CN107793679A - A kind of core-shell nano/polyvinylidene fluoride composite material and preparation method thereof - Google Patents

A kind of core-shell nano/polyvinylidene fluoride composite material and preparation method thereof Download PDF

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CN107793679A
CN107793679A CN201711236815.XA CN201711236815A CN107793679A CN 107793679 A CN107793679 A CN 107793679A CN 201711236815 A CN201711236815 A CN 201711236815A CN 107793679 A CN107793679 A CN 107793679A
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CN107793679B (en
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隋刚
汪汇源
杨小平
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Beijing University of Chemical Technology
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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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-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
    • 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
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a kind of core-shell nano/polyvinylidene fluoride composite material and preparation method thereof, belong to technical field of composite materials.Core-shell nano/polyvinylidene fluoride composite material of the present invention is combined by three-layer nuclear shell nanoparticle doped into Kynoar, the core of wherein described three-layer nuclear shell nano-particle is silica, first layer shell is that reduction-oxidation graphite is dilute, and second layer shell is chitosan.The preparation method includes：Silane coupling agent KH550 is grafted to SiO2Nanoparticle surface, graphene oxide cladding, three-layer nuclear shell nano-particle is prepared, three-layer nuclear shell nano-particle is added to Kynoar with the mixed solution of N N-dimethylformamides, removing the step such as bubble, heating film.Core-shell nano/polyvinylidene fluoride composite material prepared by the present invention has the characteristics of high-k, low-dielectric loss, and preparation technology is simple, and cost is low, and industrialized production and application are carried out suitable for various types of factories.

Description

A kind of core-shell nano/polyvinylidene fluoride composite material and preparation method thereof
Technical field
The present invention relates to a kind of polyvinylidene fluoride composite material, contains three-layer nuclear shell structure nanoparticle more particularly to one kind The high-k of son, polyvinylidene fluoride composite material of low-dielectric loss and preparation method thereof, belong to field of compound material.
Technical background
With the fast development of global IT application and electronics industry, higher performance requirement is proposed to electric equipment.Cause This, prepares polymer matrix composite, because it has concurrently well by dielectric substance and polymeric matrix by certain combination process Manufacturability, pliability and dielectric properties, and it is increasingly becoming a kind of trend of current high dielectric material research field.At present, it polymerize Thing base dielectric composite material is broadly divided into two major classes：That is ceramics polymer based composites and electric conductor polymer matrix composite wood Material.
Kynoar（Kynoar）It is a kind of thermoplastic resin, the most frequently used dielectric polymer matrix.Gather inclined fluorine The dielectric properties of ethene are very prominent, and when frequency is 1kHz, dielectric constant is up to 8-12, and dielectric loss is about 0.03-0.2, And energy storage density is high, there is good chemical resistance, processability and high temperature resistant, fatigue resistance etc., can be by filler modified or common The methods of mixed modification the excellent dielectric composite material of processability.
Dielectric loss refers to dielectric in alternating electric field, makes what dielectric generated heat in itself to show due to consumption part electric energy As.Reason, in dielectric containing can be conductive carrier, under DC Electric Field, produce conductive current, consume a part Electric energy, switch to heat energy.Represent one of index of insulation quality.
The dielectric constant of Kynoar is improved, mainly there are two kinds of approach at present：The first approach is addition ceramic packing, Ceramic packing dielectric constant itself is higher, but does not cause interfacial polarization weaker very much with electrostrictive polymer performance difference due to ceramic, because This composite dielectric constant is only capable of reaching 50-100 or so at room temperature；Meanwhile to reach dielectric constant so far, pottery The content of porcelain body, which usually requires that, reaches more than 50vol%, but high content can cause the uniformity of composite, manufacturability and soft Toughness substantially reduces；Second of approach is addition conductive filler, and conductive filler produces strong boundary by huge electrical property difference Surface polarization effect, form micro- capacitance structure or trigger seep effect to greatly improve composite dielectric constant, contain relatively low Composite dielectric constant is greatly improved under amount, but the dielectric loss for causing system simultaneously increased dramatically.
