CN107538661B - Four-layer structure polymer matrix composites and preparation method thereof - Google Patents

Four-layer structure polymer matrix composites and preparation method thereof Download PDF

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CN107538661B
CN107538661B CN201710813840.3A CN201710813840A CN107538661B CN 107538661 B CN107538661 B CN 107538661B CN 201710813840 A CN201710813840 A CN 201710813840A CN 107538661 B CN107538661 B CN 107538661B
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resin
layer structure
composite material
polymer matrix
cep
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CN107538661A (en
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梁国正
张小宝
顾嫒娟
袁莉
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Jiangsu Liyi New Material Technology Co., Ltd.
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Suzhou University
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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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers
    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/12—Making multilayered or multicoloured articles
    • B29C39/123—Making multilayered articles
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a kind of four-layer structure polymer matrix composites and preparation method thereof；The present invention constructs four-layer structure polymer matrix composites with two layers of the mica paper and carbon nanotube/thermosettiresin resin composite material that infiltrate resin, compared with insulating layer-conductor/polymer laminar structural composite material of prior art preparation, four-layer structure composite material provided by the invention has both high energy storage density, low-dielectric loss (< 0.1, @100Hz) and high dielectric constant (> 100 ,@100Hz).The four-layer structure polymer matrix composites have the characteristics that preparation process is simple, at low cost, raw material sources are wide, are suitble to large-scale application.

Description

Four-layer structure polymer matrix composites and preparation method thereof
Technical field
The present invention relates to have both high energy storage density, high dielectric constant > 100(in 100Hz) and low-dielectric loss < 0.1(exist Polymer matrix composites 100Hz) and preparation method thereof, in particular to a kind of four-layer structure polymer matrix composites and its preparation Method.
Background technique
Multifunction, micromation are the development trends of electronic device, and the passive element proportion in electronic system is more next It is bigger.In passive element, embedded capacitor has obtained extensive concern, it can play the work such as decoupling, bypass, filtering With.Material used in embedded capacitor needs to have both high energy storage density, high dielectric constant (> 100 ,@100Hz) and low dielectric It is lost (< 1 ,@100Hz).Compared to ceramics, ceramic/polymer composite has good craftsmanship and toughness.But even if The content of ceramics reaches high values (> 50 vol%), at 100Hz, the dielectric constant of ceramic/polymer composite still < 100.Meanwhile high ceramic additive amount also deteriorates the moulding process and mechanical property of polymer composites.
Conductor/polymer composites obtain high dielectric constant under low conductor content, but are usually associated with dielectric loss Increase and breakdown strength be greatly reduced.For this purpose, people have done many significant work.Prior art discovery, identical In the case of polymer and conductor, design three-decker composite material can not only make composite material obtain higher dielectric constant, And available low dielectric loss, when conductor additive amount is 3wt%, the dielectric loss of composite material is 0.21(@ 100Hz)；But its dielectric constant is only 80(@100Hz), the still not up to requirement of embedded capacitor.
For linear material, improving its dielectric constant or breakdown strength all can be such that its energy storage density is improved.It is existing There is technology Ba0.6Sr0.4TiO3Nanofiber/Kynoar (being denoted as B) and graphene oxide/Kynoar (being denoted as G), It is prepared for three-decker composite material GBG.Compared to monolayer material G, the breakdown strength of GBG improves 1 times, therefore its energy storage is close Degree is 3.3 times of G, but the dielectric constant of GBG is only 20(@100Hz)；Prior art preparation polyimides (PI)-simultaneously Multi-walled carbon nanotube (MWCNT)/PI-PI three-decker composite material, its energy storage density are higher than MWCNT/PI single layer composite wood Material, but increase rate is only 40%, especially its dielectric constant is only 26.1(@100Hz).
It can be seen that although introducing insulating layer can be improved energy storage close compared to traditional conductor/polymer monolayers material Degree, but it is to be improved on increase rate；Meanwhile the conductor containing insulating layer/polymer laminar structural composite material fails to High energy storage density, low-dielectric loss (< 0.5,100Hz) and high dielectric constant (> 100,100Hz) are had both, is not able to satisfy Requirement of the embedded capacitor material to high dielectric constant.Therefore, building meets the novel lamellar of embedded capacitor requirement Structural composite material is of great significance.
Summary of the invention
In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide have both high energy storage density, low dielectric The four-layer structure polymer matrix composites of (< 0.2 ,@100Hz) and high dielectric constant (> 150 ,@100Hz) are lost, prepare work Skill is simple, at low cost, raw material sources are wide, is suitble to large-scale application.
Realizing the technical solution of the object of the invention is
A kind of preparation method of four-layer structure polymer matrix composites, includes the following steps:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains To prepolymer；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, and it is pre- solid to obtain carbon nanotube/thermosetting resin Change piece A；
(3) two mica paper are infiltrated after can be thermally cured resin liquid respectively, is successively laid in the carbon nanometer of step (2) preparation On pipe/thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, Then solidified to obtain the four-layer structure polymer matrix composites.
The invention also discloses the four-layer structure polymer matrix composites prepared according to above-mentioned preparation method.
The invention also discloses a kind of preparation methods of four-layer structure polymer matrix composites presoma, including walk as follows It is rapid:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains To prepolymer；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, and it is pre- solid to obtain carbon nanotube/thermosetting resin Change piece A；
(3) two mica paper are infiltrated after can be thermally cured resin liquid respectively, is successively laid in the carbon nanometer of step (2) preparation On pipe/thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, Obtain four-layer structure polymer matrix composites presoma.
