CN114854174A - Multilayer structure epoxy resin composite material and preparation method and application thereof - Google Patents

Multilayer structure epoxy resin composite material and preparation method and application thereof Download PDF

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CN114854174A
CN114854174A CN202210446276.7A CN202210446276A CN114854174A CN 114854174 A CN114854174 A CN 114854174A CN 202210446276 A CN202210446276 A CN 202210446276A CN 114854174 A CN114854174 A CN 114854174A
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epoxy resin
bnns
cnts
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pda
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CN114854174B (en
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苟彬
徐华松
谢从珍
周建港
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

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Abstract

The invention discloses an epoxy resin composite material with a multilayer structure and a preparation method and application thereof. A multi-layer structural epoxy composite comprising: a first BNNS filler layer, the first BNNS filler layer comprising: BNNS and epoxy; the CNTs @ SO @ PDA filling layer is arranged on the surface of the first BNNS filling layer; the CNTs @ SO @ PDA filling layer comprises a polydopamine-coated silicon dioxide modified carbon nanotube and epoxy resin; a second BNNS filling layer, wherein the second BNNS filling layer is arranged on the surface of the CNTs @ SO @ PDA filling layer, and the components of the second BNNS filling layer comprise: BNNS and epoxy. The invention adopts a multilayer structure design, and the CNTs @ SO @ PDA filling layer is used as a reinforcing layer, and the high-insulation BNNS filling layer is used as an upper breakdown-resistant layer and a lower breakdown-resistant layer, SO that the mechanical property and the insulation property of the epoxy resin are synergistically improved.

Description

Multilayer structure epoxy resin composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to an epoxy resin composite material with a multilayer structure and a preparation method and application thereof.
Background
Epoxy resins are widely used in the fields of high voltage insulation, aerospace, construction, agriculture, and the like because of their excellent dimensional stability, corrosion resistance, heat resistance, and insulation properties. However, since epoxy resin is a thermosetting polymer material, there is a large internal stress in the epoxy resin during curing, which results in increased brittleness. The mechanical property of the epoxy resin can be obviously improved by adopting the carbon nano filler for toughening, but because the carbon nano filler has extremely high conductivity, the insulating property of the epoxy resin composite material can be greatly reduced, the performance requirement of the insulating material in high power voltage cannot be met, meanwhile, the interface performance between a resin matrix and the filler is also a key factor for limiting the overall performance of the composite material, and how to improve the mechanical strength of the composite material while ensuring the insulating property of the composite material is still a problem which needs to be solved urgently at present.
Disclosure of Invention
In order to overcome the problem that the insulating property of the composite material cannot be ensured and the mechanical strength of the composite material cannot be improved in the prior art, the invention aims to provide a multilayer-structure epoxy resin composite material, the invention aims to provide a preparation method of the multilayer-structure epoxy resin composite material, and the invention aims to provide application of the multilayer-structure epoxy resin composite material.
The concept of the invention is as follows:
the Carbon Nanotubes (CNTs) in the carbon filler have extremely high mechanical strength, are simpler in surface functionalization compared with graphene, and are suitable for surface modification, so that the Carbon Nanotubes (CNTs) are often used as filling materials to improve the mechanical strength of organic polymer materialsThe silica nano thin layer is synthesized in situ on the surface of the carbon nano tube by using a sol-gel method, so that the original structure of the CNTs can be ensured, and the conductive capacity of the CNTs can be effectively inhibited. But due to SiO 2 The modified CNTs are further coated by organic polydopamine, so that the interfacial property between the filler and a matrix can be obviously improved, meanwhile, the dopamine surface has a certain amount of amino groups and can participate in epoxy curing reaction to form covalent bonds, so that the interfacial force is further improved, however, the dopamine is an organic semiconductor, so that the electric energy loss of the composite material in a high-pressure environment is increased. In order to further improve the insulating property of the material, the mechanical property and the insulating property of the epoxy resin are synergistically improved by constructing the macroscopic multi-layer structure epoxy resin, taking CNTs @ SO @ PDA filled epoxy resin as a reinforcing layer and taking high-insulation BNNS filler filled epoxy resin as upper and lower anti-puncture layers.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the present invention provides, in a first aspect, a multilayer epoxy resin composite material comprising:
a first BNNS filler layer, the first BNNS filler layer comprising: BNNS (boron nitride nanosheet) and epoxy resin;
the CNTs @ SO @ PDA filling layer is arranged on the surface of the first BNNS filling layer; the CNTs @ SO @ PDA filling layer comprises a polydopamine-coated silicon dioxide modified carbon nanotube and epoxy resin;
the second BNNS filling layer is arranged on the surface of the CNTs @ SO @ PDA filling layer, and the components of the second BNNS filling layer comprise: BNNS and epoxy;
CNTs @ SO @ PDA is a polydopamine coated silica-modified carbon nanotube.