Graphene has high-modulus, high intensity and excellent electric conductivity, therefore is often doped to it as conductive filler Material dielectric constant is improved in polymeric matrix., also can be with gathering partially and chitosan can be as the insulating coating of graphenic surface Fluoride-based body forms a good interfacial effect.In order to improve the electric property of Kynoar, while it is not reduced again Intensity, the present invention propose a kind of brand-new three-layer nuclear shell nano-particle, it is doped in Kynoar, can improve it Dielectric constant, reduce dielectric loss.
The content of the invention
It is a primary object of the present invention to provide the three-layer nuclear shell structure nanoparticle of a kind of high-k, low-dielectric loss Son/polyvinylidene fluoride composite material and preparation method thereof, wherein, the core-shell nano/polyvinylidene fluoride composite material by Three-layer nuclear shell nanoparticle doped is combined into Kynoar, wherein the core of the three-layer nuclear shell nano-particle is dioxy SiClx, from inner outside, first layer shell is the dilute layer of reduction-oxidation graphite, and second layer shell is chitosan layer.
Present invention also offers the preparation method of the core-shell nano/polyvinylidene fluoride composite material, specifically include Following steps：
Step 1：Silane coupling agent KH550 is grafted to SiO2Nanoparticle surface, obtain being grafted with Silane coupling agent KH550 SiO2Nano-particle.
Step 2：Graphene oxide is wrapped in by the method for Electrostatic Absorption silane coupler is grafted with made from step 1 KH550 SiO2Nanoparticle surface, obtain the SiO of graphene oxide layer parcel2Nano-particle.
Step 3：The SiO that graphene oxide layer is wrapped up2Nano-particle is dispersed in acetic acid solution, and adds chitosan, 1-（3- dimethyl propyls）- 3- ethyl-carbodiimide hydrochlorides and n-hydroxysuccinimide, reaction add anti-bad after terminating The further redox graphene of hematic acid, it is SiO to obtain kernel2, first layer shell is redox graphene, and second layer shell is shell The core-shell nano of glycan, as three-layer nuclear shell nano-particle.
Step 4：The mixing that the three-layer nuclear shell nano-particle is added into Kynoar and N-N dimethylformamides is molten In liquid, it is well mixed, removes bubble, heating film, three-layer nuclear shell structure nanoparticle doped Kynoar composite wood is made Material.
Further, it is described that Silane coupling agent KH550 is grafted to SiO2The step of nanoparticle surface, is as follows：By titanium dioxide Silicon, anhydrous acetic acid, absolute ethyl alcohol and KH550 mixing, sealing, and using 90 ± 10w 30 ~ 45min of supersound process, after be placed in 50 ± 3 DEG C of oil bath 20 ~ 24h of stirring reaction, after the completion of reaction, centrifuge washing drying, obtain being grafted with Silane coupling agent KH550 SiO2Nano-particle, wherein, described silica accounts for 1.5-2.5% (m/V), and anhydrous acetic acid accounts for 1.5-2.5% (V/V), nothing Water-ethanol accounts for 95-97% (V/V), and KH550 accounts for 1.5-2.5% (V/V).
Further, the method for the Electrostatic Absorption is：By silicane coupling agent surface grafted KH550 SiO2Nano-particle point Dissipate in deionized water, ultrasonic disperse, and add graphene oxide water solution, be sufficiently stirred, filter, obtain graphene oxide layer The SiO of parcel2Nano-particle.Wherein, described graphene oxide accounts for 0.003-0.005% (m/V).
Further, pH=4 ~ 5 of the acetic acid solution.
Further, the addition of the chitosan accounts for 0.003-0.008% (m/V), 1-（3- dimethyl propyls）- 3- ethyls The addition of carbodiimide hydrochloride accounts for 0.011-0.025% (m/V), and the addition of n-hydroxysuccinimide accounts for 0.013- 0.029% (m/V)。
Further, the addition of the ascorbic acid accounts for 0.016-0.019% (m/V).
Further, in the mixed solution of the Kynoar and N-N dimethylformamides, Kynoar：N-N diformazans Base formamide=0.5g:10mL~2g:10mL.
Further, the temperature of the heating film is 120 ± 2 DEG C.
Further, the core-shell nano/polyvinylidene fluoride composite material be used for prepare electric apparatus, integrated circuit and The insulating materials of cable.