The present invention further discloses a kind of four-layer structure polymer matrix composites presoma, preparation method includes such as Lower step:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains To prepolymer；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, and it is pre- solid to obtain carbon nanotube/thermosetting resin Change piece A；
(3) two mica paper are infiltrated after can be thermally cured resin liquid respectively, is successively laid in the carbon nanometer of step (2) preparation On pipe/thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, Obtain four-layer structure polymer matrix composites presoma.
In the present invention, the carbon nanotube is single-walled carbon nanotube and/or multi-walled carbon nanotube；The carbon nanotube without Surface treatment or surface treated.Compared to other conductor materials, carbon nanotube has a clear superiority, including big draw ratio, Unique electricity and mechanical property, good heat-resisting and corrosion resistance etc..The present invention can be received using not surface treated carbon It is uniform to obtain composite property for mitron, and keeps the good electrical property of carbon nanotube.The present invention uses carbon nanotube simultaneously As conductive additive, compared with other additives, the curing performance of thermosetting resin will not influence, so that composite material solidifies Performance stable uniform afterwards improves to be conducive to dielectric constant, breakdown strength etc., and the geometry of carbon nanotube in the final product Draw ratio is usual > and 100, it is lower hence for content required for specific resistivity, solidification is neither influenced, and can reduce de- It falls.
In the present invention, the aathermoset resin system includes thermosetting resin or the aathermoset resin system includes heat Thermosetting resin and curing agent；The resin liquid that can be thermally cured is obtained by can be thermally cured resin prepolymer or the thermosetting resin liquid It is obtained by can be thermally cured resin with conductive filler pre-polymerization.
In the present invention, the thermosetting resin includes cyanate ester resin, bimaleimide resin, one in epoxy resin Kind is several；The resin that can be thermally cured includes one of cyanate ester resin, bimaleimide resin, epoxy resin or several Kind.Resin of the invention includes the combination of single resin or several resins, can not only provide excellent solidification cementability Can, guarantee that the use of multilayer material is stablized, and can be uniform in favor of multilayer materials performance, avoids local defect, it is more main If excellent interface performance can be obtained by forming four-layer structure with resin-bonded mica paper, possess more interface charge products It is tired, the higher dielectric constant of four-layer structure polymer matrix composites is assigned, at 100Hz, four-layer structure composite material is obtained High dielectric constant (158,100Hz), energy storage density are 16.5 times of conductor/polymer monolayers composite materials, are achieved imaginary Less than technical effect.
In the present invention, in step (1), the temperature of pre-polymerization is 90~150 DEG C, and the time is 4~6 hours；In step (2), in advance Cured temperature is 140~160 DEG C, and the time is 0.5~2 hour；In step (4), cured temperature is 150~240 DEG C, the time It is 10~12 hours.Solidification of the invention, pre-polymerization, precuring meet resin curing process, can choose ladder-elevating temperature, can also be with Select non-ladder-elevating temperature, the resin property after solidification is excellent, have both high energy storage density, low-dielectric loss (< 0.2 ,@100Hz) and High dielectric constant (> 150 ,@100Hz), achieves unexpected technical effect.
Compared with prior art, beneficial effect obtained by the present invention is:
1, the present invention prepares four-layer structure polymer matrix composites, has both high storage for the first time using mica paper as one of composition It can density, low-dielectric loss (< 0.2 ,@100Hz) and high dielectric constant (> 150 ,@100Hz)；And mica has in China Reserves abundant and grade height, promote mineral products utilization efficiency, and facilitate engineering application.
2, the present invention constructs four layers of knot with two layers of the mica paper and carbon nanotube/thermosettiresin resin composite material that infiltrate resin Paper mulberry resin-based composite forms fine and close mica paper layer, and two since mica paper piece interlayer is there are hole after resin infiltration There are one layer of thin resin layers between layer mica paper, to possess more interface charge accumulation in structure in a limited space, assign Give the higher dielectric constant of four-layer structure polymer matrix composites.At 100Hz, four-layer structure composite material obtains high dielectric Constant (158,100Hz), energy storage density are 16.5 times of conductor/polymer monolayers composite materials.As can be seen that present invention system Standby four-layer structure polymer matrix composites have both high dielectric constant (>150 ,@100Hz), low-dielectric loss (<0.2 ,@100Hz) And high energy storage density；Efficiently solve the prior art unsolved technical problem for a long time.
3, the preparation method simple process of four-layer structure polymer matrix composites provided by the invention, easily controllable, is easy to Scale；Meanwhile raw material sources are wide, inexpensive.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo (figure of the mica paper that uses of the embodiment of the present invention 1 before and after infiltration 1a: before mica paper infiltration；Fig. 1 b: after mica paper infiltration)；
Fig. 2 be the embodiment of the present invention 1 prepare four-layer structure polymer matrix composites between layers interface SEM shine Piece；
Fig. 3 is that four-layer structure polymer matrix composites, four-layer structure resin base prepared by the embodiment of the present invention 7 and 10 are compound Carbon nanotube/cyanic acid of cyanate/epoxy curing resin, the preparation of comparative example 2 prepared by mica paper layer, comparative example 1 in material Mica powder/CNT/CEP composite material conductivity-frequency curve prepared by ester/epoxy curing resin composite material, comparative example 5；
Fig. 4 be cyanate/epoxy curing resin (comparative example 1) of comparative example of the present invention preparation, carbon nanotube/cyanate/ Epoxy curing resin composite material (comparative example 2), CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- mica Paper-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With dielectric constant-frequency curve of the four-layer structure polymer matrix composites of 10 preparations；
Fig. 5 be cyanate/epoxy curing resin (comparative example 1) of comparative example of the present invention preparation, carbon nanotube/cyanate/ Epoxy curing resin composite material (comparative example 2), CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- mica Paper-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With dielectric loss-frequency curve of the four-layer structure polymer matrix composites of 10 preparations；
Fig. 6 be comparative example of the present invention preparation carbon nanotube/cyanate/epoxy curing resin composite material (comparative example 2), CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- mica paper-CNT/CEP three-decker composite material (compare Example 4), the four-layer structure polymer matrix composites that prepare of mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 and 10 Breakdown strength；
Fig. 7 be cyanate/epoxy curing resin (comparative example 1) of comparative example of the present invention preparation, carbon nanotube/cyanate/ Epoxy curing resin composite material (comparative example 2), CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- mica Paper-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With the energy storage density of the four-layer structure polymer matrix composites of 10 preparations.
