CN115991935B - Core-shell structure supermolecule-based dielectric elastomer composite material and preparation method and application thereof - Google Patents
Core-shell structure supermolecule-based dielectric elastomer composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N Michlers ketone Natural products C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 26
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
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Abstract
The invention discloses a core-shell structure supermolecule-based dielectric elastomer composite material, a preparation method and application thereof. The invention realizes coating of the biborate supermolecular shell on the surfaces of inorganic nanoparticle cores with different compositions, shapes and sizes by means of two supermolecular driving forces, namely B-N coordination driving force and strong surface binding force of catechol. The supermolecule@inorganic nanoparticle with the core-shell structure is used as dielectric filler to be filled into an elastomer matrix, the flexible supermolecule shell has good compatibility with the elastomer, and the polarity of the coordinated supermolecule shell with the outstanding boron group reduces the modulus and dielectric loss of the dielectric elastomer composite material, effectively improves the dielectric constant and the electric deformation, reduces the requirement of the dielectric elastomer on the electric field intensity, and has great application potential in the field of electric drive. Meanwhile, the preparation method is simple, easy to operate and easy to control the process.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a dielectric elastomer composite material.
Background
The Dielectric Elastomer (DE) material is a flexible intelligent material which can deform under the action of an electric field and recover the original shape after the electric field is removed to realize electric energy and mechanical energy conversion. By virtue of the characteristics of good flexibility, light weight, large electric deformation, easy processing and the like, the DE material can be applied to various fields of aerospace, bionics, medical rehabilitation, robots, optics and the like in the future. However, the DE materials often require high driving voltages to achieve large driving deformations, so the commercial use of DE materials is still in an immature stage. Therefore, DE to achieve high driving strain at low driving voltages is a challenging topic.
Theoretically, the driving strain of DE materials can be influenced by the dielectric constant, the applied voltage, the young's modulus (elastic modulus) of the material. According to the mechanism of DE, increasing the dielectric constant and decreasing the modulus are viable ways to achieve high driving strain at low electric fields. According to previous studies, the most common method to increase the dielectric constant of DE is to add a high dielectric ceramic filler or conductive filler to the matrix. For dielectric elastomers of the conductive filler class, based on the percolation theory, the dielectric constant increases dramatically when the concentration of the conductive filler approaches the percolation threshold, and the dielectric loss increases and the electrical breakdown strength decreases when the loading of the conductive particles reaches or exceeds the percolation threshold. Whereas the usual high dielectric ceramic fillers are incorporated into the elastomer matrix although high dielectric constants can be obtained. However, a large amount of ceramic filler causes a sharp increase in elastic modulus, and more defects occur inside the composite material, resulting in a decrease in actuation performance. Therefore, in order to overcome this problem, further improvements to the DE material are necessary.
Disclosure of Invention
Based on the prior art, the invention provides a core-shell structure supermolecule-based dielectric elastomer composite material, and a preparation method and application thereof.
The invention discovers that supermolecules depend on the interfacial interaction between strong/weak interaction and solid materials, and are important driving forces for manufacturing advanced composite materials by decorating the solid materials with a supermolecule shell. The catechol group is introduced into the supermolecule chain segment, and the strong interfacial binding force of the catechol group can effectively connect the supermolecule on the surface of various materials, so that the modification of the supermolecule on the inorganic nano particles can be simplified. The unique interface regulation mechanism of the diboron group and the advantages of supermolecule self-assembly endow the diboron ester supermolecule core-shell structure with research potential. In addition, the symmetrical small boron-linked molecules lose symmetry after coordination, so that the polarity of the boron-linked compound is improved, the promotion effect on the improvement of the dielectric property of the dielectric elastomer is achieved, and the promotion of the electro-active driving property of the dielectric elastomer is facilitated. Based on the thought, the invention provides the following technical scheme:
one of the technical schemes adopted for solving the technical problems is as follows:
the preparation method of the core-shell structure supermolecule-based dielectric elastomer composite material comprises the following specific steps:
step one (preparation of biboronate supermolecule @ inorganic nanoparticle): dispersing inorganic nano particles in an alcohol solution in an ultrasonic manner to form an inorganic nano particle dispersion liquid, adding an alcohol solution of a multi-arm catechol monomer into the dispersion liquid, stabilizing for a period of time, and then dropwise adding an alcohol solution of a diboron compound into the dispersion liquid; fully reacting to complete the reaction of supermolecule DDDP coated inorganic nano particles formed by the diboron compound and the multi-arm catechol; repeatedly washing with ethanol to purify the coated nano particles, and drying the coated nano particles in a vacuum oven overnight to obtain the biboronate supermolecule@inorganic nano particles with a core-shell structure;
step two (preparation of dielectric elastomer composite): and (3) ultrasonically dispersing the above-mentioned diboronate supermolecule@inorganic nano particles with a core-shell structure into absolute ethyl alcohol, then adding the obtained solution into a solution in which an elastomer matrix is dissolved, uniformly mixing the solution, evaporating the solvent, adding a curing agent into the evaporated mixed substance, and curing to obtain the supermolecule-based dielectric elastomer composite material doped with the core-shell structure.
