CN110564134A - preparation method of polyurethane-based composite nitrile rubber dielectric elastomer - Google Patents
preparation method of polyurethane-based composite nitrile rubber dielectric elastomer Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyurethane-based composite nitrile butadiene rubber dielectric elastomer, belonging to the technical field of dielectric elastomer materials. The invention uses the graphene oxide to wrap the nano titanium dioxide and the superconducting carbon black as the conductive filler to prepare the dielectric elastomer, the nano titanium dioxide is used as a core to play a supporting role, the graphene oxide is used as a wrapping shell layer, the nano titanium dioxide and the graphene oxide have high conductivity and large specific surface area, the micro-capacitor structure can be formed in a polymer matrix, can effectively increase the dielectric constant of the material, the superconducting carbon black has very large specific surface area and can be used as a rubber reinforcing agent, the conductivity of the carbon black is high, so the dielectric constant of the polymer can be improved by enhancing the interfacial polarization, and the spherical structure of the carbon black can not greatly improve the elastic modulus of the material, and the mixture of the carbon black and the elastomer can effectively improve the dielectric constant of the material without greatly improving the elastic modulus of the elastomer, thereby being beneficial to reducing the driving voltage when the material is applied and improving the safety.
Description
Technical Field
The invention relates to a preparation method of a polyurethane-based composite nitrile butadiene rubber dielectric elastomer, belonging to the technical field of dielectric elastomer materials.
Background
among a plurality of electroactive polymer (EAP) materials, DE attracts attention of many scholars due to the characteristics of high energy density, large deformation amount, high response speed, good load matching property, high electromechanical conversion efficiency, strong environmental adaptability, light weight, low price and the like, DE can generate huge strain (about 50 ~ 380%) under a medium stress level, has a wide energy density range (0.01 ~ 3 MJ/kg) and can generate deformation response within an electric field strength range of 70 ~ 400V/um, and the DE has wide application in the aspects of driving, sensing, power generation and the like in recent years due to the special excellent performance.
However, the current dielectric elastomer material needs a very large driving voltage to realize good electromechanical conversion performance, which severely restricts the application prospect of the dielectric elastomer. Therefore, designing and preparing new dielectric elastomer materials has become a hot point of research.
A Dielectric Elastomer (DE) is an elastic dielectric film that is covered on both surfaces with flexible electrodes and loaded with an electric field, and then the electrostatic attraction between opposite charges on the two electrodes and the repulsion between the same charges on the same electrode cause the DE to stretch in the direction of area and compress in the direction of thickness. As a result of this process, the electrical energy stored in the system is converted into mechanical energy, which is transformed from electrical energy to mechanical energy. After the electric field is removed, the DE film will return to its original shape due to elastic cycling of the DE film itself, as the interaction of free electrons on the electrodes is lost. The strain forms of DE are mainly bending, contraction and expansion, etc. Therefore, the dielectric elastomer material can be used in the forward direction (converting electric energy into mechanical energy) and used as an optimal bionic driving material for artificial muscles, such as robot design, micro mechanical drivers, bionics, medical devices and the like; the device can also be used reversely (converting mechanical energy into electric energy), and plays a role in the fields of power generation, sensing and the like, such as tidal power generation, personal portable electronic equipment, wearable electronic equipment and the like.
Commonly used dielectric elastomer materials mainly include acrylate elastomers, silicone rubbers, polyurethane elastomers, nitrile rubbers, vinylidene fluoride trifluoroethylene, and composites thereof.
The silicone rubber is a semi-inorganic polymer with Si-O bond and two hydrocarbon radicals as basic units, and is polymerized to form long chain. The most widely used silicone rubber is Polydimethylsiloxane (PDMS). The current commercial silicone rubber products include NeukasilRTV-23, Dow Corning DC3481, Nusil CF19-2186 and BJBTC 5005.
Polyurethane (PU) is a polymer with a main chain containing-NHCOO-repeating structural units, and includes various forms such as rigid polyurethane plastics, flexible polyurethane plastics, polyurethane elastomers, and the like, and is divided into two main types, namely thermoplastic and thermosetting. The polyurethane elastomer is a high molecular polymer between common rubber and hard plastic, is a typical block copolymer, is polymerized by diisocyanate, various alcohols and different vulcanizing agents, and has a complex chemical structure. Because the silicon rubber contains a large number of polar functional groups, the dielectric constant can reach about 7, which is much higher than that of silicon rubber and acrylic ester materials. However, the presence of a large number of polar functional groups results in poor insulation properties and low breakdown strength.
