon nanotube bundle/epoxy resin composite material layer
  • the electric field strength of the oriented carbon nanotube bundle/epoxy resin composite material layer with high dielectric constant is relatively large, which reduces the probability of breakdown and improves the breakdown strength of the BEB composite material. It is beneficial to increase the energy storage density of the multilayer structure composite material. Therefore, the three-layer structure resin-based composite material shows the advantage of adjusting the local electric field intensity distribution.
  • the BEB composite material provided in Example 1 has the highest energy storage density, which are the ACB/EP composite material provided in Comparative Example 1, the ACB/BTnf/EP composite material provided in Comparative Example 3, and the double-layered material provided in Comparative Example 4.
  • the energy storage density of structural composite materials ([ACB/EP] 2 ) is 12.8, 18.8 and 7.7 times. This is because the energy storage density of linear materials is proportional to the square of the dielectric constant and breakdown strength of the composite material. Therefore, the BEB three-layer structure composite material can obtain a high energy storage density with the highest dielectric constant and breakdown strength.
  • the mold Take a part of it and pour it into the preheated mold, then put the mold in the microwave oven and irradiate it for 5 cycles (the irradiation process is medium heat, heating for 30s, and cooling for 10s), and then it is solidified after natural cooling 60% oriented carbon nanotube/epoxy cured resin composite material pre-cured sheet B.
  • the mold Take a part of it and pour it into the preheated mold, then put the mold in the microwave oven and irradiate it for 5 cycles (the irradiation process is medium heat, heating for 30s, and cooling for 10s), and then it is solidified after natural cooling 60% oriented carbon nanotube/epoxy cured resin composite material pre-cured sheet B.
  • the mold Take a part of it and pour it into the preheated mold, then put the mold in the microwave oven and irradiate it for 5 cycles (the irradiation process is medium heat, heating for 30s, and cooling for 10s), and then it is solidified after natural cooling 60% oriented carbon nanotube/epoxy cured resin composite material pre-cured sheet B.