The monomer-based inorganic nanoparticles used in the first step of the invention are Chinese and abbreviated as: zinc oxide (ZnO), silicon dioxide (SiO) 2 ) Titanium dioxide (TiO) 2 )。
The diboron compound used in the first step of the invention is tetra (dimethylamino) diboron (DB-1), the multi-arm catechol monomer used in the first step is TRC with imine bond, R in the TRC is one of R1, R2, R3 or R4, and the structural formula of the compound is shown as formula I:
the reaction formula involved in the formation of the supramolecular DDDP shell layer in the first step of the invention is shown as a formula II:
the alcohol solvent in the first step of the invention comprises at least one of ethanol or methanol.
In the first step of the present invention, the concentration of the diboron compound in the alcoholic solution is in the range of 0.001 mM-1000M, the concentration of the multi-arm catechol monomer in the alcoholic solution is in the range of 0.001 mM-1000M, and the concentration of the inorganic nanoparticle (particle size of 1-500 nm) is in the range of 0-30 mg/mL, for example, 10mg/mL. The temperature of the reaction system is 35 ℃ or lower, and the reaction time is at least 3 hours, but not more than 72 hours, for example 8 hours.
In the first step of the invention, the concentration of the diboron compound and catechol directly determines the thickness of the shell layer coated by the inorganic nano particles, and the larger the monomer concentration is, the larger the thickness of the shell layer is, and the range of the thickness of the shell layer along with the monomer concentration is 1-1000 nm. And the size of the inorganic particles also determines the shell thickness, with smaller particles having smaller maximum shell thickness.
In the first step of the invention, the inorganic nanoparticle core layer can change the energy level of the supermolecule shell layer. As the shell thickness increases, the HOMO (highest occupied molecular orbital ) energy level of the shell supramolecules becomes progressively smaller and the LUMO (lowest unoccupied molecular orbital ) energy level becomes progressively larger.
In step one of the present invention, the temperature at which the material is dried overnight in a vacuum oven is, for example, 60 ℃.
In the second step of the invention, the mass ratio of the diboronate supermolecule@inorganic nanoparticle with a core-shell structure to the elastomer matrix is in the range of 0-50: 100, the mass ratio of the elastomer matrix to the curing agent ranges from 1 to 100:1.
in the second step of the invention, the elastomer matrix is rubber; the rubber is natural rubber, silicon rubber, nitrile rubber, butyl rubber or acrylic rubber. The solvent of the solution containing the elastomer matrix is, for example, tetrahydrofuran, n-hexane or the like.
In the second step of the invention, the temperature of the evaporating solvent is less than 60 ℃; the curing temperature range is 30-100 ℃; the curing time range is 1 hour or more.
In the second step of the invention, the curing agent contains hydrogen silicone oil system, sulfur system and organic peroxide system; the hydrogen-containing silicone oil system is hydrogen-containing silicone oil; the sulfur system is sulfur, zinc oxide and stearic acid; the organic peroxide system is di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the core-shell structure supermolecule-based dielectric elastomer composite material prepared by the preparation method.
The dielectric constant of the core-shell structure supermolecule-based dielectric elastomer composite material is 3-3500 at 1kHz, and the Young modulus is 0.001-10 Mpa.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
the application of the core-shell structure supermolecule-based dielectric elastomer composite material in the field of electro-actuation.
The equipment, reagents, processes, parameters, etc. according to the present invention are conventional equipment, reagents, processes, parameters, etc. unless otherwise specified, and are not exemplified.
All ranges recited herein are inclusive of all point values within the range.
In the present invention, the "room temperature" is a conventional ambient temperature, and may be 10 to 30 ℃.