Beneficial effect
This patent provides a kind of three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material, wherein, described three-layer nuclear shell is received The kernel of rice corpuscles is SiO2, and first layer shell is redox graphene, and second layer shell is chitosan, proposed by the present invention The single presence of SiO2@redox graphene@chitosan three-layer nuclear shell nano-particles, and can stablize, be uniformly dispersed in In Kynoar matrix, good interfacial effect is formed with matrix.Reduction-oxidation in the three-layer nuclear shell structure nano-particle Graphene shell produces strong interfacial polarization as electric conductor filler by huge electrical property difference between Kynoar Effect, while single core-shell particles form micro- capacitance structure, greatly improve composite dielectric constant, and its outer shell gathers Sugared shell has then obstructed the formation of the conductive network of redox graphene in system as insulating barrier, it is suppressed that its seepage flow is imitated Should, dielectric loss is maintained into a relatively low level, the two jointly for composite system provide high dielectric constant with Low dielectric loss, while SiO2Mechanical property supporter of the kernel as whole system, three has a fusion well And complementation.The present invention uses ascorbic acid as reducing agent so that graphene oxide can sufficiently be reduced into oxygen reduction fossil Black alkene, while the shelling stability of chitosan is nor affected on, three layers of independent core shell structure are formd, its performance does not change Become.
High-k, the three-layer nuclear shell structure nanoparticle doped of low-dielectric loss prepared by test, the present invention The dielectric constant of polyvinylidene fluoride composite material is 18.6, and under conditions of test frequency is 1kHz, its dielectric loss is 0.059.As can be seen here, the composite has high-k, low-dielectric loss.The composite that simultaneously prepared by the present invention Possess the advantages that good mechanical property, heat conductivility and chemical stability, the composite prepared by test, the present invention Tensile strength is between 41 ~ 50MPa.
High-k prepared by the present invention, three-layer nuclear shell structure nano-particle/Kynoar of low-dielectric loss are multiple Condensation material can be applied in fields such as electric apparatus, integrated circuit and insulated cables.Its preparation cost is low, the letter of preparation technology flow It is single, carry out industrialized production and application suitable for various types of factories.
Embodiment
By following examples and comparative example, the present invention is described in detail, but the present invention is not limited to following implementation Example.The dielectric properties data of composite use the Novocontrol wideband dielectrics of German Novocontrol GmbH companies Impedance spectrometer is tested.
Embodiment 1：
A kind of three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material of the present embodiment offer, the three-layer nuclear shell nano-particle/ Polyvinylidene fluoride composite material is prepared from the following components, specific as follows：
Component 1：SiO2Nano-particle, average grain diameter 500nm, the production of Alfa Aesar companies of the U.S.；
Component 2：Silane coupling agent KH550, purity >=97%, the production of Shanghai Mike woods Reagent Company；
Component 3：Graphene oxide powder, 0.5-5 μm of particle diameter, thickness 1-3nm, the life of Nanjing Xian Feng Nono-material Science ＆ Technology Ltd. Production；
Component 4：Chitosan, high viscosity >=400mPa.s, the production of Shanghai Aladdin Reagent Company；
Component 5：Ascorbic acid, purity >=99%, the production of Shanghai Aladdin Reagent Company；
Component 6：Kynoar, the production of Alfa Aesar companies of the U.S.；
Component 7：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
The preparation method of the three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material is as follows：
Step 1：Component 2 is grafted to the surface of component 1, obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Wherein, the step of grafting is as follows：By 2g silica, 2mL anhydrous acetic acids, 96mL absolute ethyl alcohols, 2mLKH550 mix, sealing, and using 90 ± 10w supersound process 30min, after be placed in 50 ± 3 DEG C of oil bath stirring reaction 20h, After the completion of reaction, centrifuge washing is dried, and obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Step 2：Graphene oxide is wrapped in by the method for Electrostatic Absorption silane coupler is grafted with made from step 1 KH550 SiO2Nanoparticle surface.
