CN110527225A - Transparent electroactive polyvinylidene fluoride-based composite of height of one kind and preparation method thereof - Google Patents
Transparent electroactive polyvinylidene fluoride-based composite of height of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention provides transparent electroactive polyvinylidene fluoride-based composite of height of one kind and preparation method thereof, belongs to high molecular material and advanced field of nanocomposite materials.It is to obtain after 100:0.05-10:0.01-3 is blended that the composite material is by Kynoar, ionic liquid and clay in mass ratio.The present invention also provides a kind of preparation methods of transparent electroactive polyvinylidene fluoride-based composite of height.Composite material of the invention has the polar crystal of high permeability and 100%；In addition to this, clay can inhibit the migration of ionic liquid under the electric field, reduce the dielectric loss of composite material, this has widened its application as piezoelectric material.
Description
Technical field
The invention belongs to high molecular material and advanced field of nanocomposite materials, and in particular to a kind of transparent height is electroactive poly-
Vinylidene fluoride composite material and preparation method.
Background technique
Kynoar (PVDF) is a kind of important hemicrystalline high molecular material, has excellent heat resistance, resistance toization
Corrosivity, mechanical performance and the characteristics such as piezoelectricity and ferroelectricity are learned, and each due to can be made into shape with good processing performance
Different multi-function membrane product has obtained extensive concern in academia and industrial circle.The application of PVDF thin film is very extensive, main
It is related to biomedicine, energy acquisition and storage, system, separator and the side such as filter membrane and intelligent Supports Made is monitored and controlled
Face.According to the difference of Molecular connectivity indices, PVDF shows a variety of different crystal structures (α, beta, gamma, δ, ε), wherein β and γ phase
PVDF has highest electroactive.Currently, it is high it is electroactive be usually basis of the PVDF as various applications, therefore prepare and have
High electroactive PVDF is academic and industrial with particularly important meaning.
Currently, it is considered as preparing to have efficacious prescriptions with piezoelectricity PVDF material that different functional stuffings is introduced into PVDF
Method, common functional stuffing mainly have conductive carbon-based material (carbon nanotube, graphene etc.), inorganic filler (barium titanate, dioxy
Change titanium etc.) and silicate plate layer material (montmorillonite, kaolin and lithium magnesium silicate etc.).Although these fillers can effectively promote
Into the formation of PVDF polar crystal, but high filling content makes filler difficulties in dispersion in the base, and the phase between matrix
Capacitive is deteriorated, this often reduces the transparency of material and mechanical performance etc..Therefore usually require to carry out filler pre- modification with
It improves its dispersibility in the base, but this often complicated process flow and increases production cost, industrially more difficult reality
It is existing.Other than functional stuffing, PVDF polar crystal can also effectively be induced by blending the small molecules such as ionic liquid into PVDF
Formation.Chinese patent 103102623A discloses anti-static polyvinylidene fluoride piezoelectric material and its preparation side of a kind of transparent antistatic
Method.Transparent and antistatic polyvinylidene fluoride piezoelectric composite material is prepared by simple melting mixing method.But due to
The ionic liquid adulterated conductivity with higher, therefore high dielectric loss is easy to produce in electric field polarization, this is to pressure
Electric material is unfavorable as the application such as energy storage.
Summary of the invention
The purpose of the invention is to provide a kind of polyvinylidene fluoride-based composite and preparation method thereof, the composite material
With high electroactive content, dielectric and satisfactory mechanical property.
Present invention firstly provides a kind of transparent electroactive polyvinylidene fluoride-based composite of height, which is that will gather partially
Vinyl fluoride, ionic liquid and clay are to obtain after 100:0.05-10:0.01-3 is blended in mass ratio.
Preferably, the mass ratio of the Kynoar, ionic liquid and clay is 100:0.1-3:0.1-1.
Preferably, the clay is phyllosilicate.
Preferably, the phyllosilicate is montmorillonite, kaolin or lithium magnesium silicate.
