CN102174236A - Preparation method of polyvinylidene fluoride-based composite with high dielectric constant - Google Patents
Preparation method of polyvinylidene fluoride-based composite with high dielectric constant Download PDFInfo
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- CN102174236A CN102174236A CN 201110063216 CN201110063216A CN102174236A CN 102174236 A CN102174236 A CN 102174236A CN 201110063216 CN201110063216 CN 201110063216 CN 201110063216 A CN201110063216 A CN 201110063216A CN 102174236 A CN102174236 A CN 102174236A
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Abstract
The invention provides a preparation method of a polyvinylidene fluoride-based composite with a high dielectric constant and relates to a preparation method of a polyvinylidene fluoride-based composite, and the method is used for solving the technical problem that the dielectric constant of the polyvinylidene fluoride-based composite is not high. The method comprises the following steps: adding purified multi-walled carbon nanotubes (MWNTs) in a solution containing Fe<2+> and Fe<3+> to prepare MWNTs loaded with Fe3O4; then dispersing the MWNTs in dimethylformamide to obtain a suspension, pouring the mixed solution of the suspension and the dimethylformamide solution of polyvinylidene fluoride on a glass substrate, and drying to obtain a film; and placing the film in a mould, and performing hot pressing for tabletting. In the method, the MWNTs loaded with Fe3O4, polyvinylidene fluoride (PVDF) utilized as a matrix and a melt tabletting method are utilized to prepare the Fe3O4/MWNTs/PVDF three-phase composite of which the dielectric constant is up to 4800-35000.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinylidene difluoride (PVDF) based composites.
Background technology
Growing along with the continuous progress of informationized society and people's demand, promoting electronic component and developing, making that widely used electrical condenser strides forward to the direction of high energy storage, miniaturization in electronic component to miniaturization, high energy storage, high precision, high stable and direction such as multi-functional.
The application of high-dielectric composite material aspect electronics and electric power project engineering is very extensive.Although traditional ceramic dielectric material has very excellent dielectric properties, ceramic condenser needs high-temperature calcination in manufacturing processed, and power consumption is big, complex process, and the snappiness of this dielectric material is poor, and is in use easy to crack, influences its use.Therefore, exploitation has high dielectric property, has the dielectric materials, particularly polymer matrix composite of processability simultaneously again, becomes the focus of recent researches.
At present, more about the report of high dielectric polymer based composites.Improve one of method of polymer matrix composite, carry out pottery and polymkeric substance compound exactly.People such as the Kuo of Taiwan Donghua University are with barium titanate (BaTiO
3) join in the Resins, epoxy, the dielectric properties of matrix material reach about 50.People such as Dang Zhimin are with the BaTiO of 20vol%
3(PVDF) is compounded to form complex matrix with polyvinylidene difluoride (PVDF), and then utilizes Ni particulate seepage flow to make the specific inductivity of matrix material reach more than 800.But the massfraction of the interpolation component of this matrix material is bigger, makes processing characteristics also can descend, and may crack when standing mechanical impact or violent temperature variation, has limited its application in practice.
At present, improving the method for polymer matrix composite dielectric properties, is exactly to add an amount of conductive filler material in polymeric matrix, and conductive filler material mainly contains carbon nanotube, carbon black, graphite, metal-powder or fiber etc., thereby improves the dielectric properties of matrix material.Compare with the matrix material that pottery is filled, its specific inductivity as long as a small amount of conducting particles of adding just can increase sharply particularly utilizes when exceeding the specific inductivity that oozes effect raising material.What seepage theory was described is in compound system, adds components contents near the seepage flow threshold value time, and the specific inductivity generation nonlinear mutation of compound system increases several (ten) times even several magnitude.It is still very limited that but the specific inductivity of existing polyvinylidene difluoride (PVDF) based composites improves, and needs further to improve its dielectric properties.
Summary of the invention
The objective of the invention is to the invention provides a kind of preparation method of high-k polyvinylidene difluoride (PVDF) based composites in order to solve the not high technical problem of specific inductivity of existing polyvinylidene difluoride (PVDF) based composites.