  • the mold Take a part of it and pour it into the preheated mold, then put the mold in the microwave oven and irradiate it for 5 cycles (the irradiation process is medium heat, heating for 30s, and cooling for 10s), and then it is solidified after natural cooling 60% oriented carbon nanotube/epoxy cured resin composite material pre-cured sheet B.
  • the mold Take a part of it and pour it into the preheated mold, then put the mold in the microwave oven and irradiate it for 5 cycles (the irradiation process is medium heat, heating for 30s, and cooling for 10s), and then it is solidified after natural cooling 60% oriented carbon nanotube/epoxy cured resin composite material pre-cured sheet B.
  • step (1) and step (3) are used for non-intermittent microwave irradiation and other conditions remain unchanged, the dielectric constant of the three-layer resin-based composite BEB obtained is 882.6 (@100Hz) and the breakdown strength is 3.62; if Steps (1) and (3) are heated (cured at 160°C for 60 minutes) instead of intermittent microwave, and other conditions remain unchanged.
  • the dielectric constant of the obtained three-layer resin-based composite material BEB is 738.8 (@100Hz) ), the breakdown strength is 3.38.

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Abstract

本发明公开了一种三层结构树脂基复合材料及应用。本发明通过微波固化法制备取向碳纳米管束/环氧树脂复合材料（记为B层），通过刮涂-热固化法制备钛酸钡纳米纤维/环氧树脂复合材料（记为E层），经过层层固化技术构建B-E-B三层结构复合材料。与现有技术制备的导体-绝缘层/聚合物层状结构复合材料相比，本发明提供的三层结构复合材料兼具高介电常数（>1000，@100Hz）、低介电损耗和高储能密度，并且制备工艺可控易行，生产周期短，适合大规模应用。

Description

三层结构树脂基复合材料及其应用 技术领域
本发明涉及一种兼具高储能密度、高介电常数（>1000，100Hz）和低介电损耗（<0.6，100Hz）树脂基复合材料及其应用，特别涉及一种三层结构树脂基复合材料及其应用，属于介电功能复合材料技术领域。
 背景技术
随着脉冲功率设备、电子功率系统以及紧凑型、低成本电器需求的激增，迫切需要能够存贮和瞬间输出能量的电能存储元件。电介质电容器充放电时均不涉及电化学反应，且一般为固态，不发生形态变化，并具有高的使用温度，有利于保证脉冲功率设备、电子功率系统的稳定运行及服役可靠性。高性能的介电储能材料是电介质电容器的核心材料，其中高介电常数聚合物基复合材料具有轻质、易加工、介电性能可调等优势，被公认为用于高性能介电电容器的最具希望的候选材料。
线性电介质的储能密度（ U e）正比于电介质的介电常数（ ε r）和击穿强度（ E b）的平方。迄今为止，聚合物基复合材料普遍不能兼具高介电常数和高击穿强度。例如，陶瓷/聚合物复合材料中，陶瓷含量即使高达50vol%以上，介电常数仍小于100，且结构缺陷多，击穿强度低。导体/聚合物复合材料中，利用渗流现象获得很高的介电常数，但其介电性能对导体含量非常敏感，且介电损耗高（＞1，@100Hz），易发生击穿，而且介电常数也低于350。
为了解决上述问题，近年来，人们制备了多种类型的多层结构复合材料，但现有文献报道的多层结构复合材料的介电常数普遍较低（<350，@100Hz），且工艺复杂，周期较长。
因此，如何采用简单的工艺制备低介电损耗、高 E b和高 U e的高介电常数聚合物基复合材料依然是一项十分有挑战性的工作。在功能填充体中，由许多单根碳纳米管在一定方向相互作用组成的取向碳纳米管束具有出色的力学性能、导电性和分散性，相比其他一维材料，能更有效地改善纳米复合材料的介电性能。但是，取向碳纳米管束含量较高时，所制得的聚合物基复合材料的介电常数（265，@100Hz）仍有待进一步提高；同时取向碳纳米管束/树脂复合材料同样存在介电损耗较大、击穿强度低、储能密度低的问题。
技术问题
为了克服现有技术存在的不足，本发明的目的在于提供兼具高储能密度、低介电损耗和高介电常数的新型树脂基复合材料，且建立制备工艺可控易行，生产周期短，适合大规模应用的制备方法。
 技术解决方案
实现本发明目的的技术方案是：
一种三层结构树脂基复合材料，所述三层结构树脂基复合材料的制备方法包括以下步骤：
（1）将可固化树脂体系与取向碳纳米管束混合，得到取向碳纳米管束预聚物；然后将预聚物分为第一预聚物、第二预聚物；然后将第一预聚物预固化，得到取向碳纳米管束预固化片；
（2）将能固化树脂体系与聚多巴胺包覆的钛酸钡纳米纤维混合，得到钛酸钡纳米纤维预聚物；然后将钛酸钡纳米纤维预聚物制膜后预固化得到钛酸钡纳米纤维预固化片；
