阅读说明：本技术 一种透明高电活性聚偏氟乙烯基复合材料及其制备方法 (Transparent electroactive polyvinylidene fluoride-based composite of height of one kind and preparation method thereof ) 是由 孙树林 宋士新 夏珊 刘岩 吕雪 于 2019-09-10 设计创作，主要内容包括：本发明提供一种透明高电活性聚偏氟乙烯基复合材料及其制备方法,属于高分子材料及先进纳米复合材料领域。该复合材料是将聚偏氟乙烯、离子液体和粘土按质量比为100：0.05-10：0.01-3共混后得到的。本发明还提供一种透明高电活性聚偏氟乙烯基复合材料的制备方法。本发明的复合材料具有高的透过性和100％的极性晶体；除此之外,粘土可以抑制离子液体在电场下的迁移,降低复合材料的介电损耗,这拓宽了其作为压电材料的应用。(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.)

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.

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.