Specific embodiment
Technical solution of the present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
By 0.3g hydroxyl carbon nano tube (CNT, 7-15 μm of outer diameter, 5 μm of length >), 40g bisphenol A cyanate ester and 10g Epoxy resin (trade mark E-51) mixing, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；The mixed liquor is existed Pre-polymerization 5h at 145 DEG C.After pre-polymerization, prepolymer is divided into two equal portions.A copy of it is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Then mold is put into baking oven, the precuring 1h at 150 DEG C, is obtained after cooling compound Material precuring piece, is denoted as CNT/CEP.
Two mica paper (individual is 28 μm thick) of 1.35g can be thermally cured in resin liquid in CEP and infiltrate, be placed on above-mentioned pre- solid On piece CNT/CEP, bubble is excluded, three-decker composite material is obtained, is denoted as I-CNT/CEP of 2MP；By another de-bubbled Prepolymer pour on I-CNT/CEP of 2MP, as four-layer structure polymer matrix composites presoma is then true at 150 DEG C After empty deaeration 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h of technique carry out solidification and Post-processing, obtains four-layer structure polymer matrix composites.Mica paper used in the composite material infiltration front and back SEM photograph with And the SEM photograph of obtained four-layer structure polymer matrix composites interface between layers is respectively referring to attached Fig. 1 and 2.
Referring to attached drawing 1, it is the SEM photograph for the mica paper infiltration front and back that embodiment 1 uses.There it can be seen that without There are hole (Fig. 1 a) for the mica paper of resin infiltration；And after resin infiltration, resin by hole penetrate into mica splittings it In, form fine and close structure (Fig. 1 b).
Referring to attached drawing 2, it is the interface between layers of four-layer structure polymer matrix composites made from embodiment 1 SEM photograph.Therefrom it can be seen that, thickness significantly increases after mica paper infiltration, and has one layer of infiltration tree between two mica paper Rouge, thickness are slightly less than individual mica paper.This illustrates that resin has penetrated into inside mica paper.This special four-layer structure becomes The basis of four-layer structure polymer matrix composites acquisition high dielectric constant.
Embodiment 2
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 28 μm thick) of 1.35g are infiltrated in CNT/CEP resin, are placed on above-mentioned precuring piece On, bubble is excluded, three-decker composite material is obtained, is denoted as 2MPII-CNT/CEP；By the prepolymer of another de-bubbled It pours on 2MPII-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 of technique DEG C/2h+220 DEG C/2h and 240 DEG C/4h solidified and post-processed, obtain four-layer structure polymer matrix composites.
Embodiment 3
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 44) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.05g CNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, it is ultrasonic at 90 DEG C Oscillation stirring 20min, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, by prepolymer point At two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into In baking oven, the precuring 1h at 150 DEG C obtains CNT/CEP composite material precuring piece after cooling.
Two mica paper (individual is 40 μm thick) of 1.95g are infiltrated in CEP resin, above-mentioned pre- solid on piece is placed on, excludes Bubble obtains three-decker composite material, is denoted as I-CNT/CEP of 2MP；The prepolymer of another de-bubbled is poured in 2MP On I-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 of technique DEG C/2h and 240 DEG C/4h solidified and post-processed, obtain four-layer structure polymer matrix composites.
Embodiment 4
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.9g CNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, it is ultrasonic at 90 DEG C Oscillation stirring 20min, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, by prepolymer point At two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into In baking oven, the precuring 1h at 150 DEG C obtains CNT/CEP composite material precuring piece after cooling.
Two mica paper (individual is 40 μm thick) of 1.95g are infiltrated in CEP resin, above-mentioned pre- solid on piece is placed on, excludes Bubble obtains three-decker composite material, is denoted as I-CNT/CEP of 2MP；The prepolymer of another de-bubbled is poured in 2MP On I-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 of technique DEG C/2h and 240 DEG C/4h solidified and post-processed, obtain four-layer structure polymer matrix composites.
Embodiment 5
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 40 μm thick) of 1.95g are infiltrated in CEP resin, above-mentioned pre- solid on piece is placed on, excludes Bubble obtains three-decker composite material, is denoted as I-CNT/CEP of 2MP；The prepolymer of another de-bubbled is poured in 2MP On I-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 of technique DEG C/2h and 240 DEG C/4h solidified and post-processed, obtain four-layer structure polymer matrix composites.
Embodiment 6
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 50 μm thick) of 2.23g are infiltrated in CEP resin, above-mentioned pre- solid on piece is placed on, excludes Bubble obtains three-decker composite material, is denoted as I-CNT/CEP of 2MP；The prepolymer of another de-bubbled is poured in 2MP On I-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 of technique DEG C/2h and 240 DEG C/4h solidified and post-processed, obtain four-layer structure polymer matrix composites.