（3）将钛酸钡纳米纤维预固化片浸润第二预聚物后平铺于取向碳纳米管束预固化片上；然后将第二预聚物浇注于钛酸钡纳米纤维预固化片上；再经过固化，得到三层结构树脂基复合材料。
本发明还公开了一种三层结构树脂基复合材料的制备方法，包括以下步骤：
（1）将可固化树脂体系与取向碳纳米管束混合，得到取向碳纳米管束预聚物；然后将预聚物分为第一预聚物、第二预聚物；然后将第一预聚物预固化，得到取向碳纳米管束预固化片；
（2）将能固化树脂体系与聚多巴胺包覆的钛酸钡纳米纤维混合，得到钛酸钡纳米纤维预聚物；然后将钛酸钡纳米纤维预聚物制膜后预固化得到钛酸钡纳米纤维预固化片；
（3）将钛酸钡纳米纤维预固化片浸润第二预聚物后平铺于取向碳纳米管束预固化片上；然后将第二预聚物浇注于钛酸钡纳米纤维预固化片上；再经过固化，得到三层结构树脂基复合材料。
本发明中，步骤（1）中，取向碳纳米管束的用量为可固化树脂体系质量的0.1～2%，优选0.3～1%；第一预聚物、第二预聚物等量，可以为等体积也可以为等质量，这样制备的三层结构树脂基复合材料结构匀称，利于各向性能的发挥；步骤（2）中，聚多巴胺包覆的钛酸钡纳米纤维的用量为能固化树脂体系质量的10～40%，优选15～25%，本发明无机材料添加量远低于现有技术，但是取得击穿强度为4.92的技术效果，非显而易见。
本发明中，所述可固化树脂体系包括树脂或者树脂与固化剂；所述能固化树脂体系包括树脂或者树脂与固化剂；可固化树脂体系、能固化树脂体系可以一样也可以不一样，本发明为了区分而采用两个称呼，即表示树脂体系在一定条件下（加热、光照、微波等）可以固化，达到近100%的固化度。树脂体系可以为单独的树脂、几种树脂的组合物，也可以为树脂与对应固化剂的组合，其中树脂包括双马来酰亚胺树脂、氰酸酯树脂、环氧树脂、聚酰亚胺树脂中的一种或几种，固化剂根据树脂种类常规选择，在本发明制备方法下，可以取得高储能密度、低介电损耗和高介电常数的技术效果；本发明所谓树脂、固化剂为本领域常规术语。
本发明中，所述聚多巴胺包覆的钛酸钡纳米纤维的制备方法包括以下步骤：
①将钡盐、钛酸酯化合物在溶剂中混合，然后加入粘度调节剂，得到前驱体溶液；所述前驱体溶液经过静电纺丝、煅烧后，得到钛酸钡纳米纤维；
②将盐酸多巴胺、三羟甲基氨基甲烷盐酸盐溶解在水中，然后用碱液调节pH值为8～9；然后加入钛酸钡纳米纤维进行反应，得到聚多巴胺包覆的钛酸钡纳米纤维。
上述技术方案中，钡盐为乙酸钡，钛酸酯化合物为钛酸四丁酯，溶剂为乙酸，粘度调节剂为聚乙烯吡咯烷酮；静电纺丝的参数为1.7kV/cm；煅烧为在10°C/min的升温速率和空气气氛下，于700°C下煅烧3h；碱液为氢氧化钠水溶液；反应为室温下振荡反应24h。钡盐、钛酸酯化合物的摩尔比为1；盐酸多巴胺、三羟甲基氨基甲烷盐酸盐、水、钛酸钡纳米纤维的质量比为0.2∶0.1∶100∶2。
本发明中，钛酸钡纳米纤维预固化片的厚度为50～1000μm，优选150～300μm；采用涂膜法将钛酸钡纳米纤维预聚物制膜。这样制备的三层结构树脂基复合材料能够最大程度保证高介电常数，使之保持甚至略有增大的高介电常数，同时显著提升击穿强度。
本发明中，所述取向碳纳米管束预固化片的固化度为30%～60%；钛酸钡纳米纤维预固化片的固化度为30%～60%。固化度为本领域常规术语，对原料进行预固化既可以在低粘度下增加无机成分（碳纳米管束、钛酸钡纳米纤维）的分散性，又能够避免最后固化过程中出现流动性过大导致的三层结构不稳定的问题，同时限定预聚固化度还可以提高层间固化效果。
本发明中，步骤（1）中，采用微波间歇固化的方式将第一预聚物预固化；步骤（3）中，采用微波间歇固化的方式固化。优选的，微波间歇固化每次固化的时间为10～30s，间歇的时间为5～15s。本发明没有采用树脂固化领域常规的热固化方式，而是采用微波间歇固化，即微波固化一段时间后暂停一段时间，然后再微波固化-暂停，不断循环，总的固化时间根据树脂体系决定，使得得到的三层结构树脂基复合材料固化度超过97%即可。
本发明还公开了上述三层结构树脂基复合材料在制备介电功能复合材料中的应用。
本发明公开的三层结构树脂基复合材料的制备方法，具体举例包括以下步骤：按质量计，
（1）将100份可微波固化树脂体系与0.1~2份取向碳纳米管束混合混匀，预聚，得到预聚物A；
（2）取步骤（1）制备的预聚物A平分为两部分，将其中一半进行预固化，得到取向碳纳米管束/树脂预固化片B；
（3）将100份可热固化树脂体系与10~40份聚多巴胺包覆的钛酸钡纳米纤维混合均匀，预聚，得到预聚物C；使用涂膜器，将预聚物C刮涂成50~1000μm厚度的预聚物膜D；
（4）将步骤（3）制备的预聚物膜D进行预固化，得到钛酸钡纳米纤维/热固性树脂预固化片E；
（5）将步骤（4）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（2）制备的取向碳纳米管束/树脂预固化片B上，得到双层结构复合材料B-E；
（6）将步骤（1）制备的预聚物A的另一半浇注到步骤（5）制备的双层结构复合材料B-E的钛酸钡纳米纤维/热固性树脂预固化片E一面，然后进行固化，得到三层结构树脂基复合材料B-E-B。
本发明中，所述的取向碳纳米管束可以是未经表面处理或经表面处理。
本发明的聚多巴胺包覆的钛酸钡纳米纤维的制备方法包括以下步骤：
①按摩尔量计，将1份乙酸钡和1份钛酸四丁酯溶于10份乙酸中混合均匀，添加适量聚乙烯吡咯烷酮调节粘度，形成稳定的前驱体溶液F；取前驱体溶液F，在1.7kV/cm下静电纺丝，静电纺丝结束，在40°C下干燥4h，得到初纺复合材料纳米纤维G；将初纺复合材料纳米纤维G放在马弗炉中，空气气氛下，以10°C/min的升温速率升温至700°C并保温煅烧3h，自然冷却后得到钛酸钡纳米纤维，记为BTnf。