Preferably, in the multilayer epoxy resin composite material, the mass fraction of BNNS in the first BNNS filling layer is 0.5-3 wt%; further preferably, the mass fraction of the BNNS in the first BNNS filling layer is 0.5-2.5 wt%; still further preferably, the mass fraction of BNNS in the first BNNS filler layer is 0.5-2 wt%.
Preferably, in the multilayer epoxy resin composite material, the mass fraction of BNNS in the second BNNS filling layer is 0.5-3 wt%; further preferably, the mass fraction of the BNNS in the second BNNS filling layer is 0.5-2.5 wt%; still further preferably, the mass fraction of BNNS in the second BNNS filler layer is 0.5-2 wt%.
Preferably, in the multilayer structure epoxy resin composite material, the mass fraction of the polydopamine-coated silicon dioxide modified carbon nano tube in the CNTs @ SO @ PDA filling layer is 0.5-3 wt%; further preferably, the mass fraction of the poly-dopamine-coated silicon dioxide modified carbon nanotube in the CNTs @ SO @ PDA filling layer is 0.5-2.5 wt%; still further preferably, the mass fraction of the poly-dopamine-coated silicon dioxide modified carbon nanotube in the CNTs @ SO @ PDA filling layer is 0.5-2 wt%.
Preferably, the multilayer structure epoxy resin composite material is at least one of alicyclic epoxy resin and bisphenol A epoxy resin.
Preferably, the multi-layer epoxy resin composite material, the first BNNS filling layer, the CNTs @ SO @ PDA filling layer and the second BNNS filling layer all comprise a curing agent and an accelerator.
More preferably, the curing agent is at least one of methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride; other suitable curing agents may be selected by those skilled in the art depending on the application.
More preferably, the accelerator is at least one of DMP30, triethylamine and 2-ethyl 4-methylimidazole; other suitable promoters may be selected by those skilled in the art depending on the actual circumstances.
Further preferably, in the multilayer epoxy resin composite material, the mass ratio of the epoxy resin, the curing agent and the accelerator in the first BNNS filler layer is: 1: (0.8-1.1): (0.003-0.007).
Further preferably, in the multilayer structure epoxy resin composite material, the mass ratio of the epoxy resin, the curing agent and the accelerator in the CNTs @ SO @ PDA filling layer is as follows: 1: (0.8-1.1): (0.003-0.007).
Further preferably, in the multilayer epoxy resin composite material, the mass ratio of the epoxy resin, the curing agent and the accelerator in the second BNNS filler layer is: 1: (0.8-1.1): (0.003-0.007).
Preferably, in the multilayer epoxy resin composite material, the preparation method of the polydopamine-coated silica-modified carbon nanotube is as follows:
dispersing the silicon dioxide modified carbon nano tube into a buffer solution, adding dopamine hydrochloride, stirring, reacting, and filtering to obtain a solid which is the poly-dopamine-coated silicon dioxide modified carbon nano tube.
Preferably, in the preparation method of the polydopamine-coated silica-modified carbon nanotube, the buffer solution is a Tris buffer solution, and the pH value of the buffer solution is 8.5.
Preferably, in the preparation method of the poly-dopamine-coated silicon dioxide modified carbon nanotube, the concentration of dopamine hydrochloride is 1.5-4.5mg/mL after dopamine hydrochloride is added.
Preferably, in the preparation method of the poly dopamine-coated silica-modified carbon nanotube, the mass ratio of the silica-modified carbon nanotube to dopamine hydrochloride is 1: (0.5-3); further preferably, the mass ratio of the silica-modified carbon nanotubes to dopamine hydrochloride is 1: (0.8-2.5); still further preferably, the mass ratio of the silica-modified carbon nanotubes to dopamine hydrochloride is 1: (1-2); more preferably, the mass ratio of the silica-modified carbon nanotubes to dopamine hydrochloride is 1: (1.2-1.8).
Preferably, in the preparation method of the poly-dopamine-coated silicon dioxide modified carbon nanotube, the stirring time is 40-56 hours; further preferably, the stirring time is 44-52 h; still more preferably, the stirring time is 46-50 h; more preferably, the stirring time is 47-49 h.