Embodiment 7
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 60 μm thick) of 2.5g are infiltrated in CEP resin, above-mentioned pre- solid on piece is placed on, excludes gas Bubble, obtains three-decker composite material, is denoted as I-CNT/CEP of 2MP；The prepolymer of another de-bubbled is poured in 2MP I- On CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C of technique/ 2h and 240 DEG C/4h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.Its conductivity-frequency curve, Jie Electric constant-frequency curve, dielectric loss-frequency curve, breakdown strength, energy storage density are respectively as shown in attached drawing 3,4,5,6,7.
Embodiment 8
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 40 μm thick) of 1.95g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, Bubble is excluded, three-decker composite material is obtained, is denoted as 2MPII-CNT/CEP；The prepolymer of another de-bubbled is poured In on 2MPII-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h of technique + 220 DEG C/2h and 240 DEG C/4h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.
Embodiment 9
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 50 μm thick) of 2.23g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, Bubble is excluded, three-decker composite material is obtained, is denoted as 2MPII-CNT/CEP；The prepolymer of another de-bubbled is poured In on 2MPII-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C of technique/ 2h+220 DEG C/2h and 240 DEG C/4h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.
Embodiment 10
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
Two mica paper (individual is 60 μm thick) of 2.5g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, row Bubble removing obtains three-decker composite material, is denoted as 2MPII-CNT/CEP；By the prepolymer of another de-bubbled pour in On 2MPII-CNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+ of technique 220 DEG C/2h and 240 DEG C/4h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained；Its conductivity-frequency is bent Line, dielectric constant-frequency curve, dielectric loss-frequency curve, breakdown strength, energy storage density are respectively such as 3,4,5,6,7 institute of attached drawing Show.
The preparation of 1 cyanate of comparative example/epoxy curing resin
40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, sonic oscillation stirs at 90 DEG C 20min, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is poured into preheated Mold in, the vacuum outgas 30min at 150 DEG C.Then mold is put into baking oven, according to 150 DEG C/2h+180 DEG C of technique/ 2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h is solidified and is post-processed, and obtains cyanate/curable epoxide tree after cooling Rouge；Its conductivity-frequency curve, dielectric constant-frequency curve, dielectric loss-frequency curve, energy storage density respectively as attached drawing 3, 4, shown in 5,7.
The preparation of 2 carbon nanotubes of comparative example/cyanate/epoxy curing resin composite material
0.3g hydroxyl carbon nano tube, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, in Sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, Prepolymer is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into baking oven, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C of technique/2h and 240 DEG C/4h is solidified and is post-processed, and is obtained after cooling To carbon nanotube/cyanate/epoxy curing resin composite material；Its conductivity-frequency curve, dielectric constant-frequency curve, Jie Electrical loss-frequency curve, breakdown strength, energy storage density are respectively as shown in attached drawing 3,4,5,6,7.
The preparation of 3 CNT/CEP-CNT/CEP double-layer structure composite material of comparative example
By 0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51), sonic oscillation is stirred at 90 DEG C 20min is mixed, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into two etc. Part.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into baking oven, The precuring 1h at 150 DEG C obtains CNT/CEP composite material precuring piece after cooling.Another prepolymer is slowly poured at this CNT/CEP precuring on piece, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into baking oven, according to technique 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h solidified and post-processed, bilayer is obtained after cooling Structural composite material is denoted as CNT/CEP-CNT/CEP；Its dielectric constant-frequency curve, dielectric loss-frequency curve, breakdown are strong Degree, energy storage density are respectively as shown in attached drawing 4,5,6,7.
The preparation of 4 CNT/CEP-MP-CNT/CEP three-decker composite material of comparative example
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into Two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C；Mold is then put into baking In case, the precuring 1h at 150 DEG C obtains composite material precuring piece after cooling, is denoted as CNT/CEP.
By 2.5g, individual mica paper (MP, with a thickness of 120 μm) infiltrates in CEP resin, is placed on above-mentioned pre- solid on piece, excludes Bubble obtains double-layer structure composite material, is denoted as I-CNT/CEP of MP；The prepolymer of another de-bubbled is poured in MP I- On CNT/CEP；The prepolymer of another de-bubbled is poured thereon, at 150 DEG C after vacuum defoamation 30min, according to work 150/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C of skill/2h and 240 DEG C/4h is solidified and is post-processed, and it is multiple to obtain three-decker Condensation material is denoted as CNT/CEP-MP-CNT/CEP；Its dielectric constant-frequency curve, dielectric loss-frequency curve, breakdown strength, Energy storage density is respectively as shown in attached drawing 4,5,6,7.
The preparation of 5 mica powders of comparative example/CNT/CEP composite material
By 0.3gCNT, 2.5g mica powder (mica paper is mechanically pulverized), 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) mixing, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；The mixed liquor is pre- at 145 DEG C Poly- 5h.After pre-polymerization, prepolymer is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Later according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C of technique/2h and 240 DEG C/4h is solidified and is post-processed, and is obtained after cooling Mica powder/CNT/CEP composite material；Its conductivity-frequency curve, dielectric constant-frequency curve, dielectric loss-frequency curve, Breakdown strength, energy storage density are respectively as shown in attached drawing 3,4,5,6,7.