Preferably, cation is one, two, tri-substituted imidazole cationoid in the ionic liquid, and one, two replace pyrrole
Pyridine cationoid, quaternary ammonium cationoid, pyrrolidines cation, morpholine cationoid, piperidines cationoid；Anion is Cl-、
Br-、I-、BF4 -、PF6 -、FeCl4 -、CF3SO3 -、CH3COO-。
Preferably, the ionic liquid is 1- cetyl -3- methylimidazole villaumite, 1- cetyl -3- ethylene
Base imidazoles bromide, 1- cetyl -3- methylimidazole bromide, 1- butyl -3- methylimidazole villaumite or 1- butyl -3- vinyl miaow
Azoles villaumite.
The present invention also provides a kind of preparation method of transparent electroactive polyvinylidene fluoride-based composite of height, this method packets
It includes:
In mass ratio it is 100:0.05-10:0.01-3 proportion by Kynoar, ionic liquid and clay, is added to molten
Melt in blending equipment and be kneaded at 175-200 DEG C, then by blend cold moudling, obtains polyvinylidene fluoride-based composite.
Preferably, first respectively that Kynoar, ionic liquid and clay is true at 60-80 DEG C before the mixing
The dry 24-48h of sky.
Preferably, the melt blending equipment is mixer, screw extruder or inflation film manufacturing machine.
Preferably, when the blending using mixer, closed-smelting machine rotor revolving speed is 40-60rpm, and the blending time is 4-
10min。
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of polyvinylidene fluoride-based composite and preparation method thereof, which is by polyvinylidene fluoride
Alkene, ionic liquid and clay directly carry out a step melt blending, obtain polyvinylidene fluoride composite material, and the Kynoar is multiple
Condensation material has the good transparency, high electroactive, outstanding mechanical performance and dielectric properties, wherein in melt blending process
Ion exchange occurs for intermediate ion liquid and clay, and the cationic portion of ionic liquid, which is adsorbed on clay layer, reduces argillic horizon
Between active force, and the removing of clay layer can be promoted by means of the effect of shearing force in Blending Processes, ionic liquid is deposited
The dispersibility that clay can be improved and with the compatibility of matrix so that prepared composite material have high permeability and
100% polar crystal；In addition to this, clay can inhibit the migration of ionic liquid under the electric field, reduce Jie of composite material
Electrical loss, this has widened its application as piezoelectric material.
The present invention is to pre-process without to filler by a step melting mixing method, simplify preparation process, in work
It can be prepared on a large scale in industry.It only needs few filer content to prepare polyvinylidene fluoride composite material in the present invention, reduces
Production cost.
Detailed description of the invention
Fig. 1 is the polyvinylidene fluoride composite material section scanning electron microscope picture of comparative example 1-3 and embodiment 5；
Fig. 2 is comparative example 1-3, and the polyvinylidene fluoride composite material Fourier of embodiment 3, embodiment 5 and embodiment 6 is infrared
Spectrogram；
Fig. 3 is comparative example 1-3, embodiment 3, the polyvinylidene fluoride composite material X-ray diffraction of embodiment 5 and embodiment 6
Figure；
Fig. 4 is comparative example 1-3, embodiment 3, the polyvinylidene fluoride composite material ultraviolet-visible of embodiment 5 and embodiment 6
Spectrogram；
Fig. 5 is comparative example 1-3, embodiment 3, the dielectric constant of the polyvinylidene fluoride composite material of embodiment 5 and embodiment 6
With frequency variation curve；
Fig. 6 is comparative example 1-3, embodiment 3, the dielectric loss of the polyvinylidene fluoride composite material of embodiment 5 and embodiment 6
With frequency variation curve；
Fig. 7 is comparative example 4-7, the FTIR spectrum figure of the polyvinylidene fluoride composite material of embodiment 3；
Fig. 8 is comparative example 4-7, the UV-visible spectrum of the polyvinylidene fluoride composite material of embodiment 3.