Wherein, the specific method is as follows：By the SiO of the silicane coupling agent surface grafted KH550 prepared by 2g steps 12 Nano-particle is dispersed in 300mL deionized waters, ultrasonic disperse 0.5h, 2 equal portions is then divided into, first to first part of decile It is 1mg/mL graphene oxide water solutions that 5mL concentration is added dropwise in liquid, and after being slowly stirred 1h, the liquid separation such as second part is also slowly fallen Enter, be 1mg/mL graphene oxide water solutions equally to mixed solution and dripping 5mL concentration, afterwards after being slowly stirred 1h again After stirring 24h, by filtering, the SiO of graphene oxide layer parcel is finally given2Nano-particle.
Step 3：It is SiO to prepare kernel2, first layer shell is redox graphene, and second layer shell is the nucleocapsid of chitosan Nano-particle.
The SiO that the graphene oxide layer prepared in step 2 is wrapped up2Nano-particle is all dispersed in 300mL and pH=5 In acetic acid solution, while 0.01g chitosans are added, be ultrasonically treated 0.5 ~ 2h, then add 0.033g 1-（3- dimethyl propylenes Base）- 3- ethyl-carbodiimide hydrochlorides and 0.039g n-hydroxysuccinimides, at room temperature after 6 ~ 8h of water-bath stirring 18 ~ 24h, after reaction stops, 0.05g ascorbic acid is added, in 90 ± 3 DEG C of 0.5 ~ 1.5h of heating response, vacuum filtration washs, Freeze-drying, you can obtain SiO2Nanoparticle surface wraps up one layer of redox graphene and one layer of chitosan, wherein shell gather Outer layer of the sugar layer in redox graphene layer.Finally give a kind of three-layer nuclear shell nano-particle.
Step 4：The three-layer nuclear shell nano-particle that step 3 is obtained is according to 1.1%（m/V）Addition be added to poly- inclined fluorine In the mixed solution of ethene and N-N dimethylformamides, wherein, the mixing of the Kynoar and N-N dimethylformamides In solution, Kynoar：N-N dimethylformamides=1g:10mL.Stirred after being thoroughly mixed, then by vacuumizing removing Bubble, it is film-made using linear film rod, is heated on the flat heater platform that temperature setting is 120 ± 5 DEG C, three-layer nuclear shell knot is made Structure nanoparticle doped polyvinylidene fluoride composite material.
By test, the dielectric constant for three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material that the present embodiment obtains For 18.6, in the case where test frequency is 1kHz test condition, dielectric loss 0.057.
For the core-shell nano with the dilute@chitosans of silica@reduction-oxidation graphite prepared in embodiment 1/poly- Vinylidene composite is compareed, and inventor selects 4 control groups, is respectively：Only add silica oxygen reduction fossil The polyvinylidene fluoride composite material of the dilute preparation of ink（Control group 1）, only add the dilute preparation of reduction-oxidation graphite Kynoar answer Condensation material（Control group 2）, only add silica prepare polyvinylidene fluoride composite material（Control group 3）Answered with Kynoar Condensation material（Control group 4）, the consumption proportion for the reagents such as Kynoar, SiO 2 powder, reduction-oxidation graphite is dilute, Yi Jifu The mixing of laminate resin system, filming technology are same as Example 1, and concrete operations are as follows：
Control group 1：
Component 1：SiO2Nano-particle, average grain diameter 500nm, the production of Alfa Aesar companies of the U.S..
Component 2：Silane coupling agent KH550, purity >=97%, the production of Shanghai Mike woods Reagent Company.
Component 3：Graphene oxide powder, 0.5-5 μm of particle diameter, thickness 1-3nm, the limited public affairs of Nanjing Xian Feng nano materials science and technology Department's production.
Component 4：Ascorbic acid, purity >=99%, the production of Shanghai Aladdin Reagent Company.
Component 5：Kynoar, the production of Alfa Aesar companies of the U.S..
Component 6：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
Component 2 is grafted to by the surface of component 1 using identical method, obtains being grafted with the SiO of Silane coupling agent KH5502 Nano-particle, the graphene oxide of component 3 is wrapped in by aoxidizing Electrostatic Absorption and is grafted with the SiO of Silane coupling agent KH5502 Nanoparticle surface, and reduced graphene oxide with component 4, SiO in obtained core-shell structure nanometer particle2With going back The mass ratio of former graphene oxide is 200：1.The core-shell nano is added in the mixed solution of component 5 and component 6, Stir, then by vacuumizing removing bubble, be film-made using linear film rod, in the flat heater that temperature setting is 120 DEG C Heated on platform, silica@redox graphenes core-shell structure nanometer particle doping polyvinylidene fluoride composite material is made.Its The ratio of middle Kynoar and N-N dimethylformamide is Kynoar：DMF=1g:10mL, the nuclear shell structure nano grain The mass ratio of son and Kynoar is 1：9.