The beneficial effects of the invention are as follows:
according to the invention, by means of two supermolecule driving forces, namely B-N coordination driving force and catechol strong surface binding force, the surface of inorganic nanoparticle cores with different compositions, shapes and sizes is coated with the supermolecule shell of the biboronate, the thickness of the supermolecule shell is controllable by the concentration of a monomer, and the higher the concentration of the monomer is, the larger the thickness of the shell is; and the inorganic nano particles can change the energy level of supermolecules with different shell thicknesses. In the rubber processing process, the ortho-position polyphenol of the shell layer is oxidized to form an ortho-quinone group, and the ortho-quinone group reacts with the curing agent and sulfur to establish a cross-linking structure, so that the compatibility of the core-shell structure and the silicon rubber is improved, the modulus of the composite material is reduced, and in addition, a good elastomer filling effect can be achieved by using a small amount of the ortho-polyphenol. The supermolecule of the biboronate with the core-shell structure is used as dielectric filler to be filled in an elastomer matrix, compared with TRC monomer, the molecular chain length of the supermolecule increases the semiconductor characteristic of the shell structure, and the interface polarization of the core-shell structure of the composite material is increased due to the difference of the conductivity of the supermolecule shell and the elastomer matrix; in addition, the supermolecule with the shell structure increases the diversity of molecular conformation and improves the dipole polarization of the composite material due to the synergistic effect of strong B-N coordination between the boron-linked group and the imine. The dipole polarization and the interface polarization which are synchronously increased under the action of an electric field improve the dielectric constant of the composite material, reduce the dielectric loss of the composite material and obviously improve the electro-deformation. And the electro-deformation is controlled by the thickness and the filling quantity of the shell layer of the core-shell structure. In addition, the B-N coordinated supermolecule core-shell structure reduces the requirement of the material on the electric field intensity, and has great application prospect in the field of dielectric elastomer electro-drive. Meanwhile, the preparation method is simple, easy to operate and easy to control the process.
Drawings
FIG. 1 shows that the supramolecules (DDBP) produced by DB-1 and TR1C (R in TRC is R1) are used as shell layers, znO and TiO respectively 2 And (3) a curve of different shell thicknesses for a nuclear layer and a cyclic voltammetry test.
FIG. 2 is a graph illustrating the stretching and electrostriction of different coating thickness core-shell fillers, different filler amounts of an elastomer, the elastomer used being Polydimethylsiloxane (PDMS).
Fig. 3 is a view illustrating a dark field transmission electron microscope of core-shell structures of different inorganic nanoparticles, core-shell structures of different coating thicknesses, and a transmission electron microscope thereof, wherein: (a) Is TiO 2 @DDBP ST＝28 Dark field transmission electron microscopy of (b) is TiO 2 @DDBP ST＝40 And (c) is TiO 2 @DDBP ST＝36 And (d) is TiO 2 @DDBP ST＝28 And (e) is TiO 2 @DDBP ST＝20 And (f) is TiO 2 @DDBP ST＝10 And (g) is ZnO@DDBP ST＝28 (h) is ZnO@DDBP ST＝40 Is (i) ZnO@DDBP ST＝35 And (j) is ZnO@DDBP ST＝28 (k) is ZnO@DDBP ST＝20 (l) is ZnO@DDBP ST＝10 Is a transmission electron microscope image of (a).
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
Step one: tiO is mixed with 2 Ultrasonic dispersion in an alcohol solution to form a dispersion of 10mg/mL, followed by adding 3.34mM of an alcohol solution of TR1C (R in TRC is R1) to the dispersion, stabilizing for a period of time, and then adding dropwise thereto a 5mM of DB-1 alcohol solution. Fully reacting for 8 hours to finish the formation of supermolecule DDBP formed by TR1C and DB-1 in TiO 2 Coating the material. By coolingRepeatedly washing with ethanol to purify the coating material, and drying at 60deg.C in vacuum oven overnight to obtain TiO with core-shell structure 2 @DDBP ST＝28 (fig. 3 (d)).
Step two: tiO is mixed with 2 @DDBP ST＝28 Ultrasonic dispersing into absolute ethyl alcohol, then adding into tetrahydrofuran solution dissolved with PDMS, tiO 2 @DDBP ST＝28 The mass ratio of the polymer to PDMS is 1:100; and (3) after the two solutions are uniformly mixed, evaporating the solvent, adding a hydrogen-containing silicone oil curing agent (PDMS: curing agent=10:1) into the evaporated mixed substance, and curing for 10 hours at 50 ℃ to obtain the supermolecule-based dielectric elastomer composite material doped with the core-shell structure (hereinafter referred to as dielectric elastomer composite material for short).
The dielectric elastomer composite obtained in this example was tested:
dielectric constant test: the dielectric constant was measured using a 4284A dielectric constant tester of hewlett packard. The frequency range of dielectric constant is 20-10 6 。
Elastic modulus test: tensile experiments were performed using a universal tester for SANS. The sample bars were prepared to have a length, width and height of 5 cm. Times.1 mm, respectively. The mechanical property test is carried out on the composite material sample bar at the stretching rate of 100mm/min under the room temperature condition, and the elastic modulus is obtained by carrying out linear fitting on stress strain data.
And (3) testing the electric deformation and breakdown strength: and spraying flexible electrodes on two sides of a film formed by the dielectric elastomer composite material with the thickness of 200 mu m, wherein the diameter of the flexible electrodes is 5cm multiplied by 5cm, and drying the electrodes in a blast oven for testing. The voltage is controlled by a Bohr high voltage power supply, and the deformation of the electrode area of the dielectric elastomer composite material under the stimulation of an electric field is recorded by a camera until the dielectric elastomer composite material is broken down, and the voltage and the electro-deformation amount during the breakdown are recorded.