Preferably, in the preparation method of the poly-dopamine-coated silicon dioxide modified carbon nanotube, the reaction temperature is 50-70 ℃; further preferably, the reaction temperature is 55-65 ℃; still more preferably, the temperature of the reaction is 60 ℃.
Preferably, the reaction is carried out under the condition of water bath.
Preferably, the preparation method of the polydopamine-coated silica-modified carbon nanotube comprises the following steps:
dispersing the carbon nano tube in an alcohol solution, adding ammonia water and stirring; adding tetraethoxysilane, stirring and filtering to obtain the solid which is the silicon dioxide modified carbon nano tube.
Preferably, in the preparation method of the silicon dioxide modified carbon nanotube, the alcoholic solution is an ethanol solution.
Preferably, in the preparation method of the silicon dioxide modified carbon nano tube, ammonia water is added and stirred for 5-15 min; further preferably, adding ammonia water and stirring for 8-12 min; still more preferably, ammonia is added and stirred for 10 min.
Preferably, in the preparation method of the silicon dioxide modified carbon nanotube, the mass ratio of the carbon nanotube to the tetraethoxysilane is 1: (0.004-0.015); further preferably, the mass ratio of the carbon nanotubes to the tetraethoxysilane is 1: (0.005-0.01); still further preferably, the mass ratio of the carbon nanotubes to the tetraethoxysilane is 1: (0.006-0.009).
Preferably, in the preparation method of the silicon dioxide modified carbon nano tube, tetraethoxysilane is added and stirred for 3-5 hours; further preferably, adding tetraethoxysilane and stirring for 3.5-4.5 h; still more preferably, the tetraethoxysilane is added and stirred for 3.8 to 4.2 hours.
The second aspect of the present invention provides a preparation method of the above multilayer structure epoxy resin composite material, comprising the following steps:
(1) dispersing BNNS filler in a diluent, adding epoxy resin, heating and stirring, and then adding a curing agent and an accelerator to obtain a BNNS epoxy resin filling mixed solution;
(2) dispersing the polydopamine-coated silicon dioxide modified carbon nano tube in a diluent, adding epoxy resin, heating and stirring, and then adding a curing agent and an accelerator to obtain a CNTs @ SO @ PDA filled epoxy resin mixed solution;
(3) and pouring part of the BNNS epoxy resin filled mixed solution into a mold, curing, pouring the CNTs @ SO @ PDA epoxy resin filled mixed solution into the mold, curing, pouring the rest of the BNNS epoxy resin filled mixed solution into the mold, curing, and demolding to obtain the multilayer-structure epoxy resin composite material.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, the diluent is at least one of ethanol solution, acetone solution and N, N-dimethyl formyl solution.
Preferably, the preparation method of the multilayer structure epoxy resin composite material comprises the steps of (1) ultrasonically dispersing BNNS filler in a diluent; further preferably, the ultrasonic dispersion time is 0.5-1.5 h; still further preferably, the ultrasonic dispersion time is 0.8-1.5 h; more preferably, the ultrasonic dispersion time is 1 to 1.5 hours.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the step (2), the poly dopamine coated silicon dioxide modified carbon nano tube is ultrasonically dispersed in a diluent; further preferably, the ultrasonic dispersion time is 0.5-1.5 h; still further preferably, the ultrasonic dispersion time is 0.8-1.5 h; more preferably, the ultrasonic dispersion time is 1 to 1.5 hours.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the steps (1) and (2), heating and stirring are carried out in a water bath.
Preferably, the preparation method of the multilayer structure epoxy resin composite material comprises the steps (1) and (2), wherein the heating and stirring temperature is 50-70 ℃; further preferably, the heating and stirring temperature is 55 to 65 ℃.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the steps (1) and (2), the heating and stirring time is 5-7 h; more preferably, the heating and stirring time is 5.5-6.5 h.
Preferably, in the preparation method of the epoxy resin composite material with the multilayer structure, in the step (3), part of the BNNS epoxy resin filling mixed solution is poured into a mold, and the curing temperature is 90-105 ℃.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the step (3), part of the BNNS epoxy resin filling mixed solution is poured into the mold, and the curing time is 1-1.5 h.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the step (3), CNTs @ SO @ PDA filled epoxy resin is poured into a mold, and the curing temperature is 90-105 ℃.
Preferably, in the preparation method of the multilayer structure epoxy resin composite material, in the step (3), the CNTs @ SO @ PDA filled epoxy resin is poured into a mold, and the curing time is 1-1.5 h.