In addition, unlike conventional chemically crosslinked elastomers, the macromolecules contain physical crosslinks formed by a large number of crystalline regions in the interior of the polyurethane in addition to chemical crosslinks formed by soft segments. The chemical network structure enables the Young modulus of polyurethane to be extremely high, and the polyurethane cannot be greatly pre-stretched like silicon rubber and acrylic ester materials, so that the problem of possible force and power instability during DE work is difficult to solve.
The acrylate material is made from a mixture of aliphatic acrylates, the elasticity resulting from mild crosslinking of the soft branched aliphatic groups and the acrylic polymer chains. Currently, in the research of dielectric elastomer materials, commercially available acrylate materials are commercially available adhesive tapes VHB4910 and VHB4905 from 3M company.
the acrylic material is one of the three types of dielectric elastomer materials with the most excellent performance, namely dielectricthe preferred material for elastomer research is low in price, excellent in performance and good in adhesion with a compliant electrode, can be used without processing, is favored by researchers, under the condition of large pre-strain, the maximum stress and strain of the acrylate material can reach 7.7MPa and 380 percent respectively, the dielectric constant of the acrylate material is about 4.7, and after pre-stretching, the acrylate material has incomparable breakdown strength3。
Although the dielectric properties of the acrylate materials are excellent, two problems still exist to hinder the application. On the one hand, its excellent dielectric properties are only achieved under high pre-strain conditions. However, the large pre-strain state may cause many practical problems, such as the phenomena of force and electricity instability at the joint of the elastic body and the rigid body, stress relaxation, and complicated equipment manufacture; on the other hand, the viscoelastic property of the acrylic elastomer causes the acrylic elastomer to have poor electromechanical responsiveness, low efficiency and small bandwidth (about 50 Hz) of a responsive electric signal; compared with silicon rubber, the acrylate material has poor adaptability to the environment, and basically loses electromechanical response capability below 0 ℃.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem that the prior dielectric elastomer material needs very high driving voltage when in application, provides a preparation method of a polyurethane-based composite nitrile rubber dielectric elastomer.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) placing the graphene oxide coated nano titanium dioxide and the superconducting carbon black in a stirrer, and stirring and mixing at the rotating speed of 300-360 r/min for 20-30 min at normal temperature to obtain a conductive filler;
(2) and mixing the conductive filler, magnesium stearate, nano zinc oxide powder and composite rubber particles, putting the mixture into a double-screw extruder, extruding and granulating at the rotating speed of 380-400 r/min, and standing at normal temperature for 2-4 hours to obtain the polyurethane-based composite nitrile rubber dielectric elastomer.
The composite rubber particles, the graphene oxide coated nano titanium dioxide, the superconducting carbon black, the magnesium stearate and the nano zinc oxide powder are 80-100 parts by weight of the composite rubber particles, 20-25 parts by weight of the graphene oxide coated nano titanium dioxide, 20-25 parts by weight of the superconducting carbon black, 1-3 parts by weight of the magnesium stearate and 4-5 parts by weight of the nano zinc oxide powder.
the temperatures of all zones of the double-screw extruder in the step (2) are 270 ℃ at the first zone, 270 ℃ at the second zone, 280 ℃ at the third zone, 280 ℃ at the fourth zone, 280 ℃ at the fifth zone, 280 ℃ at the sixth zone, 270 ℃ at the seventh zone and 260 ℃ at the die head.
the specific preparation steps of the composite rubber particles in the step (2) are as follows:
(1) Placing the polyurethane rubber and the nitrile rubber into a grinder to be ground for 10-15 min, then placing the ground materials into a stirrer to be stirred for 5-10 min at normal temperature at a rotating speed of 120-160 rmin to obtain a rubber mixture;
(2) And (3) placing the rubber mixture and the antioxidant BHT in a double-screw extruder, extruding and granulating at the rotating speed of 300-360 r/min, and standing at normal temperature for 2-4 hours to obtain the composite rubber particles.