The thickness of the finally obtained supermolecule shell layer is 28nm.
The dielectric elastomer composite had a dielectric constant of 3.9.
The modulus of the dielectric elastomer composite was 6KPa.
The deformation and the strength of the maximum withstand voltage of the dielectric elastomer composite were 15% and 71V/μm, respectively.
Example 2
The preparation was carried out in the same manner as in example 1, except that the concentrations of TR1C and DB-1 in step one were reduced by half, namely 1.67mM of TR1C and 2.5mM of DB-1, respectively, to give TiO 2 @DDBP ST＝20 (fig. 3 (e)).
The thickness of the finally obtained supermolecule shell layer is 20nm.
The dielectric elastomer composite had a dielectric constant of 4.2.
The modulus of the dielectric elastomer composite was 7kPa.
The deformation and the strength of the maximum withstand voltage of the dielectric elastomer composite were 11% and 54V/μm, respectively.
Example 3
The preparation method is the same as in example 2, except that TiO in step two 2 @DDBP ST＝20 The mass ratio of the polymer to PDMS is 10:100.
the thickness of the finally obtained supermolecule shell layer is 20nm.
The dielectric elastomer composite had a dielectric constant of 6.2.
The modulus of the dielectric elastomer composite was 5KPa.
The deformation and the strength of the maximum withstand voltage of the dielectric elastomer composite were 20% and 84V/μm, respectively.
Example 4
Referring to the method of example 1, the concentrations of the monomers TR1C and DB-1 and the kinds of the inorganic nanoparticles were changed (the same concentration of the monomers, coated TiO 2 The thickness of the shell layer of ZnO is basically the same), respectively preparing TiO 2 @DDBP ST＝10 (f) in FIG. 3), tiO 2 @DDBP ST＝36 (fig. 3 (c)), tiO 2 @DDBP ST＝40 (fig. 3 (b)), zno@ddbp ST＝40 (h) in FIG. 3), znO@DDBP ST＝35 (i) in FIG. 3), znO@DDBP ST＝28 (j) in FIG. 3), znO@DDBP ST＝20 (k) in FIG. 3), znO@DDBP ST＝10 (fig. 3 (l)), and the like.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. A preparation method of a core-shell structure supermolecule-based dielectric elastomer composite material is characterized by comprising the following steps: comprising the following steps:
step one: dispersing inorganic nano particles in an alcohol solution in an ultrasonic manner to form an inorganic nano particle dispersion liquid, adding an alcohol solution of a multi-arm catechol monomer into the dispersion liquid, dropwise adding an alcohol solution of a diboron compound into the dispersion liquid, and reacting for 3-72 h at the temperature of not higher than 35 ℃ to obtain the diboron ester supermolecule@inorganic nano particles with a core-shell structure; the boron-linked compound is DB-1, the multi-arm catechol monomer is TRC, and R in the TRC is one of R1, R2, R3 or R4, and the structural formula is shown as follows:
step two: dispersing the prepared supermolecule@inorganic nano particles with core-shell structure into absolute ethyl alcohol, adding the inorganic nano particles into a solution dissolved with an elastomer matrix, uniformly mixing, removing the solvent, and curing to obtain the supermolecule-based dielectric elastomer composite material doped with the core-shell structure;
the concentration range of the diboron compound in the alcohol solution is 0.001 mM-1000M, and the concentration range of the multi-arm catechol monomer in the alcohol solution is 0.001 mM-1000M;
the inorganic nano particles comprise ZnO and SiO 2 Or TiO 2 At least one of (a) and (b);
the particle size of the inorganic nano particles is 1-500 nm.
2. The method of manufacturing according to claim 1, characterized in that: the concentration of the inorganic nanoparticles in the inorganic nanoparticle dispersion is not higher than 30mg/mL.
3. The method of manufacturing according to claim 1, characterized in that: the alcohol includes at least one of ethanol or methanol; the solvent of the solution in which the elastomer matrix is dissolved in the second step comprises at least one of tetrahydrofuran or n-hexane.
4. The method of manufacturing according to claim 1, characterized in that: the elastomer matrix is rubber; the rubber is natural rubber, silicon rubber, nitrile rubber, butyl rubber or acrylic rubber.
5. A core-shell structure supramolecular-based dielectric elastomer composite prepared according to the preparation method of any one of claims 1 to 4.
6. The core-shell structure supramolecular-based dielectric elastomer composite of claim 5, wherein: the dielectric constant of the core-shell structure supermolecule-based dielectric elastomer composite material is 3-3500 under 1kHz, and the Young modulus is 0.001-10 Mpa.
7. Use of a core-shell structured supermolecule based dielectric elastomer composite according to claim 5 or 6 in electro-actuation.
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