Preferably, in the step (3), the remaining mixed BNNS epoxy resin solution is poured into a mold, pre-cured at the low temperature of 90-105 ℃ for 1h-1.5h, heated to 115-125 ℃ for medium-temperature curing for 1-2h, and finally cured at the high temperature of 135-145 ℃ for 0.5-1h, and then demolded, thereby obtaining the multilayer epoxy resin composite material.
The third aspect of the invention provides the application of the multilayer epoxy resin composite material in an insulating material.
The invention has the beneficial effects that:
1. the invention adopts a multilayer structure design, and the CNTs @ SO @ PDA filling layer is used as a reinforcing layer, and the high-insulation BNNS filling layer is used as an upper breakdown-resistant layer and a lower breakdown-resistant layer, SO that the mechanical property and the insulation property of the epoxy resin are synergistically improved.
2. The CNTs @ SO @ PDA filling layer adopts a polydopamine-coated silicon dioxide modified carbon nano tube, wherein SiO 2 The modified carbon nano tube reduces the conductivity of the carbon nano tube on the basis of ensuring the structure of the carbon filler, so that the filler can be applied to the field of electric insulation; in addition, dopamine performs surface functionalization on the silicon dioxide modified carbon nano tube, and improves the interface compatibility between the filler and the epoxy resin matrix.
Drawings
Fig. 1 is a schematic view of a process for preparing an epoxy resin composite material having a multilayer structure according to an embodiment.
FIG. 2 is an infrared spectrum of Carbon Nanotubes (CNTs) of example 1, as well as prepared silica-modified carbon nanotubes (CNTs @ SO) and polydopamine-coated silica-modified carbon nanotubes (CNTs @ SO @ PDA).
FIG. 3 is an X-ray diffraction pattern of Carbon Nanotubes (CNTs) from example 1, as well as prepared silica-modified carbon nanotubes (CNTs @ SO) and polydopamine coated silica-modified carbon nanotubes (CNTs @ SO @ PDA).
FIG. 4 is a transmission electron micrograph of silica modified carbon nanotubes (CNTs @ SO), polydopamine coated silica modified carbon nanotubes (CNTs @ SO @ PDA), and Carbon Nanotubes (CNTs) prepared in example 1.
FIG. 5 is an elemental energy spectrum scan of the polydopamine coated silica modified carbon nanotubes (CNTs @ SO @ PDA) prepared in example 1.
FIG. 6 is a scanning electron microscope cross-sectional view of a nano-filled epoxy resin composite (CNTs @ SO @ PDA/EP) with a layered structure prepared in example 1.
FIG. 7 is a Weibull plot of breakdown field strength for epoxy composites prepared in examples 1-8 and neat Epoxy (EP).
FIG. 8 is a stress plot of the epoxy resin composites prepared in examples 2-5 and neat epoxy resin (EP).
FIG. 9 is a stress diagram of the multi-layer epoxy resins prepared in examples 1, 6 to 8.
FIG. 10 is a graph of elongation at break, tensile strength for epoxy composites prepared in examples 2-5 and neat Epoxy (EP).
FIG. 11 is a graph showing elongation at break and tensile strength of the epoxy resins having a multilayer structure prepared in examples 1, 6 to 8.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The examples are described only for the purpose of facilitating understanding of the invention and are not intended to limit the scope of the invention. The materials, reagents and the like used in the examples are those obtained from commercial sources unless otherwise specified.
The preparation of the epoxy resin composite material, which comprises the preparation of the silica-modified carbon nanotube, the preparation of the polydopamine-coated silica-modified carbon nanotube, and the preparation of the multilayer-structure nano-filled epoxy resin composite material, is carried out by using the flow chart of the preparation of the multilayer-structure epoxy resin composite material shown in the attached figure 1.
Example 1
The preparation method of the silica-modified carbon nanotube of the present example is as follows:
(1) mixing 10mL of deionized water and 200mL of ethanol, and pouring into a beaker; adding 0.5g of CNTs, and performing ultrasonic dispersion for 30 min; then 12mL of ammonia water is added, and the mixture is magnetically stirred for 10min at room temperature;
(2) then adding 4mL of ethyl orthosilicate, and reacting for 4 hours at room temperature by magnetic stirring; performing suction filtration on the mixture after reaction, repeatedly washing the obtained solid for 3 times by using ethanol, finally placing the solid in a drying oven at 80 ℃ for drying for 24 hours, and collecting to obtain a silicon dioxide modified carbon nanotube (CNTs @ SO);
the preparation method of the poly-dopamine-coated silica-modified carbon nanotube of the embodiment is as follows:
s1, weighing a certain amount of Tris (hydroxymethyl) aminomethane (Tris) to be dissolved in 500mL of distilled water, and slowly dropwise adding a concentrated HCl solution until the pH value of the solution is 8.5 to obtain a Tris buffer solution with the pH value of 8.5;
s2, weighing 1g of the prepared CNTs @ SO filler, dissolving the CNTs @ SO filler in a Tris buffer solution, and performing ultrasonic dispersion for 1 h;
s3, weighing 3mg/mL dopamine hydrochloride, dissolving in the reaction solution, and placing in a 60 ℃ water bath to stir for reaction for 48 hours;
s4, carrying out suction filtration on the reacted solution, washing the solid with distilled water for 5 times, and drying for 12h by adopting a vacuum freezing device to obtain the poly-dopamine coated silicon dioxide modified carbon nano tube (CNTs @ SO @ PDA).