The preparation method of high-k polyvinylidene difluoride (PVDF) based composites of the present invention realizes by following steps:
One, Fe
3O
4The preparation of/multi-walled carbon nano-tubes: the multi-walled carbon nano-tubes adding of purifying is contained Fe
2+And Fe
3+Solution in, stir mixed solution, under whipped state, in mixed solution, drip NaOH solution then, regulate pH value to 9～14 backs and continue to stir 1～3h, leave standstill crystallization 20～50min then, again washing, at 40～60 ℃ of following vacuum-drying 24～48h, get Fe then
3O
4The multi-walled carbon nano-tubes of load, i.e. Fe
3O
4/ multi-walled carbon nano-tubes wherein, contains Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+Mol ratio be 1: 1～1.5, the multi-walled carbon nano-tubes quality with contain Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+The ratio of molar weight be 1g: 62mol;
Two, the Fe that step 1 is obtained
3O
4/ multi-walled carbon nano-tubes adds in the dimethyl formamide, and ultra-sonic dispersion 30～60min gets suspension, then suspension is mixed with the dimethyl formamide solution of polyvinylidene difluoride (PVDF), and ultra-sonic dispersion 1～2h gets mixing solutions, wherein, and Fe in the control mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.0%～3.0% of a polyvinylidene difluoride (PVDF) quality;
Three, the mixing solutions that step 2 is got is poured on the glass substrate, then glass substrate is placed dry 15～24h under 60～120 ℃ the condition, then film is peeled from glass substrate, Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material film is placed in the mould composite material film is folding again, and hot-forming polyvinylidene difluoride (PVDF) based composites promptly gets Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material is finished the preparation of high-k polyvinylidene difluoride (PVDF) based composites.
The purification process of the multi-walled carbon nano-tubes of purifying is in the step 1 of the present invention: multi-walled carbon nano-tubes after calcining under 500～600 ℃ of conditions, is added and carries out ultra-sonic dispersion 1～3h in rare nitric acid; Under 30～50 ℃ of conditions, stir then and soak 5～8h; Use the B suction filtration again, distilled water wash is to neutral, and last 100～130 ℃ are descended dry 10～15h, can obtain the multi-walled carbon nano-tubes of purifying.
The compound method of the dimethyl formamide solution of polyvinylidene difluoride (PVDF) is in the step 2 of the present invention: dimethyl formamide is warming up to 50～60 ℃ and insulation, then polyvinylidene difluoride (PVDF) is added stirring and dissolving in the dimethyl formamide, promptly get the dimethyl formamide solution of polyvinylidene difluoride (PVDF).The molecular weight of polyvinylidene difluoride (PVDF) is 40～600,000 in the step 2.
Hot-forming in the step 3 of the present invention is that hot pressing 8～15min finishes under 200～240 ℃, 8～12MPa condition.
The Fe that the present invention prepares
3O
4Fe in/multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material
3O
4The quality of/multi-walled carbon nano-tubes is 2.0%～3.0% of a polyvinylidene fluoride physique amount.
The present invention is by selecting the multi-walled carbon nano-tubes (MWNTs) that has than big L/D ratio for use, and on MWNTs load Fe
3O
4, be matrix with polyvinylidene difluoride (PVDF) (PVDF), the method with the fusion compressing tablet prepares Fe at last
3O
4/ MWNTs/PVDF three-phase composite material.By in the PVDF polymeric matrix, disperseing Fe
3O
4/ MWNTs realizes Fe
3O
4With the two coupling of MWNTs, utilize seep effect simultaneously, make Fe
3O
4/ MWNTs/PVDF three-phase composite material have a high specific inductivity, up to 4800～35000, have good dielectric properties.
The present invention Z 250 (nano ferriferrous oxide (Fe
3O
4) be a kind of important magneticsubstance, at magnetic fluid, magnetic recording material, aspects such as absorbing material have important use) (carbon nanotube has particular structure because of it to coat or fill multi-walled carbon nano-tubes, electricity, mechanics, performances such as Chu Qing, so at nano electron device, superpower matrix material, hydrogen storage material, many frontiers such as support of the catalyst prospect that has a very wide range of applications), the multi-walled carbon nano-tubes of load Z 250 has excellent more optical property, conductivity, mechanical property, absorption property, absorbing property and capability of electromagnetic shielding etc., again it is dispersed in the polyvinylidene fluoride polymer, obtains good mechanical properties, the polyvinylidene difluoride (PVDF) based composites of specific inductivity height (4800～35000).