The polyurethane rubber, the nitrile rubber and the antioxidant BHT are 60-80 parts by weight of polyurethane rubber, 30-40 parts by weight of nitrile rubber and 1-3 parts by weight of antioxidant BHT.
The temperature of each zone of the double-screw extruder in the step (2) is 260 ℃ of the first zone, 260 ℃ of the second zone, 270 ℃ of the third zone, 270 ℃ of the fourth zone, 280 ℃ of the fifth zone, 280 ℃ of the sixth zone, 260 ℃ of the seventh zone and 260 ℃ of the die head.
The specific preparation steps of the graphene oxide coated nano titanium dioxide in the step (1) are as follows:
(1) adding nano titanium dioxide into 1/3 deionized water, stirring at the normal temperature at the rotating speed of 800-1000 r/min for 20-40 min, placing the mixture in an ultrasonic cleaning machine for ultrasonic treatment for 10-20 min, and then placing the mixture in a probe ultrasonic device for ultrasonic treatment for 1-2 h to obtain nano titanium dioxide dispersion liquid;
(2) adding graphene oxide into the rest 2/3 of deionized water, stirring at the rotating speed of 200-240 r/min for 10-15 min at normal temperature, and then placing the mixture in a probe ultrasonic device for ultrasonic treatment for 1-2 h to obtain a graphene oxide solution;
(3) slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 30-40 mL/min, and stirring for 2-4 hours at the constant temperature of 300-360 r/min under the water bath condition of 30-40 ℃ to obtain a mixed dispersion liquid;
(4) Concentrating the mixed dispersion liquid at 60-80 ℃ for 2-4 h, and cooling at normal temperature to obtain a concentrated dispersion liquid;
(5) and placing the concentrated dispersion liquid into a vacuum suction filter, carrying out suction filtration under the condition of 600-800 Pa, taking the filter cake, washing the filter cake with deionized water for 3-5 times, and placing the filter cake at the temperature of-4-0 ℃ for freeze drying for 20-24 hours to obtain the graphene oxide coated nano titanium dioxide.
the graphene oxide, the nano titanium dioxide and the deionized water are 60-80 parts by weight of graphene oxide, 30-40 parts by weight of nano titanium dioxide and 270-360 parts by weight of deionized water.
The power of the ultrasonic cleaning machine in the step (1) is 800-1000W, and the power of the probe ultrasonic device is 400-500W.
And (3) the power of the probe ultrasonic device in the step (2) is 400-500W.
Compared with other methods, the method has the beneficial technical effects that:
(1) The invention takes polyurethane blending nitrile rubber as an elastomer substrate to prepare a dielectric elastomer, the polyurethane elastomer is a special class in the elastomer, and comprises polyester polyurethane and polyether polyurethane, the polyurethane elastomer is prepared by the polycondensation reaction of oligomer polyol, polyisocyanate and a chain extender, the chemical structure of the polyurethane elastomer contains repeated urethane chain segments, the polyurethane elastomer contains a large number of oxygen bonds, imino functional groups from a hard segment are proton donors, urethane carbonyl and urea carbonyl from a hard segment, ether oxygen from a polyether soft segment or ester carbonyl from a polyester soft segment are proton acceptors, 80 to 90 percent of imino participates in the formation of hydrogen bonds at room temperature, most of the hydrogen bonds exist between the hard segment and the hard segment, a small part of the hydrogen bonds exist between the hard segment and the soft segment, the hydrogen bonds are stronger intermolecular forces, the number of the hydrogen bonds is more, the stronger the intermolecular acting force is, the higher the strength of the material is, so the dielectric elastomer prepared by taking polyurethane as a base material has good mechanical strength, the polyurethane can be processed by a plastic processing method due to the particularity of polyurethane crosslinking, the thermoplasticity of the polyurethane is very suitable for processing and forming, the dielectric elastomer is prepared so as to reduce the operating voltage of the material, the polyurethane has good polarization capacity, meanwhile, the polyurethane has very high dielectric constant, electrostriction and breakdown voltage, and is a good dielectric elastomer matrix, the nitrile rubber is polar rubber obtained by polymerizing butadiene and acrylonitrile, has good oil resistance and mechanical property, high dielectric constant, low modulus and viscoelasticity, and is an elastomer with excellent performance, and the mechanical property and breakdown strength of the elastomer matrix can be effectively improved by blending the nitrile rubber and the polyurethane, the dielectric constant of the elastomer is improved, and the elastic modulus is reduced, so that the electrorheological property of the dielectric elastomer under low voltage is improved, the driving voltage of the material in application is effectively reduced, and the safety is improved;