The infrared spectrogram of the Carbon Nano Tube (CNTs) and the prepared silicon dioxide modified carbon nano tube (CNTs @ SO) and the polydopamine coated silicon dioxide modified carbon nano tube (CNTs @ SO @ PDA) is shown in figure 2; the X-ray diffraction patterns of the Carbon Nanotubes (CNTs) used in the above process, the prepared silica-modified carbon nanotubes (CNTs @ SO), and the polydopamine-coated silica-modified carbon nanotubes (CNTs @ SO @ PDA) are shown in fig. 3. As can be seen from FIGS. 2 to 3, the sol-gel method is usedSiO-coated film 2 Then, the infrared spectrum of the modified CNTs is 798 to 1103cm -1 Position appears to be SiO 2 Furthermore, the modified CNTs still retain the 002 and 100 crystal face peaks of the graphite structure as can be seen from an X-ray diffraction spectrum, which proves that the carbon nano tube structure is not damaged.
The transmission electron microscope images of the prepared silica modified carbon nanotubes (CNTs @ SO), polydopamine coated silica modified carbon nanotubes (CNTs @ SO @ PDA) and Carbon Nanotubes (CNTs) are shown in FIG. 4; an element energy spectrum scanning diagram of the prepared polydopamine-coated silicon dioxide modified carbon nanotube (CNTs @ SO @ PDA) is shown in FIG. 5; as can be seen from FIG. 4, the CNTs have a distinct amorphous layer on the surface after being modified with polydopamine by a sol-gel method. As can be seen from FIG. 5, it can be seen from the results of the energy spectrum scan that the SiO component is 2 The Si element and the N element of the polydopamine are uniformly distributed on the surfaces of the CNTs, which shows that SiO is 2 Successful coating with polydopamine.
The preparation method of the epoxy resin composite material with a multilayer structure of the embodiment is as follows:
1) weighing 3.89g of the prepared CNTs @ SO @ PDA, dissolving in 200mL of diluent acetone, and ultrasonically dispersing for 1 h; adding 100g of bisphenol A epoxy resin, stirring with a glass rod until the solution is completely mixed with the epoxy resin, placing the mixed solution in a water bath kettle, heating at 60 ℃ and stirring for 6h, respectively weighing 90g of curing agent methyl hexahydrophthalic anhydride and 0.5g of accelerant 2-ethyl-4-methylimidazole, adding into the mixture, stirring at room temperature for 30min, and placing in a vacuum box to remove bubbles; obtaining a mixed solution of the CNTs @ SO @ PDA filled epoxy resin;
2) weighing 7.78g of BNNS filler, dissolving in 400mL of diluent acetone, and performing ultrasonic dispersion for 1 h; adding 200g of bisphenol A epoxy resin, stirring with a glass rod until the solution is completely mixed with the epoxy resin, placing the mixed solution in a water bath kettle, heating at 60 ℃ and stirring for 6 hours, respectively weighing 180 g of curing agent methyl hexahydrophthalic anhydride and 1g of accelerant 2-ethyl-4-methylimidazole, adding the mixture, stirring at room temperature for 30min, and placing in a vacuum box to remove bubbles; obtaining a BNNS filling epoxy resin mixed solution;
3) pouring a half of the BNNS epoxy resin filled mixed solution obtained in the step 2) into a mold, controlling the height of the solution to be 1/3 of the mold, and placing the mold into a heating box for precuring for 1h at 90 ℃ until the mold is semi-cured; pouring the same amount of the CNTs @ SO @ PDA filled epoxy resin solution into a mold, placing the mold into a heating box for precuring for 1h at a low temperature of 90 ℃ until an intermediate layer is semi-cured, then pouring the other half of the BNNS filled epoxy resin mixed solution into the mold by the same flow, precuring for 1h at a low temperature of 90 ℃, raising the temperature to 115 ℃ for curing for 1h at a medium temperature, finally curing for 0.5h at a high temperature of 135 ℃, and demolding to obtain the nano filled epoxy resin composite material (CNTs @ SO @ PDA/EP) with a multilayer structure.