Polyvinylidene difluoride (PVDF) based composites (the Fe that the present invention prepares
3O
4/ MWNTs/PVDF three-phase composite material) has a good application prospect in fields such as absorbing material, electromagnetic shielding materials.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the multi-walled carbon nano-tubes of purifying in the step 1 of embodiment 12; Fig. 2 is the scanning electron photomicrograph of the multi-walled carbon nano-tubes of purifying in the step 1 of embodiment 12; Fig. 3 is the Fe that the step 1 of embodiment 12 obtains
3O
4The X-ray diffraction spectrogram of/multi-walled carbon nano-tubes; Fig. 4 is the Fe that the step 1 of embodiment 12 obtains
3O
4The scanning electron photomicrograph of/multi-walled carbon nano-tubes; Fig. 5 is the Fe that embodiment 12 prepares
3O
4The scanning electron photomicrograph of/multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is the preparation method of high-k polyvinylidene difluoride (PVDF) based composites, and it is realized by following steps:
One, Fe
3O
4The preparation of/multi-walled carbon nano-tubes: the multi-walled carbon nano-tubes adding of purifying is contained Fe
2+And Fe
3+Solution in, stir mixed solution, under whipped state, in mixed solution, drip NaOH solution then, regulate pH value to 9～14 backs and continue to stir 1～3h, leave standstill crystallization 20～50min then, again washing, at 40～60 ℃ of following vacuum-drying 24～48h, get Fe then
3O
4The multi-walled carbon nano-tubes of load, i.e. Fe
3O
4/ multi-walled carbon nano-tubes wherein, contains Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+Mol ratio be 1: 1～1.5, the multi-walled carbon nano-tubes quality with contain Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+The ratio of molar weight be 1g: 62mol;
Two, the Fe that step 1 is obtained
3O
4/ multi-walled carbon nano-tubes adds in the dimethyl formamide, and ultra-sonic dispersion 30～60min gets suspension, then suspension is mixed with the dimethyl formamide solution of polyvinylidene difluoride (PVDF), and ultra-sonic dispersion 1～2h gets mixing solutions, wherein, and Fe in the control mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.0%～3.0% of a polyvinylidene difluoride (PVDF) quality;
Three, the mixing solutions that step 2 is got is poured on the glass substrate, then glass substrate is placed dry 15～24h under 60～120 ℃ the condition, then film is peeled from glass substrate, Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material film is placed in the mould composite material film is folding again, and hot-forming polyvinylidene difluoride (PVDF) based composites promptly gets Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material is finished the preparation of high-k polyvinylidene difluoride (PVDF) based composites.
The multi-walled carbon nano-tubes of purifying adopts existing open method to carry out purifying in the present embodiment step 1, and the multi-walled carbon nano-tubes of employing is the commercially available prod or adopts existing open method to prepare.The molecular weight of the polyvinylidene difluoride (PVDF) in the step 2 in the dimethyl formamide solution of polyvinylidene difluoride (PVDF) is 40～600,000.
Present embodiment is by selecting the multi-walled carbon nano-tubes (MWNTs) that has than big L/D ratio for use, and on MWNTs load Fe
3O
4, be matrix with polyvinylidene difluoride (PVDF) (PVDF), the method with the fusion compressing tablet prepares Fe at last
3O
4/ MWNTs/PVDF three-phase composite material.By in the PVDF polymeric matrix, disperseing Fe
3O
4/ MWNTs realizes Fe
3O
4With the two coupling of MWNTs, utilize seep effect simultaneously, make Fe
3O
4/ MWNTs/PVDF three-phase composite material have a high specific inductivity, up to 4800～35000.
In the present embodiment with magnetic nano-particle Fe
3O
4Be loaded on the multi-walled carbon nano-tubes magnetic nano-particle Fe
3O
4Have physical influences such as surface effects, small-size effect, quantum size effect and macroscopic quantum tunnelling, the characteristic of novelties such as the superparamagnetism that is produced, upfield non-reversibility and high saturation magnetic field makes magnetic Nano material be widely used as a kind of special functional materials.
Embodiment two: present embodiment and embodiment one are different is that the purification process of the multi-walled carbon nano-tubes of purifying in the step 1 is: multi-walled carbon nano-tubes after calcining under 500～600 ℃ of conditions, is added and carries out ultra-sonic dispersion 1～3h in rare nitric acid; Under 30～50 ℃ of conditions, stir then and soak 5～8h; Use the B suction filtration again, distilled water wash is to neutral, and last 100～130 ℃ are descended dry 10～15h, can obtain the multi-walled carbon nano-tubes of purifying.Other step and parameter are identical with embodiment one.