Specific embodiment
Present invention firstly provides a kind of transparent electroactive polyvinylidene fluoride-based composite of height, which is that will gather partially
Vinyl fluoride, ionic liquid and clay are to obtain after 100:0.05-10:0.01-3 is blended in mass ratio.The present invention should be controlled strictly
The content of composite material intermediate ion liquid and clay processed, specifically, when the content of ionic liquid is less than 0.05%, it is very few from
Sub- content liquid cannot effectively facilitate the removing of clay, not have due effect, when ionic liquid content is excessive, composite wood
Biggish dielectric loss is had in material, this is unfavorable for the application of material, therefore ionic liquid content is limited to ratio
Within 10%；For the content of clay, in low content, the transparency of obtained composite material is more preferable, when loading is more
When, the dispersibility in the base of montmorillonite is deteriorated, and then leads to mechanics or the transparency decline of material.
Preferably, the mass ratio of the Kynoar, ionic liquid and clay is 100:0.1-3:0.1-1.
According to the present invention, the clay is phyllosilicate, and the phyllosilicate is preferably montmorillonite, kaolin
Or lithium magnesium silicate.
According to the present invention, cation is one, two, tri-substituted imidazole cationoid in the ionic liquid, and one, two replace
Pyridine cationoid, quaternary ammonium cationoid, pyrrolidines cation, morpholine cationoid, piperidines cationoid；Anion is
Cl-、Br-、I-、BF4 -、PF6 -、FeCl4 -、CF3SO3 -、CH3COO-, it is more preferably 1- cetyl -3- methylimidazole villaumite, 1-
Cetyl -3- vinyl imidazole bromide, 1- cetyl -3- methylimidazole bromide, 1- butyl -3- methylimidazole villaumite or 1-
Butyl -3- vinyl imidazole villaumite, most preferably 1- cetyl -3- methylimidazole villaumite, ionic liquid of the present invention
Source is preferably purchased from marine origin victory chemical company commercially available from being.
The present invention also provides a kind of preparation method of transparent electroactive polyvinylidene fluoride-based composite of height, this method packets
It includes:
In mass ratio it is 100:0.05-10:0.01-3 proportion by Kynoar, ionic liquid and clay, is added to molten
Melt in blending equipment and be kneaded at 175-200 DEG C, then by blend cold moudling, obtains polyvinylidene fluoride-based composite.
According to the present invention, before the mixing, preferably first respectively by Kynoar, ionic liquid and clay in 60-80
24-48h is dried in vacuo at DEG C.
According to the present invention, the melt blending equipment is mixer, screw extruder or inflation film manufacturing machine.Mixing is used when stating
When machine is blended, closed-smelting machine rotor revolving speed is preferably 40-60rpm, and it is preferably 4-10min that the time, which is blended,；When use screw extruder
When blending, screw speed is preferably 40-60rpm；When being blended using inflation film manufacturing machine, screw speed is preferably 40-60rpm.
Further detailed description is done to the present invention combined with specific embodiments below, the raw material being related in embodiment is
It is commercially available.
Comparative example 1
(1) Kynoar is dried in vacuo for 24 hours at 70 DEG C；
(2) Kynoar in 60g step (1) is added in mixer, melting mixing 5min is carried out at 190 DEG C,
Spinner velocity is 60rpm, obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride material.