②按质量计，将0.2份盐酸多巴胺和0.1份三羟甲基氨基甲烷盐酸盐溶解在100份水中，得到溶液H；将0.5份氢氧化钠溶解在100份水中，得到氢氧化钠水溶液；用氢氧化钠水溶液调节溶液H的pH值至8.5，得到溶液I；将2份钛酸钡纳米纤维浸没在溶液I中，在室温下振荡24h；反应结束后将其取出、清洗并干燥，得到聚多巴胺包覆的钛酸钡纳米纤维，记为PDA@BTnf。
本发明的预聚工艺、预固化工艺、固化工艺取决于所采用的树脂体系，预聚程度没有特别限制，控制预固化的固化度在30%-60%、固化的固化度>97%。
 有益效果
与现有技术相比，本发明取得的有益效果是：
1、本发明以取向碳纳米管束、钛酸钡纳米纤维为功能体，设计了一种新颖的三层结构树脂基复合材料，其兼具高储能密度、高介电常数（>1000，@100Hz）和低介电损耗（<0.6，@100Hz）。
2、本发明以取向碳纳米管束作为导体，并采用微波固化方式固化，构成的介电层具有独特的高介电常数。首先，独特的管束结构使复合材料内部构成更多微电容结构，达到更高的介电常数。其次，微波固化所需的固化时间短，功能体得以在树脂中分散良好。第三，在微波辐照过程中，与取向碳纳米管束的轴平行方向上的磁化率和极化率不同于取向碳纳米管束的轴垂直方向上的磁化率和极化率，从而沿电磁场方向取向，即功能体在树脂基体中沿一定方向取向，因此所得到的碳纳米管束树脂基材料层产生更高的电极化，具备高介电常数。
3、钛酸钡具有优异的介电储能性能，其中平行排列的钛酸钡纳米纤维能够在低添加量下达到高击穿强度。本发明以钛酸钡纳米纤维平行排列的树脂复合材料作为高击穿强度层，确保了三层复合材料具有高的击穿强度。此外，钛酸钡层的介电常数低，而碳纳米管束层的介电常数高，当施加外部电场时，两层层间的介电常数之差增大，低介电常数层将承受更高的局部电场，从而缓解了高介电常数层的电场强度，使材料免受完全击穿；且由于局部电场重分布，三层结构复合材料具备更高的介电常数。
4、钛酸钡层存在于两个碳纳米管束层之间，能够显著限制材料内部电荷的迁移，从而起到很好的降低介电损耗的作用。
5、本发明提供的三层结构树脂基复合材料的制备工艺可控，易于规模化生产，且周期短，适合大规模应用；由于三层结构复合材料兼具高介电常数和高击穿强度，从而赋予三层结构复合材料出色的储能密度。
 附图说明
图1是本发明实施例1提供的三层结构树脂基复合材料分别在X、Y、Z方向的扫描电镜（SEM）照片。
图2是本发明实施例1提供的三层结构树脂基复合材料中钛酸钡纳米纤维/环氧树脂复合材料以及三层复合材料层与层界面处的扫描电镜照片。
图3是本发明实施例1提供的三层结构树脂基复合材料层与层之间界面处的扫描电镜照片。
图4是本发明实施例1提供的三层结构树脂基复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料、比较例2提供的钛酸钡纳米纤维/环氧树脂复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的电导率-频率曲线。
图5是本发明实施例1提供的三层结构树脂基复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料、比较例2提供的钛酸钡纳米纤维/环氧树脂复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的介电常数-频率曲线。
图6是本发明实施例1提供的三层结构树脂基复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料、比较例2提供的钛酸钡纳米纤维/环氧树脂复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的介电损耗-频率曲线。
图7是本发明实施例1提供的三层结构树脂基复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的击穿强度。
图8是本发明实施例1提供的三层结构树脂基复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的储能密度。
本发明的实施方式
下面结合附图、实施例和比较例，对本发明技术方案作进一步的描述。
实施例1
       （1）将0.12g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，为第一预聚物、第二预聚物，取第一预聚物倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）在50°C的磁力搅拌中，将4.38g乙酸钡和5.84g钛酸四丁酯加入乙酸（20mL）中混合均匀，添加5g聚乙烯吡咯烷酮调节粘度，形成稳定的前驱体溶液F。将前驱体溶液F在1.7kV/cm下静电纺丝，纺丝环境为恒温恒湿，其中温度为30°C，相对湿度50%。静电纺丝进样速率为0.8mL/h。静电纺丝得到的初纺复合材料纳米纤维G在40°C下干燥。而后，在空气气氛下，放入马弗炉中，以10°C/min的升温速率升温至700°C后保温煅烧3h，自然冷却后得到钛酸钡纳米纤维，记为BTnf。
（3）将0.4g盐酸多巴胺和0.2g三羟甲基氨基甲烷盐酸盐溶解在200mL水中，得到溶液H；将1g氢氧化钠溶解在200mL水中，得到氢氧化钠水溶液；用氢氧化钠水溶液调节溶液H的pH值至8.5，得到溶液I；将4gBTnf加入到溶液I中，在室温下搅拌反应24h；反应结束后将其取出、清洗并干燥，得到聚多巴胺包覆的钛酸钡纳米纤维，记作PDA@BTnf。
（4）将4gPDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为200μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（5）将步骤（4）制备的预固化片E浸润步骤（1）制备的预聚物A（第二预聚物）后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。B-E-B中取向碳纳米管束分布扫描电镜照片、钛酸钡纳米纤维分布扫描电镜照片、层与层之间界面处的扫描电镜照片、电导率-频率曲线、介电常数-频率曲线、介电损耗-频率曲线、击穿强度、储能密度分别如附图1、2、3、4、5、6、7、8所示。