(2) The invention uses the nano titanium dioxide and the superconducting carbon black wrapped by the graphene oxide as the conductive filler to prepare the dielectric elastomer, the nano titanium dioxide is used as the core and is wrapped by the graphene oxide to obtain the conductive filler, the nano titanium dioxide is used as the core to play a supporting role, the graphene oxide is used as the wrapping shell layer, the nano titanium dioxide and the graphene oxide have high conductivity and large specific surface area, a micro-capacitor structure is favorably formed in a polymer matrix, the dielectric constant of the material can be effectively increased, the superconducting carbon black has very large specific surface area and can be used as a rubber reinforcing agent, the conductivity of the carbon black is high, therefore, the dielectric constant of the polymer can be increased by enhancing the interface polarization, the elastic modulus of the material cannot be greatly increased by the spherical structure of the carbon black, the dielectric constant of the material can be effectively increased by mixing the nano titanium dioxide and the superconducting carbon black, the driving voltage is reduced when the material is applied, and the safety is improved.
Detailed Description
Respectively weighing 60-80 parts of graphene oxide, 30-40 parts of nano titanium dioxide and 270-360 parts of deionized water according to parts by weight, adding the nano titanium dioxide into 1/3 of the deionized water, stirring for 20-40 min at the rotating speed of 800-1000 r/min at normal temperature, placing in an ultrasonic cleaner, performing ultrasonic treatment for 10-20 min at the power of 800-1000W, placing in a probe ultrasonic device, performing ultrasonic treatment for 1-2 h at the power of 400-500W to obtain nano titanium dioxide dispersion liquid, adding the graphene oxide into the rest 2/3 of the deionized water, stirring for 10-15 min at the rotating speed of 200-240 r/min at normal temperature, placing in the probe ultrasonic device, performing ultrasonic treatment for 1-2 h at the power of 400-500W to obtain graphene oxide solution, slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 30-40 mL/min, placing the mixture in a water bath at 30-40 ℃ and stirring the mixture for 2-4 h at a constant speed of 300-360 r/min to obtain a mixed dispersion, placing the mixed dispersion in a water bath at 60-80 ℃ for concentrating for 2-4 h, cooling the mixture at normal temperature to obtain a concentrated dispersion, placing the concentrated dispersion in a vacuum filter, carrying out suction filtration under the condition of 600-800 Pa, taking a filter cake to wash with deionized water for 3-5 times, placing the filter cake at-4-0 ℃ for freeze drying for 20-24 h to obtain graphene oxide coated nano titanium dioxide, respectively weighing 60-80 parts by weight of polyurethane rubber, 30-40 parts by weight of nitrile rubber and 1-3 parts by weight of antioxidant BHT, placing the polyurethane rubber and the nitrile rubber in a crusher to crush for 10-15 min, placing the crushed products in a stirrer, stirring the stirred products at a normal temperature of 120-160 rmin for 5-10 min to obtain a rubber mixture, mixing the rubber mixture, Placing antioxidant BHT in a double-screw extruder, extruding and granulating at 300-360 r/min under the conditions of first-zone temperature 260 ℃, second-zone temperature 260 ℃, third-zone temperature 270 ℃, fourth-zone temperature 270 ℃, fifth-zone temperature 280 ℃, sixth-zone temperature 280 ℃, seventh-zone temperature 260 ℃ and die head temperature 260 ℃ for 2-4 h at normal temperature to obtain composite rubber particles, respectively placing 80-100 parts by weight of composite rubber particles, 20-25 parts by weight of graphene oxide coated nano titanium dioxide, 20-25 parts by weight of superconducting carbon black, 1-3 parts by weight of magnesium stearate and 4-5 parts by weight of nano zinc oxide powder in a stirrer, stirring and mixing at normal temperature at 300-360 r/min for 20-30 min to obtain conductive filler, mixing the conductive filler, the magnesium stearate, the nano zinc oxide powder and the composite rubber particles, placing in the double-screw extruder, extruding and granulating at the rotating speed of 380-400 r/min under the conditions of the temperature of a first zone of 270 ℃, the temperature of a second zone of 270 ℃, the temperature of a third zone of 280 ℃, the temperature of a fourth zone of 280 ℃, the temperature of a fifth zone of 280 ℃, the temperature of a sixth zone of 280 ℃, the temperature of a seventh zone of 270 ℃ and the temperature of a die head of 260 ℃, and standing at normal temperature for 2-4 hours to obtain the polyurethane-based composite nitrile rubber dielectric elastomer.