Comparative example 2
(1) Kynoar and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) it by the 60g Kynoar and 0.3g montmorillonite addition mixer after drying, is melted at 190 DEG C
It is kneaded 5min, spinner velocity 60rpm obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Comparative example 3
(1) Kynoar and 1- cetyl -3- methylimidazole villaumite are dried in vacuo for 24 hours at 70 DEG C；
(2) by the 60g Kynoar and 0.6g1- cetyl -3- methylimidazole villaumite addition mixer after drying
In, melting mixing 5min is carried out at 190 DEG C, spinner velocity 60rpm obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 1
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.06g1- cetyl -3- methylimidazole villaumite and the 0.06g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 2
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.3g1- cetyl -3- methylimidazole villaumite and the 0.06g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 3
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.06g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 4
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 1.8g1- cetyl -3- methylimidazole villaumite and the 0.06g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 5
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.3g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Polyvinylidene fluoride composite material in comparative example 1-3 and embodiment 5 is scanned electron microscope observation, sample is crisp
It has no progeny and is observed after spraying layer gold on section；As shown in Figure 1, comparative example 1 is compared, Kynoar is compound in comparative example 3
Material occurs without apparent mutually separation, shows that ionic liquid and Kynoar have good compatibility.Comparative example 2 is only
Add the polyvinylidene fluoride composite material of montmorillonite, it can be seen that montmorillonite is not removed in the base, is illustrated only by cutting
Shear force is difficult to realize the removing of phyllosilicate in the base.However, it can be observed that the illiteracy largely removed in embodiment 5
De- soil lamella is embedded in Kynoar matrix, is shown that ionic liquid is added and can effectively be promoted under shearing force
Into removing of the montmorillonite layer in Kynoar matrix, while the presence of ionic liquid improves between montmorillonite and matrix
Compatibility.
Embodiment 6
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.6g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Anti-static polyvinylidene fluoride piezoelectric material prepared by comparative example 1-3 and embodiment 3,5,6 is subjected to FTIR spectrum
Detection, using reflective-mode, wave-number range is 500-4000 centimetres-1.As shown in Fig. 2, Kynoar exists in comparative example 1-3
765,976 centimetres-1Place shows strong absorption peak, shows that only adding montmorillonite or ionic liquid cannot effectively induce and gather partially
In the formation of vinyl fluoride polar crystal, embodiment 3, embodiment 5 and embodiment 6 in the infrared spectrum of polyvinylidene fluoride composite material
Non-Polar Crystal is at 765,976 centimetres-1The absorption peak at place completely disappears, at 839,1234,1274 centimetres-1Place occurs obviously
Polar crystal absorption peak, show the synergistic effect of montmorillonite and ionic liquid induction of the complete of Kynoar polar crystal
Portion is formed.
Anti-static polyvinylidene fluoride piezoelectric material prepared by comparative example 1-3 and embodiment 1-6 is subjected to X-ray diffraction detection, angle
Degree range is 5-35 degree.As shown in figure 3, embodiment 3, embodiment 5 and 6 Kynoar of embodiment are multiple compared to comparative example 1-3
17.68 ° in the diffraction spectrogram of condensation material, 18.4 ° of angles of diffraction disappear, and apparent polar crystal occur at 20.3 ° of the angle of diffraction
Diffracted absorption peak, further demonstrate that the synergistic effect of ionic liquid and montmorillonite can effectively promote Kynoar polarity
The generation of crystal.
Anti-static polyvinylidene fluoride piezoelectric material prepared by comparative example 1-3 and embodiment 3,5,6 is subjected to ultraviolet-visible spectrum inspection
It surveys, thickness of sample is about 0.2 millimeter, and using the mode of penetrating, wave-length coverage is 200-800 nanometers.As shown in figure 4, compared to right
The translucency of ratio 1-3, embodiment 3, embodiment 5 and the polyvinylidene fluoride composite material in embodiment 6 obviously increases, material table
Reveal the excellent transparency, illustrates only just to be able to achieve polyvinylidene fluoride composite material with cooperateing with for montmorillonite by ionic liquid
High transparency.
Anti-static polyvinylidene fluoride piezoelectric material prepared by comparative example 1-3 and embodiment 3,5,6 is subjected to measurement, is used
LCR table is 102-106It is tested in frequency range, sample sprays 8 millimeters of silver electrodes up and down.As shown in figure 5, comparative example 1
There is almost the same dielectric constant with comparative example 2, it is several to show that only addition montmorillonite influences the dielectric properties of Kynoar
It is zero.In contrast, polyvinylidene fluoride composite material has highest dielectric constant in comparative example 3, illustrate in comparative example 3
Ion transfer has occurred under electric field action in ionic liquid, leads to higher dielectric constant.But the free migration of ionic liquid
Composite material is also resulted in very high dielectric loss, as shown in comparative example 3 in Fig. 6.However, high dielectric loss would generally
It generates thermal energy and then loses the energy stored by dielectric material, this is unfavorable as the application such as energy storage for dielectric material.