The dielectric constant of silica@redox graphenes core-shell nano/polyvinylidene fluoride composite material is 17.6, dielectric loss is 0.089 under conditions of test frequency is 1kHz.
Control group 2：
Component 1：Graphene oxide powder, 0.5-5 μm of particle diameter, thickness 1-3nm, Nanjing Xian Feng Nono-material Science ＆ Technology Ltd. Production.
Component 2：Ascorbic acid, purity >=99%, the production of Shanghai Aladdin Reagent Company.
Component 3：Kynoar（Kynoar）, the production of Alfa Aesar companies of the U.S..
Component 4：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
Component 2 will be added in component 1, obtain redox graphene, and be added to the mixed solution of component 3 and component 4 In, stir, then by vacuumizing removing bubble, be film-made using linear film rod, add in the flat board that temperature setting is 120 DEG C Heated in thermal station, redox graphene nanoparticle doped polyvinylidene fluoride composite material is made.Wherein, Kynoar with The ratio of N-N dimethylformamides is Kynoar：DMF=1g：The matter of 10mL, redox graphene and Kynoar Amount is than being 1：2000.
The dielectric constant of the redox graphene nano-particle/polyvinylidene fluoride composite material is 28.8, in test frequency When rate is 1kHz, dielectric loss 0.485.
Control group 3：
Component 1：SiO2Nano-particle, average grain diameter 500nm, the production of Alfa Aesar companies of the U.S..
Component 2：Silane coupling agent KH550, purity >=97%, the production of Shanghai Mike woods Reagent Company.
Component 3：Kynoar（Kynoar）, the production of Alfa Aesar companies of the U.S..
Component 4：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
Component 2 is grafted to the surface of component 1, the ratio of Nano particles of silicon dioxide and Silane coupling agent KH550 is SiO2： KH550=1g：1mL, obtain being grafted with the SiO of Silane coupling agent KH5502Nano-particle.Silane coupler is grafted with by described KH550 SiO2Nano-particle is added in the mixed solution of component 3 and component 4, is stirred, then by vacuumizing removing gas Bubble, it is film-made using linear film rod, is heated on the flat heater platform that temperature setting is 120 DEG C, SiO is made2Nano-particle is mixed Miscellaneous polyvinylidene fluoride composite material.The ratio of Kynoar and N-N dimethylformamides is Kynoar：DMF=1g： 10mL, SiO2The mass ratio of nano-particle and Kynoar is 1：9.
The dielectric constant of the SiO2 nano-particles/polyvinylidene fluoride composite material is 9.19, is 1kHz's in test frequency Under test condition, dielectric loss 0.0563.
Control group 4：
Component 1：Kynoar（Kynoar）, the production of Alfa Aesar companies of the U.S..
Component 2：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
Component 1 and component 2 are mixed, obtain homogeneous solution, then by vacuumizing removing bubble, uses linear film Rod is film-made, and is heated on the flat heater platform that temperature setting is 120 DEG C, polyvinylidene fluoride composite material is made.Kynoar Ratio with N-N dimethylformamides is Kynoar：DMF=1g：10mL.
The dielectric constant of the polyvinylidene fluoride composite material is 8.48, in the case where test frequency is 1kHz test condition, is situated between Electrical loss is 0.0237.
As a result show the reduction-oxidation graphite it is dilute/dielectric constant of polyvinylidene fluoride composite material is 28.8, dielectric loss For 0.485（Test frequency is 1kHz）.And the dielectric constant of pure polyvinylidene fluoride composite material is 8.48, dielectric loss is 0.0237（Test frequency is 1kHz）.Compared with embodiments of the invention 1, it is multiple that three-layer nuclear shell nano-particle/PVDF can be protruded The high-k of condensation material and the performance advantage of low-dielectric loss.