The multi-walled carbon nano-tubes that present embodiment adopts is the commercially available prod or adopts existing open method to prepare.
Embodiment three: what present embodiment was different with embodiment one or two is to contain Fe in the step 1
2+And Fe
3+Solution in, Fe
2+Provide Fe by a kind of in iron protochloride, ferrous sulfate and the Iron nitrate or wherein several combination
3+Provide by iron nitrate and/or ferric sulfate.Other step and parameter are identical with embodiment one or two.
Work as Fe in the present embodiment
2+Be when wherein several combinations of substances provide, between several materials with any than combination.Work as Fe
3+When providing, make up with any ratio between iron nitrate and ferric sulfate by iron nitrate and ferric sulfate.
Embodiment four: present embodiment and embodiment one, two or three are different is Fe in the suspension in the step 2
3O
4The content of/multi-walled carbon nano-tubes is 0.003～0.005g/mL.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: present embodiment is different with one of embodiment one to four is that the compound method of the dimethyl formamide solution of polyvinylidene difluoride (PVDF) in the step 2 is: dimethyl formamide is warming up to 50～60 ℃ and insulation, then polyvinylidene difluoride (PVDF) is added stirring and dissolving in the dimethyl formamide, promptly get the dimethyl formamide solution of polyvinylidene difluoride (PVDF).Other step and parameter are identical with one of embodiment one to four.
The molecular weight of the polyvinylidene difluoride (PVDF) that uses in the present embodiment is 40～600,000.
Embodiment six: present embodiment is different with one of embodiment one to five is that the ratio of polyvinylidene difluoride (PVDF) quality and dimethyl formamide volume is 1.5g: 10～15mL in the dimethyl formamide solution of polyvinylidene difluoride (PVDF) in the step 2.Other step and parameter are identical with one of embodiment one to five.
The volume fraction of polyvinylidene difluoride (PVDF) is 5%～8% in the dimethyl formamide solution of the polyvinylidene difluoride (PVDF) of present embodiment.
Embodiment seven: what present embodiment was different with one of embodiment one to six is to control Fe in the mixed solution in the step 2
3O
4The quality of/multi-walled carbon nano-tubes is 2.3%～2.8% of a polyvinylidene difluoride (PVDF) quality.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different with one of embodiment one to six is to control Fe in the mixed solution in the step 2
3O
4The quality of/multi-walled carbon nano-tubes is 2.5% of a polyvinylidene difluoride (PVDF) quality.Other step and parameter are identical with one of embodiment one to six.
Embodiment nine: present embodiment is different with one of embodiment one to eight is in the step 3 glass substrate to be placed dry 18～22h under 80～100 ℃ the condition.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different with one of embodiment one to eight is in the step 3 glass substrate to be placed dry 20h under 90 ℃ the condition.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 11: present embodiment is different with one of embodiment one to ten be hot-forming in the step 3 be that hot pressing 8～15min finishes under 200～240 ℃, 8～12MPa condition.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: present embodiment is the preparation method of high-k polyvinylidene difluoride (PVDF) based composites, and it is realized by following steps:
One, Fe
3O
4The preparation of/multi-walled carbon nano-tubes: the multi-walled carbon nano-tubes adding of purifying is contained Fe
2+And Fe
3+Solution in, stir mixed solution, under whipped state, in mixed solution, drip NaOH solution then, regulate pH value to 12 back and continue to stir 3h, leave standstill crystallization 30min then, washing more then at 50 ℃ of following vacuum-drying 36h, gets Fe
3O
4The multi-walled carbon nano-tubes of load, i.e. Fe
3O
4/ multi-walled carbon nano-tubes wherein, contains Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+Mol ratio be 1: 1.5, the multi-walled carbon nano-tubes quality with contain Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+The ratio of molar weight be 1g: 62mol, wherein Fe
2+By FeCl
24H
2O provides, Fe
3+By Fe (NO
3)
39H
2O provides;
Two, the Fe that step 1 is obtained
3O
4/ multi-walled carbon nano-tubes adds in the dimethyl formamide, and ultra-sonic dispersion 30～60min gets suspension, then suspension is mixed with the dimethyl formamide solution of polyvinylidene difluoride (PVDF), and ultra-sonic dispersion 1～2h gets mixing solutions, wherein, and Fe in the control mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.0% of a polyvinylidene difluoride (PVDF) quality;
Three, the mixing solutions that step 2 is got is poured on the glass substrate, then glass substrate is placed dry 20h under 90 ℃ the condition, then film is peeled from glass substrate, Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material film is placed in the mould composite material film is folding again, and hot-forming polyvinylidene difluoride (PVDF) based composites promptly gets Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material is finished the preparation of high-k polyvinylidene difluoride (PVDF) based composites.