In the present invention, since ion exchange has occurred during melt blending in ionic liquid and montmorillonite, so that ionic liquid is consolidated
It is scheduled on montmorillonite layer and between lamella, this greatly limits the movement of ionic liquid under the electric field, as Fig. 5 and figure
Shown in embodiment 3 in 6, embodiment 5 and embodiment 6, the polyvinylidene fluoride composite material of ionic liquid and montmorillonite synergistic effect
Not only there is the dielectric constant of enhancing, while still remain very low dielectric loss.Compared to comparative example 1, comparative example 2 and right
Ratio 3, the polyvinylidene fluoride composite material in embodiment have excellent dielectric properties.
Embodiment 7
1) Kynoar, 1- cetyl -3- vinyl imidazole bromide and montmorillonite are dried in vacuo at 70 DEG C
24h；
(2) 60g Kynoar, 0.6g1- cetyl -3- vinyl imidazole bromide and the 0.06g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 8
1) Kynoar, 1- cetyl -3- vinyl imidazole bromide and montmorillonite are dried in vacuo at 70 DEG C
24h；
(2) 60g Kynoar, 0.6g1- cetyl -3- vinyl imidazole bromide and the 0.3g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 9
1) Kynoar, 1- cetyl -3- vinyl imidazole bromide and montmorillonite are dried in vacuo at 70 DEG C
24h；
(2) 60g Kynoar, 0.6g1- cetyl -3- vinyl imidazole bromide and the 0.6g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 10
1) Kynoar, 1- cetyl -3- methylimidazole bromide and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole bromide and the 0.3g montmorillonite after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 11
1) Kynoar, 1- butyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.6g 1- butyl -3- methylimidazole villaumite and the 0.3g montmorillonite after drying are added
In mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 12
1) Kynoar, 1- butyl -3- vinyl imidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.6g1- butyl -3- vinyl imidazole villaumite and the 0.3g montmorillonite after drying are added
Enter in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 13
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 300g Kynoar, 3g1- cetyl -3- methylimidazole villaumite and the 0.3g montmorillonite after drying are added
Enter into screw extruder, the melting mixing at 180 DEG C, rate of feeding 50rpm obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 14
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 300g Kynoar, 3g1- cetyl -3- methylimidazole villaumite and the 1.5g montmorillonite after drying are added
Enter in screw extruder, the melting mixing at 180 DEG C, rate of feeding 50rpm obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 15
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 300g Kynoar, 3g1- cetyl -3- methylimidazole villaumite and the 3g montmorillonite after drying are added
In screw extruder, the melting mixing at 180 DEG C, rate of feeding 50rpm obtains mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 16
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 300g Kynoar, 3g1- cetyl -3- methylimidazole villaumite and the 1.5g montmorillonite after drying are added
Enter into inflation film manufacturing machine, melting mixing blowing film forming, obtained film are used directly to test at 180 DEG C.
Embodiment 17
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and kaolin are dried in vacuo for 24 hours at 70 DEG C；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.06g kaolin after drying
It is added in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Embodiment 18
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and lithium magnesium silicate are dried in vacuo at 70 DEG C
24h；
(2) by 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.06g magnesium silicate after drying
Lithium is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Comparative example 4
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 0.003g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Comparative example 5
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.6g1- cetyl -3- methylimidazole villaumite and the 3g montmorillonite after drying are added
Enter in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Comparative example 6
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 0.006g1- cetyl -3- methylimidazole villaumite and the 0.3g after drying are covered de-
Soil is added in mixer, and the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Comparative example 7
1) Kynoar, 1- cetyl -3- methylimidazole villaumite and montmorillonite are dried in vacuo for 24 hours at 70 DEG C；
(2) 60g Kynoar, 7g1- cetyl -3- methylimidazole villaumite and the 0.3g montmorillonite after drying are added
Enter in mixer, the melting mixing 5min at 190 DEG C, spinner velocity 60rpm obtain mixture；
(3) the mixture cold moudling under tablet press machine for obtaining step (2), obtains polyvinylidene fluoride composite material.