参见附图1，它是本发明实施例1提供的B-E-B三层结构树脂基复合材料中取向碳纳米管束在环氧树脂基体中分布的扫描电镜照片，其中图中的X、Y、Z表示分别在X、Y、Z方向的扫描电镜图。从中可见，取向碳纳米管束在环氧树脂中的分布并不是随机的，而是均匀分散、有规排布的，并且更倾向于沿着Z方向排布。
参见附图2，它是本发明实施例1提供的B-E-B三层结构树脂基复合材料中钛酸钡纳米纤维在环氧树脂中分布的扫描电镜照片。钛酸钡纳米纤维分散均匀，但其排列更倾向沿水平方向排列。
参见附图3，它是本发明实施例1提供的B-E-B三层结构树脂基复合材料层与层之间界面处的扫描电镜照片。从中可以看到，层间结合较好，没有空隙等缺陷存在。
比较例1  取向碳纳米管束/环氧树脂复合材料的制备
将0.12g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A倒入预热好的模具，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），冷却后得到固化度>97%的取向碳纳米管/环氧树脂复合材料，记作ACB/EP；其电导率-频率曲线、介电常数-频率曲线、介电损耗-频率曲线、击穿强度、储能密度分别如附图4、5、6、7、8所示。
比较例2  钛酸钡纳米纤维/环氧树脂复合材料的制备
将4g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌搅拌10min，加入0.8g2-乙基-4-甲基咪唑继续超声震荡搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A倒入预热好的模具，放入烘箱中，而后按照80°C/2h+100°C/2h+120°C工艺固化，并在150°C下后处理4h，自然冷却后，即得到固化度>97%的钛酸钡纳米纤维/环氧树脂复合材料，记作BTnf/EP；其电导率-频率曲线、介电常数-频率曲线、介电损耗-频率曲线分别如附图4、5、6所示。
比较例3  取向碳纳米管束/钛酸钡纳米纤维/环氧树脂复合材料的制备
将0.12g未经表面处理的取向碳纳米管（长度20-100μm，直径2-5μm），4g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌搅拌10min；而后加入0.8g的2-乙基-4-甲基咪唑继续超声震荡搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A倒入预热好的模具，放入烘箱中，而后按照80°C/2h+100°C/2h+120°C工艺固化，并在150°C下后处理4h，自然冷却后，即得到固化度>97%的取向碳纳米管/钛酸钡纳米纤维/环氧树脂复合材料，记作ACB/BTnf/EP；其电导率-频率曲线、介电常数-频率曲线、介电损耗-频率曲线、击穿强度、储能密度分别如附图4、5、6、7、8所示。
比较例4  双层结构复合材料（[ACB/EP] 2）的制备
将0.12g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。将步骤（1）制备的预聚物A的另一半浇注到预固化片B上，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的双层结构复合材料，记为[ACB/EP] 2；其电导率-频率曲线、介电常数-频率曲线、介电损耗-频率曲线、击穿强度、储能密度分别如附图4、5、6、7、8所示。
参见附图4，它是本发明实施例1提供的三层结构树脂基复合材料B-E-B复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料（ACB/EP）、比较例2提供的钛酸钡纳米纤维/环氧树脂（BTnf/EP）复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂（ACB/BTnf/EP）复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的电导率-频率曲线。从中得知，比较例1提供的ACB/EP复合材料、比较例2提供的BTnf/EP复合材料、比较例3提供的ACB/BTnf/EP复合材料、比较例4提供的双层结构复合材料（[ACB/EP] 2）、实施例1提供的B-E-B复合材料的电导率分别达10 -7、10 -11、10 -9、10 -9、10 -10数量级（@1Hz）。实施例1提供的B-E-B复合材料的电导率最低，这是因为聚多巴胺包覆的钛酸钡纳米纤维/环氧树脂复合材料层的存在对复合材料内部的导电通路起到了阻碍效果，降低了复合材料的漏电现象。
参见附图5，它是本发明实施例1提供的三层结构树脂基复合材料B-E-B复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料（ACB/EP）、比较例2提供的钛酸钡纳米纤维/环氧树脂（BTnf/EP）复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂（ACB/BTnf/EP）复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的介电常数-频率曲线。从中可知，实施例1提供的B-E-B复合材料拥有最高的介电常数。在100Hz下，比较例1提供的ACB/EP复合材料、比较例2提供的BTnf/EP复合材料、比较例3提供的ACB/BTnf/EP复合材料、比较例4提供的双层结构复合材料（[ACB/EP] 2）、实施例1提供的B-E-B复合材料介电常数分别为797.6、21.1、350.4、828、1080.9。其中，实施例1提供的B-E-B复合材料的介电常数值是最优值，高于迄今已报到的含绝缘层的导体/聚合物多层复合材料的值；比较例2提供的BTnf/EP复合材料的介电常数值是最差值，为21.1（@100Hz），如果直接采用钛酸钡纳米纤维而不是聚多巴胺包覆的钛酸钡纳米纤维，介电常数为16.9（@100Hz）。