Referring to attached drawing 3, it is the four-layer structure polymer matrix composites of the preparation of the embodiment of the present invention 7 and 10, four-layer structure Carbon nanotube/cyanate/epoxy curing resin composite material of mica paper layer, the preparation of comparative example 2 in polymer matrix composites, Mica powder/CNT/CEP composite material conductivity-frequency curve prepared by comparative example 5.It can be seen that prepared by comparative example 1 The four of carbon nanotube/cyanate/epoxy curing resin composite material, the preparation of embodiment 7 and 10 prepared by CEP resin, comparative example 2 The conductivity of mica paper layer is respectively 6.3 × 10 at 100Hz in layer structural resin based composites-10S/cm、1.5×10-5 S/cm、7.2×10-10S/cm and 1.8 × 10-8S/cm.The difference of the conductivity of adjacent two layers makes interface layer charge occur Accumulation causes interfacial polarization.Conductivity difference is bigger, and charge accumulated is more, to assign composite material higher dielectric constant. Although the conductivity of the mica paper in embodiment 7 and the conductivity difference of CNT/CEP composite material are greater than the cloud in embodiment 10 The conductivity of female paper and the conductivity difference of CNT/CEP composite material, but between the mica paper and two layers of mica paper in embodiment 7 Resin CEP conductivity difference is infiltrated far below the infiltration resin CNT/CEP between the mica paper and two layers of mica paper in embodiment 10 Conductivity difference.Therefore, the four-layer structure composite material that prepared by embodiment 10 is accumulated with more interface charges, to possess More interfacial polarization layers.
The conductivity of four-layer structure polymer matrix composites prepared by embodiment 7 and 10 is only 1.2 × 10 at 100Hz- 9S/cm and 0.3 × 10-6S/cm, the carbon nanotube/cyanate/epoxy curing resin composite material point prepared compared to comparative example 2 4,2 orders of magnitude are not reduced, are shown that mica paper plays obstruction effect to the conductive path of composite inner, are reduced The leaky of composite material；And the mica paper Jing Guo CEP resin infiltration is to the obstruction effect of conductive path much larger than warp The mica paper of CNT/CEP composite material infiltration.And mica powder/CNT/CEP composite material conductivity prepared by comparative example 5 is 0.8×10-4S/cm(@100Hz), show that the addition of mica powder does not hinder the formation of its internal conductive paths not only, promotees instead It is further formed its conductive network, increases the leaky of composite material.
Referring to attached drawing 4, it is the CEP resin (comparative example 1) of comparative example preparation of the present invention, carbon nanotube/cyanate/epoxy Solidified resin composite material (comparative example 2), CNT/CEP- CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- MP-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With dielectric constant-frequency curve of the four-layer structure polymer matrix composites of 10 preparations.As seen from the figure, prepared by embodiment 7 and 10 Four-layer structure polymer matrix composites possess highest dielectric constant, at 100Hz, dielectric constant respectively reached 158, 182.The value be also it is current it has been reported that conductor/polymer-insulation laminate composite material peak.
Compared to carbon nanotube/cyanate/epoxy curing resin composite material prepared by comparative example 2, embodiment 7 and 10 is made Standby four-layer structure polymer matrix composites exist since macroscopic interface is polarized and have more high dielectric constant.But due to implementing The interfacial polarization number of plies of four-layer structure composite material prepared by example 7 is less than embodiment 10, therefore four layers of knot prepared by embodiment 10 Structure composite material has highest dielectric constant.
CNT/CEP- prepared by CNT/CEP-CNT/CEP double-layer structure composite material and comparative example 4 prepared by comparative example 3 MP-CNT/CEP three-decker composite material, they possess similar dielectric constant at 100Hz.Although CNT/CEP-MP- The thickness of individual mica paper of CNT/CEP three-decker composite material is 120 μm of four-layer structure trees prepared with embodiment 7 and 10 The thickness summation that resin-based composite two opens mica paper is equal, but four-layer structure resin base composite wood prepared by embodiment 7 and 10 There is also infiltration resin layer between two layers of mica paper of material, i.e., possess more interfacial polarization layers in structure in a limited space, Therefore possess higher dielectric constant.
Mica powder/CNT/CEP composite material dielectric constant prepared by comparative example 5 is higher than carbon nanometer prepared by comparative example 2 Pipe/cyanate/epoxy curing resin composite material value, but it is multiple far below four-layer structure resin base prepared by embodiment 7 and 10 Condensation material.This is because the addition of mica powder so that mica powder/CNT/CEP composite inner possess it is compound more than CNT/CEP The micro interface of material internal polarizes, but inside it caused by not formed macroscopic interface polarization.
Referring to attached drawing 5, it is the CEP resin (comparative example 1) of comparative example preparation of the present invention, carbon nanotube/cyanate/epoxy Solidified resin composite material (comparative example 2), CNT/CEP- CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- MP-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With dielectric loss-frequency curve of the four-layer structure polymer matrix composites of 10 preparations.CEP resin prepared by comparative example 1 does not have Conductor exists, therefore has extremely low dielectric loss.Carbon nanotube/cyanate/epoxy curing resin prepared by comparative example 2 is compound Material is since CNT content is greater than its percolation threshold, therefore it is with very high dielectric loss.CNT/CEP- prepared by comparative example 3 CNT/CEP double-layer structure composite material reduces dielectric loss due to occurring CNT tomography between two layers to a certain extent, Its dielectric loss is 3.03 at 100Hz.CNT/CEP-MP-CNT/CEP three-decker composite material prepared by comparative example 4, in Between the presence of single layer mica paper hinder the formation of conductive path, and inhibition is better than the CNT/CEP- of the preparation of comparative example 3 CNT/CEP double-layer structure composite material, therefore make which give low dielectric loss, it is 0.45 at 100Hz.Comparative example 5 is made Standby mica powder/CNT/CEP composite material has higher dielectric loss, this is because the addition of mica powder does not hinder not only The formation of its internal conductive paths promotes its conductive network to be further formed instead, increases the leaky of composite material, makes Its dielectric loss has reached 1830 at 100Hz.