Embodiment 2：
A kind of three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material of the present embodiment offer, the three-layer nuclear shell nano-particle/ Polyvinylidene fluoride composite material is prepared from the following components, specific as follows：
Component 1：SiO2Nano-particle, particle diameter are 400 ~ 600nm, and Alfa Aesar companies of the U.S. produce；
Component 2：Silane coupling agent KH550, purity >=97%, the production of Shanghai Mike woods Reagent Company；
Component 3：Graphene oxide powder, 0.5-5 μm of particle diameter, thickness 1-3nm, the life of Nanjing Xian Feng Nono-material Science ＆ Technology Ltd. Production；
Component 4：Chitosan, high viscosity >=400mPa.s, the production of Shanghai Aladdin Reagent Company；
Component 5：Ascorbic acid, purity >=99%, the production of Shanghai Aladdin Reagent Company；
Component 6：Kynoar, the production of Alfa Aesar companies of the U.S.；
Component 7：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
The preparation method of the three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material is as follows：
Step 1：Component 2 is grafted to the surface of component 1, obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Wherein, the step of grafting is as follows：By 2.5g silica, 2.5mL anhydrous acetic acids, 95mL absolute ethyl alcohols, 2.5mLKH550 mix, sealing, and using 90 ± 10w supersound process 45min, after be placed in 50 ± 3 DEG C of oil bath stirring reactions 24h, after the completion of reaction, centrifuge washing is dried, and obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Step 2：Graphene oxide is wrapped in by the method for Electrostatic Absorption silane coupler is grafted with made from step 1 KH550 SiO2Nanoparticle surface.
Wherein, the specific method is as follows：By the silicane coupling agent surface grafted KH550's prepared by 2.5g steps 1 SiO2Nano-particle is dispersed in 400mL deionized waters, ultrasonic disperse 2h, 2 equal portions is then divided into, first to first part etc. It is 2mg/mL graphene oxide water solutions that 3.125mL concentration is added dropwise in liquid separation, and after being slowly stirred 2h, the liquid separation such as second part is also delayed Slowly pour into, be that 2mg/mL graphene oxides are water-soluble equally to mixed solution and dripping 3.125mL concentration after being slowly stirred 2h again Liquid, after stirring 36h afterwards, filter, finally give the SiO of graphene oxide layer parcel2Nano-particle.
Step 3：It is SiO to prepare kernel2, first layer shell is redox graphene, and second layer shell is the nucleocapsid of chitosan Nano-particle.
The SiO that the graphene oxide layer prepared in step 2 is wrapped up2Nano-particle is all dispersed in 400mL and pH=4 In acetic acid solution, while 0.02g chitosans are added, be ultrasonically treated 0.5 ~ 2h, then add 0.065g 1-（3- dimethyl propylenes Base）- 3- ethyl-carbodiimide hydrochlorides and 0.078g n-hydroxysuccinimides, at room temperature after 6 ~ 8h of water-bath stirring 18 ~ 24h, after reaction stops, 0.063g ascorbic acid is added, in 90 ± 3 DEG C of 0.5 ~ 1.5h of heating response, vacuum filtration washs, Freeze-drying, you can obtain SiO2Nanoparticle surface wraps up one layer of redox graphene and one layer of chitosan, wherein shell gather Outer layer of the sugar layer in redox graphene layer.Finally give a kind of three-layer nuclear shell nano-particle.
Step 4：The three-layer nuclear shell nano-particle that step 3 is obtained is according to 2.2%（m/V）Addition be added to poly- inclined fluorine In the mixed solution of ethene and N-N dimethylformamides, wherein, the mixing of the Kynoar and N-N dimethylformamides In solution, Kynoar：N-N dimethylformamides=2g:10mL.Stirred after being thoroughly mixed, then by vacuumizing removing Bubble, it is film-made using linear film rod, is heated on the flat heater platform that temperature setting is 120 ± 5 DEG C, three-layer nuclear shell knot is made Structure nanoparticle doped polyvinylidene fluoride composite material.
Originally it is that the dielectric for three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material that embodiment obtains is normal by test Number is 18.2, in the case where test frequency is 1kHz test condition, dielectric loss 0.059.