The purification process of the multi-walled carbon nano-tubes of purifying is in the present embodiment step 1: multi-walled carbon nano-tubes after calcining under 600 ℃ of conditions, is added in the rare nitric acid of 20% (quality) and carries out ultra-sonic dispersion 2h; Under 40 ℃ of conditions, stir then and soak 6h; Use the B suction filtration again, distilled water wash is to neutral, and last 120 ℃ are descended dry 12h, can obtain the multi-walled carbon nano-tubes of purifying.The multi-walled carbon nano-tubes that adopts is to buy in nanometer port, Shenzhen company limited.
The concentration of NaOH solution is 1～3mol/L in the present embodiment step 1.
Fe in the suspension of present embodiment step 2
3O
4The content of/multi-walled carbon nano-tubes is 0.004g/mL;
The compound method of the dimethyl formamide solution of polyvinylidene difluoride (PVDF) is in the present embodiment step 2: dimethyl formamide is warming up to 50～60 ℃ and insulation, then polyvinylidene difluoride (PVDF) is added stirring and dissolving in the dimethyl formamide, promptly get the dimethyl formamide solution of polyvinylidene difluoride (PVDF); Wherein the ratio of polyvinylidene difluoride (PVDF) quality and dimethyl formamide volume is 1.5g: 10～15mL.
Hot-forming in the present embodiment step 3 is that hot pressing 15min finishes under 240 ℃, 12MPa condition.
The X-ray diffraction spectrogram of the multi-walled carbon nano-tubes of purifying and scanning electron photomicrograph are respectively as depicted in figs. 1 and 2 in the present embodiment step 1, as seen from Figure 1, MWNTs after the processing 2 θ be 26.0 ° locate with 2 θ be 42.4 ° of characteristic peaks of locating to occur MWNTs, do not have the appearance of other impurity peaks, explanation can be clean with the Impurity removal among the MWNTs; As seen from Figure 2, the MWCNTs bonded after acid treatment is looser, and wrapping phenomena alleviates to some extent, and more port occurs, also can effectively remove the impurity among the MWCNTs.
The Fe that the present embodiment step 1 obtains
3O
4The X-ray diffraction spectrogram of/multi-walled carbon nano-tubes and scanning electron photomicrograph are distinguished as shown in Figure 3 and Figure 4, and as seen from Figure 3, that occur in the XRD figure spectrum all is Fe
3O
4With the MWNTs charateristic avsorption band, there is not the appearance of other impurity peaks, illustrate to have obtained purer Fe
3O
4/ MWNTs; As seen from Figure 4, Fe
3O
4Nanoparticle loads on MWNTs uniformly, simultaneously Fe
3O
4Agglomeration does not appear in nanoparticle yet, and Fe is described
3O
4The charge capacity of nanoparticle is moderate.
The Fe that this enforcement prepares
3O
4The scanning electron photomicrograph of/multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material as shown in Figure 5, as seen from Figure 5, Fe
3O
4/ multi-walled carbon nano-tubes is evenly distributed in the polyvinylidene difluoride (PVDF) matrix, does not have agglomeration.
The Fe of present embodiment to preparing
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material carries out dielectric properties tests, and testing method is: adopt the accurate electric impedance analyzer of U.S. Agilent 4294A, measure under the room temperature condition, the impedance of frequency when 1000Hz, and then obtain specific inductivity.The specific inductivity that test obtains the polyvinylidene difluoride (PVDF) based composites of present embodiment is 4800.
Embodiment 13: Fe in the different last step 2 control mixed solution of present embodiment and embodiment 12
3O
4The quality of/multi-walled carbon nano-tubes is 2.5% of a polyvinylidene difluoride (PVDF) quality.Other step and parameter are identical with embodiment 12.
The specific inductivity that adopts embodiment 12 described testing method tests to obtain the polyvinylidene difluoride (PVDF) based composites of present embodiment reaches 35000.