Anti-static polyvinylidene fluoride piezoelectric material prepared by embodiment 3 and comparative example 4-7 is subjected to FTIR spectrum detection,
Using reflective-mode, wave-number range is 500-4000 centimetres-1.As shown in fig. 7, compared with example 3, comparative example 5 and 7, comparative example 4
With 6 in anti-static polyvinylidene fluoride piezoelectric material at 765,976 centimetres-1Place still have stronger absorption peak, show in piezoelectric material according to
So with the presence of part Non-Polar Crystal, this illustrates only to add minute quantity when ionic liquid or fixed montmorillonite content
Montmorillonite or ionic liquid not can induce the complete formation of Kynoar polar crystal.
Anti-static polyvinylidene fluoride piezoelectric material prepared by embodiment 3 and comparative example 4-7 is subjected to ultraviolet-visible spectrum detection,
Thickness of sample is about 0.2 millimeter, and using the mode of penetrating, wave-length coverage is 200-800 nanometers.As shown in figure 8, compared to embodiment
3, the translucency of polyvinylidene fluoride composite material decreases in comparative example 4, and the Kynoar composite wood in comparative example 5-7
The translucency of material is then substantially reduced, and illustrates that excessive ionic liquid or montmorillonite content can reduce the transparency of composite material.
Therefore, the high transparency of polyvinylidene fluoride composite material is only just able to achieve under appropriate ionic liquid and the content of montmorillonite.
Claims (10)
1. a kind of transparent electroactive polyvinylidene fluoride-based composite of height, which is characterized in that the composite material is by polyvinylidene fluoride
Alkene, ionic liquid and clay are to obtain after 100:0.05-10:0.01-3 is blended in mass ratio.
2. the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 1, which is characterized in that described
Kynoar, ionic liquid and clay mass ratio be 100:0.1-3:0.1-1.
3. the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 1, which is characterized in that described
Clay be phyllosilicate.
4. the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 3, which is characterized in that described
Phyllosilicate be montmorillonite, kaolin or lithium magnesium silicate.
5. the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 1, which is characterized in that described
Ionic liquid in cation be one, two, tri-substituted imidazole cationoid, one, disubstituted pyridines cationoid, quaternary amines sun from
Son, pyrrolidines cation, morpholine cationoid, piperidines cationoid；Anion is Cl-、Br-、I-、BF4 -、PF6 -、FeCl4 -、
CF3SO3 -、CH3COO-。
6. the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 5, which is characterized in that described
Ionic liquid be 1- cetyl -3- methylimidazole villaumite, 1- cetyl -3- vinyl imidazole bromide, 1- cetyl -
3- methylimidazole bromide, 1- butyl -3- methylimidazole villaumite or 1- butyl -3- vinyl imidazole villaumite.
7. the preparation method of the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 1, special
Sign is, this method comprises:
In mass ratio it is 100:0.05-10:0.01-3 proportion by Kynoar, ionic liquid and clay, is added to melting altogether
It is kneaded at 175-200 DEG C in mixing device, then by blend cold moudling, obtains polyvinylidene fluoride-based composite.
8. the preparation method of the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 7, special
Sign is, before the mixing, Kynoar, ionic liquid and clay are first dried in vacuo 24- at 60-80 DEG C respectively
48h。
9. the preparation method of the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 7, special
Sign is that the melt blending equipment is mixer, screw extruder or inflation film manufacturing machine.
10. the preparation method of the transparent electroactive polyvinylidene fluoride-based composite of height of one kind according to claim 7, special
Sign is, when the use mixer is blended, closed-smelting machine rotor revolving speed is 40-60rpm, and the blending time is 4-10min.
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