Embodiment 3：
A kind of three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material of the present embodiment offer, the three-layer nuclear shell nano-particle/ Polyvinylidene fluoride composite material is prepared from the following components, specific as follows：
Component 1：SiO2Nano-particle, particle diameter are 400 ~ 600nm, and Alfa Aesar companies of the U.S. produce；
Component 2：Silane coupling agent KH550, purity >=97%, the production of Shanghai Mike woods Reagent Company；
Component 3：Graphene oxide powder, 0.5-5 μm of particle diameter, thickness 1-3nm, the life of Nanjing Xian Feng Nono-material Science ＆ Technology Ltd. Production；
Component 4：Chitosan, high viscosity >=400mPa.s, the production of Shanghai Aladdin Reagent Company；
Component 5：Ascorbic acid, purity >=99%, the production of Shanghai Aladdin Reagent Company；
Component 6：Kynoar, the production of Alfa Aesar companies of the U.S.；
Component 7：N-N dimethylformamides（DMF）, purity >=99.5%, the production of Tong Guang fine chemistry industries company of Beijing.
The preparation method of the three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material is as follows：
Step 1：Component 2 is grafted to the surface of component 1, obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Wherein, the step of grafting is as follows：By 1.5g silica, 1.5mL anhydrous acetic acids, 97mL absolute ethyl alcohols, 1.5mLKH550 mix, sealing, and using 90 ± 10w supersound process 45min, after be placed in 50 ± 3 DEG C of oil bath stirring reactions 24h, after the completion of reaction, centrifuge washing is dried, and obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle.
Step 2：Graphene oxide is wrapped in by the method for Electrostatic Absorption silane coupler is grafted with made from step 1 KH550 SiO2Nanoparticle surface.
Wherein, the specific method is as follows：By the silicane coupling agent surface grafted KH550's prepared by 1.5g steps 1 SiO2Nano-particle is dispersed in 200mL deionized waters, ultrasonic disperse 1h, 2 equal portions is then divided into, first to first part etc. It is 1mg/mL graphene oxide water solutions that 3.75mL concentration is added dropwise in liquid separation, after being slowly stirred 0.5h, by the liquid separation such as second part It is poured slowly into, is 1mg/mL graphene oxides equally to mixed solution and dripping 3.75mL concentration after being slowly stirred 0.5h again The aqueous solution, after stirring 18h afterwards, filter, finally give the SiO of graphene oxide layer parcel2Nano-particle.
Step 3：It is SiO to prepare kernel2, first layer shell is redox graphene, and second layer shell is the nucleocapsid of chitosan Nano-particle.
The SiO that the graphene oxide layer prepared in step 2 is wrapped up2Nano-particle is all dispersed in 200mL and pH=4.5 Acetic acid solution in, while add 0.015g chitosans, be ultrasonically treated 0.5 ~ 2h, then add 0.049g 1-（3- dimethyl propylenes Base）- 3- ethyl-carbodiimide hydrochlorides and 0.058g n-hydroxysuccinimides, at room temperature after 6 ~ 8h of water-bath stirring 18 ~ 24h, after reaction stops, 0.038g ascorbic acid is added, in 90 ± 3 DEG C of 0.5 ~ 1.5h of heating response, vacuum filtration washs, Freeze-drying, you can obtain SiO2Nanoparticle surface wraps up one layer of redox graphene and one layer of chitosan, wherein shell gather Outer layer of the sugar layer in redox graphene layer.Finally give a kind of three-layer nuclear shell nano-particle.
Step 4：The three-layer nuclear shell nano-particle that step 3 is obtained is according to 0.55%（m/V）Addition be added to poly- inclined fluorine In the mixed solution of ethene and N-N dimethylformamides, wherein, the mixing of the Kynoar and N-N dimethylformamides In solution, Kynoar：N-N dimethylformamides=0.5g:10mL.Stirred after being thoroughly mixed, then it is de- by vacuumizing Bubble removing, it is film-made using linear film rod, is heated on the flat heater platform that temperature setting is 120 ± 5 DEG C, three-layer nuclear shell is made Structure nano particle adulterates polyvinylidene fluoride composite material.
Originally it is that the dielectric for three-layer nuclear shell nano-particle/polyvinylidene fluoride composite material that embodiment obtains is normal by test Number is 18.5, in the case where test frequency is 1kHz test condition, dielectric loss 0.058.