Embodiment 7 and 10 prepare four-layer structure polymer matrix composites dielectric loss at 100Hz be only 0.07, 0.18.This is because two layers of mica paper and in-between infiltration resin layer have huge inhibition to the formation of conductive path, Their conductivity reduce 4 compared to carbon nanotube/cyanate/epoxy curing resin composite material prepared by comparative example 2 respectively A and 2 orders of magnitude, hinder leaky, so that them be made to have lower dielectric loss.But prepared by embodiment 7 four layers Resin is infiltrated to the inhibition of conductive network between mica paper and two mica paper in structural resin based composites Much higher than embodiment 10, therefore leaky is less, so that four-layer structure polymer matrix composites prepared by embodiment 7 Dielectric loss is far below embodiment 10.
Referring to attached drawing 6, it is carbon nanotube/cyanate/epoxy curing resin composite material of comparative example preparation of the present invention (comparative example 2), CNT/CEP- CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP-MP-CNT/CEP three-layered node Four layers of knot prepared by structure composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 and 10 The breakdown strength of paper mulberry resin-based composite.As seen from the figure, carbon nanotube/cyanate/epoxy curing resin prepared by comparative example 2 The breakdown strength of composite material is extremely low, and only 0.89.CNT/CEP-CNT/CEP double-layer structure composite material prepared by comparative example 3 Breakdown strength be slightly below CNT/CEP composite material, this is because the presence of interface layer causes electric field the lopsided institute in part occur It causes.The presence of CNT/CEP-MP-CNT/CEP three-decker composite material prepared by comparative example 4 due to layer mica paper, breakdown Intensity is improved compared to carbon nanotube/cyanate/epoxy curing resin composite material prepared by comparative example 2, but improves Amplitude is only 30%.Mica powder/CNT/CEP composite material breakdown strength prepared by comparative example 5 not because mica powder there are due to Its breakdown strength is set to be improved significantly.
Four-layer structure polymer matrix composites prepared by embodiment 7 and 10, their breakdown strength, which has respectively reached, to be compared 2.4,1.6 times of carbon nanotube/cyanate/epoxy curing resin composite material of the preparation of example 2.Due to two layers mica paper and its it Between polymer inhibition is played to the formation of conductive path, keep their breakdown strength made much larger than comparative example 2-5 Standby composite material.But the infiltration in the four-layer structure polymer matrix composites prepared due to embodiment 10 between two mica paper Polymer contains CNT, therefore CNT does not form tomography in composite inner, the four-layer structure tree prepared compared to comparative example 7 Resin-based composite is easier to cause the formation of breakdown path.Therefore, four-layer structure polymer matrix composites prepared by embodiment 7 With higher breakdown strength.
Referring to attached drawing 7, it is the CEP resin (comparative example 1) of comparative example preparation of the present invention, carbon nanotube/cyanate/epoxy Solidified resin composite material (comparative example 2), CNT/CEP- CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP- MP-CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 With the energy storage density of the four-layer structure polymer matrix composites of 10 preparations.As seen from the figure, four-layer structure prepared by embodiment 7 and 10 Polymer matrix composites have highest energy storage density, the carbon nanotube/cyanate/curable epoxide prepared compared to comparative example 2 The amplification of resin composite materials is up to 1550%, 880% respectively.This is because the energy storage density of linear material be proportional to respectively it is compound The dielectric constant of material and square of breakdown strength, therefore, four-layer structure polymer matrix composites rely on higher breakdown strength Higher energy storage density has been obtained with dielectric constant.Although the dielectric of four-layer structure polymer matrix composites prepared by embodiment 7 Constant is lower than embodiment 10, but its breakdown strength is 1.5 times of composite material prepared by embodiment 10.And their energy storage Density is proportional to square of breakdown strength, therefore four-layer structure polymer matrix composites prepared by embodiment 7 possess highest storage It can density.
Referring to table 1, it is that CEP resin (comparative example 1), carbon nanotube/cyanate/epoxy prepared by comparative example of the present invention are solid Change resin composite materials (comparative example 2), CNT/CEP-CNT/CEP double-layer structure composite material (comparative example 3), CNT/CEP-MP- CNT/CEP three-decker composite material (comparative example 4), mica powder/CNT/CEP composite material (comparative example 5) and embodiment 7 and 10 The dielectric constants of the four-layer structure polymer matrix composites of preparation, dielectric loss, energy storage density are compared with their energy storage density In carbon nanotube/cyanate/epoxy curing resin composite material amplification prepared by comparative example 2.As shown in Table 1,7 He of embodiment The four-layer structure polymer matrix composites of 10 preparations have higher dielectric constant, and 158,182 have been respectively reached at 100Hz. This is because four-layer structure polymer matrix composites prepared by embodiment 7 and 10 possess more boundaries in structure in a limited space The accumulation of surface charge, so as to cause the polarization of more macroscopic interfaces.Therefore, they obtain highest dielectric constant.Meanwhile two The four-layer structure polymer matrix composites that the presence for opening mica paper prepares embodiment 7 are answered compared to prepared by comparative example 2-5 Condensation material is able to bear higher voltage, obtains higher breakdown strength.Although cyanate/curable epoxide prepared by comparative example 1 Resin has high breakdown strength, but the dielectric constant point of the four-layer structure polymer matrix composites of the preparation of embodiment 7 and 10 It is not prepared by comparative example 1 52,60 times of cyanate/epoxy curing resin (@100Hz).Therefore the four of the preparation of embodiment 7 and 10 Layer structural resin based composites are obtained by big dielectric constant and high breakdown strength much higher than comparative example 1-5 preparation The energy storage density of composite material.