The multilayer epoxy composite (CNTs @ SO @ PDA/EP) prepared in this example had a BNNS mass fraction in the upper BNNS filling layer of 2 wt%, a CNTs @ SO @ PDA filling layer in the middle layer of 2 wt%, and a BNNS mass fraction in the lower BNNS filling layer of 2 wt%.
The sectional scanning electron microscope image of the multilayer structure nano-filled epoxy resin composite material prepared above is shown in fig. 6. The cross section of the carbon nanotube is of an obvious three-layer structure, the surfaces of the upper layer and the lower layer are rough due to the flaky filler, and the middle layer of epoxy resin filled with the modified carbon nanotubes is smooth. The multilayer structure can be found to be well combined under a scanning electron microscope, and has no interface defects. In addition, through local amplification of different layers, BNNS and CNTs @ SO @ PDA can be obviously and uniformly distributed in a polymer matrix, and no obvious agglomeration phenomenon exists.
Example 2
The preparation method of the epoxy resin composite material of the embodiment is as follows:
1) weighing 11.67g of BNNS filler, dissolving in 600mL of diluent acetone, and ultrasonically dispersing for 1 h; adding 300g of bisphenol A epoxy resin, stirring with a glass rod until the solution is completely mixed with the epoxy resin, placing the mixed solution in a water bath kettle, heating at 60 ℃ and stirring for 6h, respectively weighing 270g of curing agent methyltetrahydrophthalic anhydride and 1.5g of accelerant 2-ethyl-4-methylimidazole, adding the mixture into the mixture, stirring for 30min at room temperature, and placing in a vacuum box to remove bubbles; obtaining a BNNS filling epoxy resin mixed solution;
2) pouring the BNNS epoxy resin filled mixed solution obtained in the step 1) into a mold, controlling the height of the solution to be 1/3 of the mold, and placing the mold into a heating box for precuring for 1h at 90 ℃ until the solution is semi-cured; pouring the 1/3BNNS epoxy resin filling mixed solution into a mold, placing the mold into a heating box for precuring for 1h at a low temperature of 90 ℃ until the middle layer is semi-cured, then pouring the rest BNNS epoxy resin filling mixed solution into the mold by adopting the same flow, precuring for 1h at a low temperature of 90 ℃ and raising the temperature to 115 ℃ for curing for 1h at a medium temperature, finally curing for 0.5h at a high temperature of 135 ℃ and then demolding to obtain the nano filling epoxy resin composite material (BNNS/EP).
Example 3
This example differs from example 2 in that the BNNS filler was replaced with CNTs, and the resulting nano-filled epoxy resin composite (CNTs/EP) was prepared in this example.
Example 4
This example differs from example 2 in that the BNNS filler was replaced with CNTs @ SO prepared as described above in example 1, and the resulting nano-filled epoxy resin composite (CNTs @ SO/EP) was prepared in this example.
Example 5
This example differs from example 2 in that the BNNS filler was replaced with CNTs @ SO @ PDA, prepared as described above in example 1, and the nano-filled epoxy composite (CNTs @ SO @ PDA/EP) prepared in this example.
Example 6
This example differs from example 1 in that CNTs @ SO @ PDA was used in an amount of 0.96g, a bisphenol A type epoxy resin was used in an amount of 100g, a curing agent was used in an amount of 90g, and an accelerator was used in an amount of 0.5g in step 1) of the method for producing an epoxy resin composite material having a multilayer structure.
The multilayer epoxy composite (CNTs @ SO @ PDA/EP) prepared in this example had a BNNS mass fraction in the upper BNNS filling layer of 2 wt%, a CNTs @ SO @ PDA filling layer in the middle layer of 0.5 wt%, and a BNNS mass fraction in the lower BNNS filling layer of 2 wt%.
Example 7
This example differs from example 1 in that CNTs @ SO @ PDA was used in an amount of 1.92g, a bisphenol A type epoxy resin was used in an amount of 100g, a curing agent was used in an amount of 90g, and an accelerator was used in an amount of 0.5g in step 1) of the method for producing an epoxy resin composite material having a multilayer structure.
The multilayer epoxy composite (CNTs @ SO @ PDA/EP) prepared in this example had a BNNS mass fraction in the upper BNNS filling layer of 2 wt%, a CNTs @ SO @ PDA filling layer in the middle layer of 1 wt%, and a BNNS mass fraction in the lower BNNS filling layer of 2 wt%.