Claims (10)

  1. A kind of 1. core-shell nano/polyvinylidene fluoride composite material, it is characterised in that：The core-shell nano/gather inclined fluorine Ethene composite is combined by three-layer nuclear shell nanoparticle doped into Kynoar, wherein the three-layer nuclear shell nanometer The core of particle is silica, and from inner outside, first layer shell is the dilute layer of reduction-oxidation graphite, and second layer shell is chitosan layer.
  2. 2. a kind of preparation method of core-shell nano/polyvinylidene fluoride composite material described in claim 1, its feature exist In：The preparation method comprises the following steps：
    Step 1：Silane coupling agent KH550 is grafted to SiO2Nanoparticle surface, obtain being grafted with Silane coupling agent KH550 SiO2Nano-particle；
    Step 2：Graphene oxide is wrapped in by the method for Electrostatic Absorption silane coupler is grafted with made from step 1 KH550 SiO2Nanoparticle surface, obtain the SiO of graphene oxide layer parcel2Nano-particle；
    Step 3：The SiO that graphene oxide layer is wrapped up2Nano-particle is dispersed in acetic acid solution, and adds chitosan, 1-（3- Dimethyl propyl）- 3- ethyl-carbodiimide hydrochlorides and n-hydroxysuccinimide, reaction add ascorbic acid after terminating and entered One step redox graphene, it is SiO that kernel, which is prepared,2, first layer shell is redox graphene, and second layer shell is that shell gathers The core-shell nano of sugar, as three-layer nuclear shell nano-particle；
    Step 4：The three-layer nuclear shell nano-particle is added to the mixed solution of Kynoar and N-N dimethylformamides In, it is well mixed, removes bubble, heating film, three-layer nuclear shell structure nanoparticle doped polyvinylidene fluoride composite material is made.
  3. 3. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：It is described that Silane coupling agent KH550 is grafted to SiO2The step of nanoparticle surface, is as follows：By silica, anhydrous acetic acid, Absolute ethyl alcohol and KH550 mixing, sealing, and using 90 ± 10w 30 ~ 45min of supersound process, after be placed in 50 ± 3 DEG C of oil baths and stir 20 ~ 24h of reaction is mixed, after the completion of reaction, centrifuge washing is dried, and obtains being grafted with the SiO of Silane coupling agent KH5502Nano-particle； Wherein, described silica accounts for 1.5-2.5% (m/V), and anhydrous acetic acid accounts for 1.5-2.5% (V/V), and absolute ethyl alcohol accounts for 95-97% (V/V), KH550 accounts for 1.5-2.5% (V/V).
  4. 4. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：The method of the Electrostatic Absorption is：By silicane coupling agent surface grafted KH550 SiO2Nano-particle is dispersed in deionized water In, ultrasonic disperse, and graphene oxide water solution is added, it is sufficiently stirred, filters, obtains the SiO of graphene oxide layer parcel2Receive Rice corpuscles, wherein, described graphene oxide accounts for 0.003-0.005% (m/V).
  5. 5. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：PH=4 ~ 5 of the acetic acid solution.
  6. 6. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：The SiO of the graphene oxide layer parcel2The addition of nano-particle is：The addition of chitosan accounts for 0.003-0.008% (m/V), 1-（3- dimethyl propyls）The addition of -3- ethyl-carbodiimide hydrochlorides accounts for 0.011-0.025% (m/V), N- hydroxyls The addition of base succinimide accounts for 0.013-0.029% (m/V).
  7. 7. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：The addition of the ascorbic acid accounts for 0.016-0.019% (m/V).
  8. 8. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：In the mixed solution of the Kynoar and N-N dimethylformamides, Kynoar：N-N dimethylformamides= 0.5g:10mL~2g:10mL。
  9. 9. the preparation method of core-shell nano/polyvinylidene fluoride composite material according to claim 2, its feature exist In：The temperature of the heating film is 120 ± 2 DEG C.
  10. A kind of 10. new application of core-shell nano/polyvinylidene fluoride composite material described in claim 1, it is characterised in that Core-shell nano/the polyvinylidene fluoride composite material is used for the insulating materials for preparing electric apparatus, integrated circuit and cable.
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