钛酸钡纳米纤维是陶瓷功能体，添加量20wt%时的比较例2提供的BTnf/EP复合材料介电常数最低。与比较例1提供的ACB/EP复合材料相比，比较例3提供的ACB/BTnf/EP复合材料中钛酸钡纳米纤维的存在阻断了取向碳纳米管束导电网络的形成，因此它的介电常数远低于比较例1的介电常数。
与比较例1提供的ACB/EP复合材料相比，比较例4提供的双层结构复合材料（[ACB/EP] 2）多一个界面层，有较强的界面极化效应，因此介电常数略高。实施例1提供的B-E-B复合材料有更高的介电常数，这是由于其存在两个界面层存在空间电荷极化。此外，取向碳纳米管束/环氧树脂复合材料层（A层）和钛酸钡纳米纤维/环氧树脂复合材料层（B层）的电导率分别为10 -7和10 -11（@1Hz），它们的层间会形成比[ACB/EP] 2层间更多的电荷积累，从而形成更加显著的界面极化。因此实施例1提供的B-E-B复合材料的介电常数大幅提升。另一方面，取向碳纳米管束/环氧树脂复合材料层和钛酸钡纳米纤维/环氧树脂复合材料层的介电常数差异导致复合材料处于电场中时产生局部电场强度重新分布，介电常数低的钛酸钡纳米纤维/环氧树脂复合材料层（21.1，@100Hz）在更高的电场下极化，电极化程度更高，因此B-E-B复合材料的介电常数会增大。
参见附图6，它是本发明实施例1提供的三层结构树脂基复合材料B-E-B复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料（ACB/EP）、比较例2提供的钛酸钡纳米纤维/环氧树脂（BTnf/EP）复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂（ACB/BTnf/EP）复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的介电损耗-频率曲线。从中可知，实施例1提供的B-E-B树脂基复合材料的介电损耗相比比较例1提供的ACB/EP复合材料有降低，实施例1提供的B-E-B复合材料中存在钛酸钡纳米纤维/环氧树脂复合材料层的介电损耗最低（0.59，@100Hz），存在能够显著限制材料内部电荷的迁移，起到很好的降低介电损耗的作用。
参见附图7，它是本发明实施例1提供的三层结构树脂基复合材料B-E-B复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料（ACB/EP）、比较例2提供的钛酸钡纳米纤维/环氧树脂（BTnf/EP）复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂（ACB/BTnf/EP）复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的击穿强度图。从中可知，实施例1提供的B-E-B复合材料的击穿强度达到了4.92，是比较例3提供的ACB/BTnf/EP复合材料的击穿强度的2.5倍，这是因为B-E-B中的击穿路径长，由于中间界面层的存在，延长了击穿路径。特别的，在外加电场时，局部电场强度重新分布后，介电常数小的钛酸钡纳米纤维/环氧树脂复合材料层（可以承受高于取向碳纳米管束/环氧树脂复合材料层的电场强度）的电场强度较大，介电常数高的取向碳纳米管束/环氧树脂复合材料层局部电场强度较小，降低了击穿发生概率，从而提高B-E-B复合材料的击穿强度，这也有利于提高多层结构复合材料的储能密度。因此三层结构树脂基复合材料显示出调整局部电场强度分布的优势。
参见附图8，它是本发明实施例1提供的三层结构树脂基复合材料B-E-B复合材料、比较例1提供的取向碳纳米管束/环氧树脂复合材料（ACB/EP）、比较例2提供的钛酸钡纳米纤维/环氧树脂（BTnf/EP）复合材料、比较例3提供的取向碳纳米管束/钛酸钡纳米纤维/环氧树脂（ACB/BTnf/EP）复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的储能密度。从中可知，实施例1提供的B-E-B复合材料的储能密度最高，分别是比较例1提供的ACB/EP复合材料、比较例3提供的ACB/BTnf/EP复合材料和比较例4提供的双层结构复合材料（[ACB/EP] 2）的储能密度的12.8、18.8和7.7倍。这是因为线性材料的储能密度正比于复合材料的介电常数和击穿强度的平方，因此，B-E-B三层结构复合材料可以凭借最高的介电常数和击穿强度得到了高储能密度。这些数据说明本发明通过结构与组成设计，可以制得兼具低介电损耗、高介电常数和高击穿强度的复合材料，从而获得了高储能密度高的材料。
实施例2
（1）将0.02g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将2g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为160μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例3
（1）将0.12g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将6g实施例1制备的聚多巴胺包覆的0酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为180μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例4