Example 8
This example differs from example 1 in that CNTs @ SO @ PDA was used in an amount of 5.89g, a bisphenol A type epoxy resin was used in an amount of 100g, a curing agent was used in an amount of 90g, and an accelerator was used in an amount of 0.5g in step 1) of the method for producing an epoxy resin composite material having a multilayer structure.
The multilayer epoxy composite (CNTs @ SO @ PDA/EP) prepared in this example had a BNNS mass fraction in the upper BNNS filling layer of 2 wt%, a CNTs @ SO @ PDA filling layer in the middle layer of 3 wt%, and a BNNS mass fraction in the lower BNNS filling layer of 2 wt%.
The Weibull plots of breakdown field strength of the epoxy composites prepared in examples 1-8 above and neat Epoxy (EP) are shown in FIG. 7. In the figure S 0.5 Represents the multilayer epoxy resin, S, prepared in example 6 1 Represents the multilayer epoxy resin, S, prepared in example 7 2 Represents the multilayer epoxy resin, S, prepared in example 1 3 The multilayer epoxy resin prepared in example 8 is shown. As can be seen from FIG. 7, the breakdown field strengths of the pure epoxy resin, the BNNS filled epoxy resin, the CNTs @ SO filled epoxy resin and the CNTs @ SO @ PDA filled epoxy resin are respectively: 17.12 kV/mm, 19.69 kV/mm, 4.86 kV/mm, 15.64 kV/mm and 17.99kV/mm, wherein the breakdown field strengths of the multi-layer structure epoxy resin with different mass fractions of the interlayer filler are respectively as follows: 19.40, 19.49, 19.61 and 17.15 kV/mm. It can be seen that when the multilayer structure is adopted and the mass fraction of the intermediate layer CNTs @ SO @ PDA is 2%, the breakdown strength is the highest, and is improved by 13.37% compared with that of pure epoxy resin, and is 4 times that of the CNTs epoxy resin which is only filled with 2%, but the difference that the mass fraction of the intermediate layer CNTs @ SO @ PDA is 0.5-2% is not great.
Epoxy resin composites and pure rings prepared in examples 2-5 aboveThe stress diagram of the oxygen resin (EP) is shown in FIG. 8; the stress patterns of the multi-layer structure epoxy resin and the virgin epoxy resin (EP) prepared in the above examples 1, 6 to 8 are shown in FIG. 9, S in FIG. 9 0.5 Represents the multilayer epoxy resin, S, prepared in example 6 1 Represents the multilayer epoxy resin, S, prepared in example 7 2 Represents the multilayer epoxy resin, S, prepared in example 1 3 The multilayer epoxy resin prepared in example 8 is shown. The elongation at break and tensile strength of the epoxy resin composites prepared in examples 2-5 and the neat epoxy resin (EP) are shown in FIG. 10; the elongation at break and tensile strength of the multilayer epoxy resins prepared in examples 1, 6 and 8 are shown in FIG. 11, where S in FIG. 11 0.5 Represents the multilayer epoxy resin, S, prepared in example 6 1 Represents the multilayer epoxy resin, S, prepared in example 7 2 Represents the multilayer epoxy resin, S, prepared in example 1 3 The multilayer epoxy resin prepared in example 8 is shown. As shown in FIG. 10, the tensile strengths of the pure epoxy resin, BNNS filled epoxy resin, CNTs @ SO filled epoxy resin and CNTs @ SO @ PDA filled epoxy resin are respectively: 52.19, 47.91, 47.14, 56.28 and 62.71MPa, and the breaking elongation is respectively as follows: 4.37, 3.28, 2.76, 3.71 and 5.41 percent. As shown in fig. 11, the tensile strengths of the multi-layer epoxy resin with different mass fractions of the interlayer filler are respectively as follows: 59.76, 59.94, 64.84 and 62.85MPa, and an elongation at break of: 5.46, 5.26, 5.18, 3.96 percent. It can be seen that when the multilayer structure is adopted and the mass fraction of the intermediate layer CNTs @ SO @ PDA is 2%, the tensile strength is the highest, and is improved by 24.24% and the elongation at break is improved by 27.12% compared with pure epoxy resin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A multilayer epoxy composite comprising:
a first BNNS fill layer, the first BNNS fill layer composition comprising: BNNS and epoxy;
the CNTs @ SO @ PDA filling layer is arranged on the surface of the first BNNS filling layer; the CNTs @ SO @ PDA filling layer comprises a polydopamine-coated silicon dioxide modified carbon nanotube and epoxy resin;
a second BNNS filling layer, said second BNNS filling layer being disposed on a surface of said CNTs @ SO @ PDA filling layer, said second BNNS filling layer comprising: BNNS and epoxy.