Four-layer structure polymer matrix composites prepared by embodiment 7 and 10 are compared to composite material prepared by comparative example 2-5 With lower dielectric loss, this is because two mica paper and the infiltration resin layer between them make the obstruction of conductive path With electric leakage image more greatly, is significantly reduced, so that the loss of material is greatly reduced.
The correlation performance parameters of material prepared by 1 comparative example 1-5 of table and embodiment 7 and 10
Compared with carbon nanotube/cyanate/epoxy curing resin composite material prepared by comparative example 2, although other compare The energy storage density of the composite material of example preparation is improved, but amplification is far below four-layer structure resin prepared by embodiment 7 and 10 Based composites (1550%, 880%).This be also it is current it has been reported that conductor/polymer-insulation laminate composite material In highest amplification.
Embodiment 11
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.8g carboxylated single-walled carbon nanotube, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, Sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.Pre-polymerization terminates Afterwards, prepolymer is divided into two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.And Mold is put into baking oven afterwards, the precuring 1h at 150 DEG C, obtains carboxylated single-walled carbon nanotube (SCNT)/CEP tree after cooling Resin composite material precuring piece.
Two mica paper (individual is 60 μm thick) of 2.5g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, row Bubble removing obtains three-decker composite material, is denoted as I-SCNT/CEP of 2MP；By the prepolymer of another de-bubbled pour in On I-SCNT/CEP of 2MP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+ of technique 220 DEG C/2h and 240 DEG C/6h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.
Embodiment 12
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
By 0.2g multi-walled carbon nanotube, 0.2g single-walled carbon nanotube and 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) mixing, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；The mixed liquor is pre- at 145 DEG C Poly- 5h.After pre-polymerization, prepolymer is divided into two equal portions.Wherein 1 part is poured into preheated mold, the vacuum at 150 DEG C De-bubbled 30min.Then mold is put into baking oven, the precuring 1h at 150 DEG C, mixing carbon nanotube is obtained after cooling (HCNT)/CEP resin composite materials precuring piece.
Two mica paper (individual is 60 μm thick) of 2.5g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, row Bubble removing obtains three-decker composite material, is denoted as 2MPII-HCNT/CEP；By the prepolymer of another de-bubbled pour in On 2MPII-HCNT/CEP, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C of technique / 2h+220 DEG C/2h and 220 DEG C/8h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.
Embodiment 13
0.3gCNT, 40g bisphenol A cyanate ester and 10g epoxy resin (trade mark E-51) are mixed, the ultrasound vibration at 90 DEG C Stirring 20min is swung, be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain resin, be denoted as CNT/CEP, make To can be thermally cured resin liquid.
0.2g multi-walled carbon nanotube, 40g bisphenol A cyanate ester and 10g N, N ' -4,4 '-diphenyl-methane span are carried out into acyl Imide monomers mixing, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By mixed liquor pre-polymerization at 145 DEG C 5h.After pre-polymerization, prepolymer is divided into two equal portions.Wherein 1 part is poured into preheated mold, vacuum is de- at 150 DEG C Bubble 30min.Then mold is put into baking oven, the precuring 1h at 150 DEG C, obtains multi-walled carbon nanotube/cyanic acid after cooling Ester-bismaleimide resin composite material precuring piece, is denoted as MWCNT/CEM.
Two mica paper (individual is 60 μm thick) of 2.5g are infiltrated in CNT/CEP resin, are placed on above-mentioned pre- solid on piece, row Bubble removing obtains three-decker composite material, is denoted as 2MPII-MWCNT/CEM；The prepolymer of another de-bubbled is poured In on 2MPII-MWCNT/CEM, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C of technique/ 2h+220 DEG C/2h and 220 DEG C/8h is solidified and is post-processed, and four-layer structure polymer matrix composites are obtained.
Embodiment 14
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
By 0.16g single-walled carbon nanotube, 28.74g N, N ' -4,4 '-diphenyl methane dimaleimide and 21.26g 2, The mixing of 2 '-diallyl bisphenols, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；The mixed liquor is existed Pre-polymerization 5h at 145 DEG C.After pre-polymerization, prepolymer is divided into two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into baking oven, the precuring 1h at 150 DEG C, obtains single wall after cooling Carbon nanotube/bismaleimide resin composite material precuring piece, is denoted as SWCNT/BD.
2.23g two is opened into mica paper (individual is 50 μm thick) in CEP resin infiltration, above-mentioned pre- solid on piece is placed on, excludes bubble, Three-decker composite material is obtained, I-CNT/BD of 2MP is denoted as；The prepolymer of another de-bubbled is poured in I-CNT/ of 2MP On BD, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 240 DEG C/4h of technique Solidified and post-processed, obtains four-layer structure polymer matrix composites.
Embodiment 15
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.5gCNT and 50g bisphenol A cyanate ester is mixed, sonic oscillation stirs 20min at 90 DEG C, is uniformly mixed Close liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h.After pre-polymerization, prepolymer is divided into two equal portions.Will wherein 1 part pour into it is pre- In the good mold of heat, 30min is steeped in vacuum outgas at 150 DEG C.Then mold is put into baking oven, the precuring 1h at 150 DEG C, CNT/ cyanate ester resin composite material precuring piece is obtained after cooling, is denoted as CNT/CE.
1.95g two is opened mica paper (individual is 40 μm thick) to infiltrate in CEP resin, above-mentioned pre- solid on piece is placed on, excludes gas Bubble, obtains three-decker composite material, is denoted as I-CNT/CE of 2MP；The prepolymer of another de-bubbled is poured in 2MP I- On CNT/CE, at 150 DEG C after vacuum defoamation 30min, according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h of technique Solidified and post-processed with 250 DEG C/3h, obtains four-layer structure polymer matrix composites.