（1）将0.12g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将8g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为210μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例5
（1）将0.11g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将4g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为400μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例6
（1）将0.15g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将3.5g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为200μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例7
（1）将0.13g表面羟基化的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将4g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为300μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B，介电常数为1072.1（@100Hz），击穿强度达到了4.76。如果将步骤（3）中预聚物A的另一半浇注到B-E的预固化片B一侧，其他条件不变，得到的三层结构树脂基复合材料B-B-E的介电常数为798.6（@100Hz），击穿强度3.03。
实施例8
（1）将0.07g表面羟基化的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照4个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为40%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将2g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为150μm的预聚物膜D，在80°C下固化45min，自然冷却后，得到固化度为40%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例9
（1）将0.16g表面羟基化的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min后，加入0.8g的2-乙基-4-甲基咪唑，继续搅拌10min后，在60°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热10s、冷却10s），自然冷却后，得到固化度为30%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将6g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于60°C下超声震荡搅拌10min，加入0.8g的2-乙基-4-甲基咪唑，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为275μm的预聚物膜D，在80°C下固化1h，自然冷却后，得到固化度为30%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例10
（1）将0.19g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm）和20g双酚A型环氧树脂（牌号E-51）混合，于80°C下超声震荡搅拌10min后，加入5g二氨基二苯甲烷，继续搅拌10min后，在80°C下真空脱气泡20min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照4个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为50%的取向碳纳米管/环氧固化树脂复合材料预固化片B。
（2）将8g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf和20g双酚A型环氧树脂（牌号E-51）混合，于80°C下超声震荡搅拌10min，加入5g二氨基二苯甲烷，继续超声震荡搅拌10min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为270μm的预聚物膜D，在80°C下固化45min，自然冷却后，得到固化度为50%的钛酸钡纳米纤维/环氧树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。
实施例11
（1）将10g双马来酰亚胺基二苯甲烷与8.6g二烯丙基双酚A化合物在130°C搅拌加热至透明溶液，然后加入0.1g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm），140°C下预聚50min，倒入预热好的模具，在140°C下真空脱气泡30min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/双马来酰亚胺树脂复合材料预固化片B。