Embodiment 14: Fe in the different last step 2 control mixed solution of present embodiment and embodiment 12
3O
4The quality of/multi-walled carbon nano-tubes is 3.0% of a polyvinylidene difluoride (PVDF) quality.Other step and parameter are identical with embodiment 12.
The specific inductivity that adopts embodiment 12 described testing method tests to obtain the polyvinylidene difluoride (PVDF) based composites of present embodiment reaches 11000.
Claims (10)
1. the preparation method of a high-k polyvinylidene difluoride (PVDF) based composites is characterized in that the preparation method of high-k polyvinylidene difluoride (PVDF) based composites realizes by following steps:
One, Fe
3O
4The preparation of/multi-walled carbon nano-tubes: the multi-walled carbon nano-tubes adding of purifying is contained Fe
2+And Fe
3+Solution in, stir mixed solution, under whipped state, in mixed solution, drip NaOH solution then, regulate pH value to 9～14 backs and continue to stir 1～3h, leave standstill crystallization 20～50min then, again washing, at 40～60 ℃ of following vacuum-drying 24～48h, get Fe then
3O
4The multi-walled carbon nano-tubes of load, i.e. Fe
3O
4/ multi-walled carbon nano-tubes wherein, contains Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+Mol ratio be 1: 1～1.5, the multi-walled carbon nano-tubes quality with contain Fe
2+And Fe
3+Solution in Fe
2+And Fe
3+The ratio of molar weight be 1g: 62mol;
Two, the Fe that step 1 is obtained
3O
4/ multi-walled carbon nano-tubes adds in the dimethyl formamide, and ultra-sonic dispersion 30～60min gets suspension, then suspension is mixed with the dimethyl formamide solution of polyvinylidene difluoride (PVDF), and ultra-sonic dispersion 1～2h gets mixing solutions, wherein, and Fe in the control mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.0%～3.0% of a polyvinylidene difluoride (PVDF) quality;
Three, the mixing solutions that step 2 is got is poured on the glass substrate, then glass substrate is placed dry 15～24h under 60～120 ℃ the condition, then film is peeled from glass substrate, Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material film is placed in the mould composite material film is folding again, and hot-forming polyvinylidene difluoride (PVDF) based composites promptly gets Fe
3O
4/ multi-walled carbon nano-tubes/polyvinylidene difluoride (PVDF) three-phase composite material is finished the preparation of high-k polyvinylidene difluoride (PVDF) based composites.
2. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1, the purification process that it is characterized in that the multi-walled carbon nano-tubes of purifying in the step 1 is: multi-walled carbon nano-tubes after calcining under 500～600 ℃ of conditions, is added and carries out ultra-sonic dispersion 1～3h in rare nitric acid; Under 30～50 ℃ of conditions, stir then and soak 5～8h; Use the B suction filtration again, distilled water wash is to neutral, and last 100～130 ℃ are descended dry 10～15h, can obtain the multi-walled carbon nano-tubes of purifying.
3. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that containing in the step 1 Fe
2+And Fe
3+Solution in, Fe
2+Provide Fe by a kind of in iron protochloride, ferrous sulfate and the Iron nitrate or wherein several combination
3+Provide by iron nitrate and/or ferric sulfate.
4. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that Fe in the suspension in the step 2
3O
4The content of/multi-walled carbon nano-tubes is 0.003～0.005g/mL.
5. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that the ratio of polyvinylidene difluoride (PVDF) quality and dimethyl formamide volume is 1.5g: 10～15mL in the dimethyl formamide solution of polyvinylidene difluoride (PVDF) in the step 2.
6. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that controlling in the step 2 Fe in the mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.3%～2.8% of a polyvinylidene difluoride (PVDF) quality.
7. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that controlling in the step 2 Fe in the mixed solution
3O
4The quality of/multi-walled carbon nano-tubes is 2.5% of a polyvinylidene difluoride (PVDF) quality.
8. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that in the step 3 glass substrate placed dry 18～22h under 80～100 ℃ the condition.
9. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that in the step 3 glass substrate placed dry 20h under 90 ℃ the condition.
10. the preparation method of a kind of high-k polyvinylidene difluoride (PVDF) based composites according to claim 1 and 2 is characterized in that hot-forming in the step 3 is that hot pressing 8～15min finishes under 200～240 ℃, 8～12MPa condition.
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