Embodiment 16
By bis- (the 4- cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 40g2,2'- and 10g epoxy resin (trade mark E- 51) it mixes, sonic oscillation stirs 20min at 90 DEG C, and be uniformly mixed liquid；By the mixed liquor at 145 DEG C pre-polymerization 5h, obtain To resin, it is denoted as CEP, as can be thermally cured resin liquid.
0.7g CNT and 50g epoxy resin (trade mark E-44) monomer is mixed, sonic oscillation stirs 20min at 80 DEG C, Be uniformly mixed liquid；The mixed liquor is added into 2g triethylene diamine (curing agent) pre-polymerization 30min at 80 DEG C.After pre-polymerization, Prepolymer is divided into two equal portions.Wherein 1 part is poured into preheated mold, 30min is steeped in vacuum outgas at 80 DEG C.Then Mold is put into baking oven, the precuring 1h at 80 DEG C, obtains CNT/ epoxy resin composite material precuring piece after cooling, be denoted as CNT/EP。
1.35g two is opened mica paper (individual is 28 μm thick) to infiltrate in CEP resin, above-mentioned pre- solid on piece is placed on, excludes gas Bubble, obtains three-decker composite material, is denoted as I-CNT/EP of 2MP；The prepolymer of another de-bubbled is poured in 2MP I- On CNT/EP, at 80 DEG C after vacuum defoamation 30min, carried out according to the technique of 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h of technique Solidify and post-process 4h at 150 DEG C, obtains four-layer structure polymer matrix composites.

Claims (9)

1. a kind of preparation method of four-layer structure polymer matrix composites, which comprises the steps of:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains pre- Polymers；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, obtains carbon nanotube/thermosetting resin precuring piece A；
(3) two mica paper are infiltrated respectively after can be thermally cured resin liquid, be successively laid in step (2) preparation carbon nanotube/ On thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, then Solidified to obtain the four-layer structure polymer matrix composites.
2. the preparation method of four-layer structure polymer matrix composites according to claim 1, it is characterised in that: the carbon nanometer Pipe is single-walled carbon nanotube and/or multi-walled carbon nanotube；The non-surface treated of the carbon nanotube or surface treated.
3. the preparation method of four-layer structure polymer matrix composites according to claim 1, it is characterised in that: the thermosetting property Resin system includes thermosetting resin or the aathermoset resin system includes thermosetting resin and curing agent；It is described can thermosetting Change that resin liquid is obtained by can be thermally cured resin prepolymer or the resin liquid that can be thermally cured is by can be thermally cured resin and conductive filler Pre-polymerization obtains.
4. the preparation method of four-layer structure polymer matrix composites according to claim 3, it is characterised in that: the thermosetting property Resin includes one or more of cyanate ester resin, bimaleimide resin, epoxy resin；It is described to can be thermally cured resin packet Include one or more of cyanate ester resin, bimaleimide resin, epoxy resin.
5. the preparation method of four-layer structure polymer matrix composites according to claim 1, it is characterised in that: in step (1), The temperature of pre-polymerization is 90~150 DEG C, and the time is 4~6 hours；In step (2), the temperature of precuring is 140~160 DEG C, the time It is 0.5~2 hour；In step (4), cured temperature is 150~240 DEG C, and the time is 10~12 hours.
6. a kind of preparation method of four-layer structure polymer matrix composites presoma, which comprises the steps of:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains pre- Polymers；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, obtains carbon nanotube/thermosetting resin precuring piece A；
(3) two mica paper are infiltrated respectively after can be thermally cured resin liquid, be successively laid in step (2) preparation carbon nanotube/ On thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, is obtained Four-layer structure polymer matrix composites presoma.
7. the preparation method of four-layer structure polymer matrix composites presoma according to claim 6, it is characterised in that: institute Stating carbon nanotube is single-walled carbon nanotube and/or multi-walled carbon nanotube；The non-surface treated of the carbon nanotube or through surface at Reason；The aathermoset resin system includes thermosetting resin or the aathermoset resin system includes thermosetting resin and solidification Agent；It is described to can be thermally cured that resin liquid is obtained by can be thermally cured resin prepolymer or the resin liquid that can be thermally cured is by can be thermally cured tree Rouge is obtained with conductive filler pre-polymerization；In step (1), the temperature of pre-polymerization is 90~150 DEG C, and the time is 4~6 hours；Step (2) In, the temperature of precuring is 140~160 DEG C, and the time is 0.5~2 hour.
8. the preparation method of four-layer structure polymer matrix composites presoma according to claim 7, it is characterised in that: institute Stating thermosetting resin includes one or more of cyanate ester resin, bimaleimide resin, epoxy resin；It is described can thermosetting Changing resin includes one or more of cyanate ester resin, bimaleimide resin, epoxy resin.
9. a kind of four-layer structure polymer matrix composites presoma, which is characterized in that the four-layer structure resin base composite wood The preparation method of material presoma includes the following steps:
(1) by weight, 100 parts of aathermoset resin systems are mixed with 0.1~1.8 part of carbon nanotube；Then pre-polymerization obtains pre- Polymers；
(2) half for the prepolymer for taking step (1) to prepare carries out precuring, obtains carbon nanotube/thermosetting resin precuring piece A；
(3) two mica paper are infiltrated respectively after can be thermally cured resin liquid, be successively laid in step (2) preparation carbon nanotube/ On thermosetting resin precuring piece A, three-decker composite material B is obtained；
(4) half for the prepolymer for taking step (1) to prepare is poured on the three-decker composite material B of step (3) preparation, is obtained Four-layer structure polymer matrix composites presoma.
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