（2）将10g双马来酰亚胺基二苯甲烷与8.6g二烯丙基双酚A化合物在130°C搅拌加热至透明溶液，然后加入8g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf，140°C下预聚50min，倒入预热好的模具，在140°C下真空脱气泡30min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为250μm的预聚物膜D，在140°C下固化50min，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/双马来酰亚胺树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B，介电常数为1062.8（@100Hz），击穿强度达到了4.79。如果将步骤（1）与步骤（3）采用不间歇微波辐照，其他条件不变，得到的三层结构树脂基复合材料B-E-B的介电常数为882.6（@100Hz），击穿强度3.62；如果将步骤（1）与步骤（3）采用加热方式（160°C下固化60min）替换间歇微波方式，其他条件不变，得到的三层结构树脂基复合材料B-E-B的介电常数为738.8（@100Hz），击穿强度3.38。
实施例12
（1）将10g双马来酰亚胺基二苯甲烷与8g二烯丙基双酚A化合物在130°C搅拌加热至透明溶液，然后加入0.37g未经表面处理的取向碳纳米管束（长度20-100μm，直径2-5μm），140°C下预聚50min，倒入预热好的模具，在140°C下真空脱气泡30min，得到预聚物A；将预聚物A平分为两部分，取一部分倒入预热好的模具，而后，将模具放入微波炉中，循环辐照5个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后，得到固化度为60%的取向碳纳米管/双马来酰亚胺树脂复合材料预固化片B。
（2）将10g双马来酰亚胺基二苯甲烷与8g二烯丙基双酚A化合物在130°C搅拌加热至透明溶液，然后加入4g实施例1制备的聚多巴胺包覆的钛酸钡纳米纤维PDA@BTnf，140°C下预聚50min，倒入预热好的模具，在140°C下真空脱气泡30min，得到预聚物C；在预热好的聚四氟乙烯板上刮涂厚度为200μm的预聚物膜D，在140°C下固化50min，自然冷却后，得到固化度为60%的钛酸钡纳米纤维/双马来酰亚胺树脂复合材料预固化片E。
（3）将步骤（2）制备的预固化片E浸润步骤（1）制备的预聚物A后，平铺在步骤（1）制备的预固化片B上，排除气泡，得到双层结构复合材料B-E；再将步骤（1）制备的预聚物A的另一半浇注到双层结构复合材料B-E的预固化片E一侧，而后将模具放入微波炉中，循环辐照15个周期（每个周期辐照工艺均为中火、加热30s、冷却10s），自然冷却后得到固化度>97%的三层结构树脂基复合材料，记作B-E-B。

Claims (10)

  1. 一种三层结构树脂基复合材料，其特征在于，所述三层结构树脂基复合材料的制备方法包括以下步骤：
    （1）将可固化树脂体系与取向碳纳米管束混合，得到取向碳纳米管束预聚物；然后将预聚物分为第一预聚物、第二预聚物；然后将第一预聚物预固化，得到取向碳纳米管束预固化片；
    （2）将能固化树脂体系与聚多巴胺包覆的钛酸钡纳米纤维混合，得到钛酸钡纳米纤维预聚物；然后将钛酸钡纳米纤维预聚物制膜后预固化得到钛酸钡纳米纤维预固化片；
    （3）将钛酸钡纳米纤维预固化片浸润第二预聚物后平铺于取向碳纳米管束预固化片上；然后将第二预聚物浇注于钛酸钡纳米纤维预固化片上；再经过固化，得到三层结构树脂基复合材料。
  2. 根据权利要求1所述三层结构树脂基复合材料，其特征在于，步骤（1）中，取向碳纳米管束的用量为可固化树脂体系质量的0.1～2%，第一预聚物、第二预聚物等量；步骤（2）中，聚多巴胺包覆的钛酸钡纳米纤维的用量为能固化树脂体系质量的10～40%。
  3. 根据权利要求1所述三层结构树脂基复合材料，其特征在于，所述可固化树脂体系包括树脂或者树脂与固化剂；所述能固化树脂体系包括树脂或者树脂与固化剂；所述聚多巴胺包覆的钛酸钡纳米纤维的制备方法包括以下步骤：
    ①将钡盐、钛酸酯化合物在溶剂中混合，然后加入粘度调节剂，得到前驱体溶液；所述前驱体溶液经过静电纺丝、煅烧后，得到钛酸钡纳米纤维；
    ②将盐酸多巴胺、三羟甲基氨基甲烷盐酸盐溶解在水中，然后用碱液调节pH值为8～9；然后加入钛酸钡纳米纤维进行反应，得到聚多巴胺包覆的钛酸钡纳米纤维。
  4. 根据权利要求3所述三层结构树脂基复合材料，其特征在于，所述树脂包括双马来酰亚胺树脂、氰酸酯树脂、环氧树脂、聚酰亚胺树脂中的一种或几种；钡盐为乙酸钡，钛酸酯化合物为钛酸四丁酯，溶剂为乙酸，粘度调节剂为聚乙烯吡咯烷酮；静电纺丝的参数为1.7kV/cm；煅烧为在10°C/min的升温速率和空气气氛下，于700°C下煅烧3h；碱液为氢氧化钠水溶液；反应为室温下振荡反应24h。
  5. 根据权利要求3所述三层结构树脂基复合材料，其特征在于，钡盐、钛酸酯化合物的摩尔比为1；盐酸多巴胺、三羟甲基氨基甲烷盐酸盐、水、钛酸钡纳米纤维的质量比为0.2∶0.1∶100∶2。
  6. 根据权利要求1所述三层结构树脂基复合材料，其特征在于，钛酸钡纳米纤维预固化片的厚度为50～1000μm；采用涂膜法将钛酸钡纳米纤维预聚物制膜。
  7. 根据权利要求1所述三层结构树脂基复合材料，其特征在于，所述取向碳纳米管束预固化片的固化度为30%～60%；钛酸钡纳米纤维预固化片的固化度为30%～60%。
  8. 根据权利要求1所述三层结构树脂基复合材料，其特征在于，步骤（1）中，采用微波间歇固化的方式将第一预聚物预固化；步骤（3）中，采用微波间歇固化的方式固化。
  9. 根据权利要求8所述三层结构树脂基复合材料，其特征在于，微波间歇固化每次固化的时间为10～30s，间歇的时间为5～15s。
  10. 权利要求1所述三层结构树脂基复合材料在制备介电功能复合材料中的应用。
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