2. The multi-layer epoxy composite of claim 1, wherein the BNNS in said first BNNS filler layer is present in an amount of 0.5 to 3 wt%.
3. The multilayer structure epoxy resin composite material of claim 1, wherein the mass fraction of the poly-dopamine-coated silica-modified carbon nanotubes in the CNTs @ SO @ PDA filler layer is 0.5 to 3 wt%.
4. The multi-layer epoxy composite of claim 1, wherein the first BNNS filler layer, CNTs @ SO @ PDA filler layer, and second BNNS filler layer components each comprise a curing agent and an accelerator.
5. The multilayer structure epoxy resin composite material according to any one of claims 1 to 4, wherein the polydopamine-coated silica-modified carbon nanotube is prepared by the following method:
dispersing the silicon dioxide modified carbon nano tube into a buffer solution, adding dopamine hydrochloride, stirring, reacting, and filtering to obtain a solid which is the poly-dopamine-coated silicon dioxide modified carbon nano tube.
6. The multilayer structure epoxy resin composite material according to claim 5, wherein the mass ratio of the silica-modified carbon nanotubes to dopamine hydrochloride is 1: (0.5-3).
7. The multilayer structure epoxy resin composite material according to claim 5, wherein the silica-modified carbon nanotubes are prepared by the following method:
dispersing the carbon nano tube in an alcohol solution, adding ammonia water and stirring; adding tetraethoxysilane, stirring and filtering to obtain solid which is the silicon dioxide modified carbon nano tube.
8. The multilayer structure epoxy resin composite material according to claim 7, wherein the mass ratio of the carbon nanotubes to the tetraethoxysilane is 1: (0.004-0.015).
9. A method for preparing the multilayer structure epoxy resin composite material as claimed in claim 4, characterized by comprising the following steps:
(1) dispersing BNNS filler in a diluent, adding epoxy resin, heating and stirring, and then adding a curing agent and an accelerator to obtain a BNNS filled epoxy resin mixed solution;
(2) dispersing the poly dopamine coated silicon dioxide modified carbon nano tube in a diluent, adding epoxy resin, heating and stirring, and then adding a curing agent and an accelerator to obtain a CNTs @ SO @ PDA filled epoxy resin mixed solution;
(3) and pouring part of the BNNS epoxy resin filling mixed solution into a mold, curing, pouring the CNTs @ SO @ PDA epoxy resin filling mixed solution into the mold, curing, pouring the rest of the BNNS epoxy resin filling mixed solution into the mold, curing, and demolding to obtain the multilayer-structure epoxy resin composite material.
10. Use of the multilayer epoxy resin composite material according to any one of claims 1 to 8 in an insulating material.
CN202210446276.7A 2022-04-26 2022-04-26 Multilayer structure epoxy resin composite material and preparation method and application thereof Active CN114854174B (en)

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Publication number Priority date Publication date Assignee Title
CN105778427A (en) * 2016-05-20 2016-07-20 安徽大学 Method for synergistically modifying epoxy resin by using boron nitride-carbon nanotube nano composite
CN108250898A (en) * 2017-12-18 2018-07-06 常州二维碳素科技股份有限公司 A kind of electro-thermal anti-ice and deicing system and preparation method thereof
CN112063301A (en) * 2020-07-31 2020-12-11 新昌县易纵新材料科技有限公司 High-strength heat-conducting modified epoxy resin composite coating and preparation method thereof
CN112266710A (en) * 2020-09-10 2021-01-26 廊坊艾格玛新立材料科技有限公司 Powder coating with super-weather resistance and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105778427A (en) * 2016-05-20 2016-07-20 安徽大学 Method for synergistically modifying epoxy resin by using boron nitride-carbon nanotube nano composite
CN108250898A (en) * 2017-12-18 2018-07-06 常州二维碳素科技股份有限公司 A kind of electro-thermal anti-ice and deicing system and preparation method thereof
CN112063301A (en) * 2020-07-31 2020-12-11 新昌县易纵新材料科技有限公司 High-strength heat-conducting modified epoxy resin composite coating and preparation method thereof
CN112266710A (en) * 2020-09-10 2021-01-26 廊坊艾格玛新立材料科技有限公司 Powder coating with super-weather resistance and preparation method and application thereof

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