example 1
Respectively weighing 60 parts of graphene oxide, 30 parts of nano titanium dioxide and 270 parts of deionized water according to parts by weight, adding the nano titanium dioxide into 1/3 of the deionized water, stirring for 20min at the rotating speed of 800r/min at normal temperature, placing the mixture in an ultrasonic cleaner, performing ultrasonic treatment for 10min under the condition of 800W of power, placing the mixture in a probe ultrasonic device, performing ultrasonic treatment for 1h under the condition of 400W of power to obtain nano titanium dioxide dispersion liquid, adding the graphene oxide into the rest 2/3 of the deionized water, stirring for 10min at the rotating speed of 200r/min at normal temperature, placing the mixture in the probe ultrasonic device, performing ultrasonic treatment for 1h under the condition of 400W of power to obtain graphene oxide solution, slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 30mL/min, placing the mixture in a water bath at the temperature of 30 ℃ and stirring for 2h at the constant temperature of 300r/min, obtaining mixed dispersion liquid, concentrating the mixed dispersion liquid at 60 ℃ for 2h, cooling at normal temperature to obtain concentrated dispersion liquid, placing the concentrated dispersion liquid in a vacuum filter, carrying out suction filtration under the condition of 600Pa, taking filter cakes, washing with deionized water for 3 times, placing the filter cakes in a-4 ℃ condition, freeze-drying for 20h to obtain graphene oxide coated nano titanium dioxide, respectively weighing 60 parts of polyurethane rubber, 30 parts of nitrile rubber and 1 part of antioxidant BHT according to parts by weight, placing the polyurethane rubber and the nitrile rubber in a crusher, crushing for 10min, placing the crushed polyurethane rubber and the nitrile rubber in a stirrer, stirring for 5min at normal temperature at 120rmin rotating speed to obtain a rubber mixture, placing the rubber mixture and the antioxidant BHT in a double-screw extruder, and carrying out extrusion treatment at a first-zone temperature of 260 ℃, a second-zone temperature of 260 ℃, a third-zone temperature of 270 ℃, a fourth-zone temperature of 270 ℃, a fifth-zone temperature of 280 ℃ and a sixth-zone temperature, Extruding and granulating at a rotating speed of 300r/min under the conditions that the temperature of a seven zone is 260 ℃ and the temperature of a die head is 260 ℃, standing at normal temperature for 2 hours to obtain composite rubber particles, respectively putting 80 parts by weight of the composite rubber particles, 20 parts by weight of graphene oxide coated nano titanium dioxide, 20 parts by weight of superconducting carbon black, 1 part by weight of magnesium stearate and 4 parts by weight of nano zinc oxide powder into a stirrer, stirring and mixing at a rotating speed of 300r/min at normal temperature for 20 minutes to obtain a conductive filler, mixing the conductive filler, the magnesium stearate, the nano zinc oxide powder and the composite rubber particles, putting the mixture into a double-screw extruder, extruding and granulating at a rotating speed of 380r/min under the conditions that the temperature of a first zone is 270 ℃, the temperature of a three zone is 270 ℃, the temperature of a four zone is 280 ℃, the temperature of a five zone is 280 ℃, the temperature of a six zone is 280 ℃, the temperature of a seven zone is 270 ℃ and, standing for 2h at normal temperature to obtain the polyurethane-based composite nitrile butadiene rubber dielectric elastomer.
example 2
Respectively weighing 70 parts of graphene oxide, 35 parts of nano titanium dioxide and 315 parts of deionized water according to parts by weight, adding the nano titanium dioxide into 1/3 of the deionized water, stirring for 30min at the rotation speed of 900r/min at normal temperature, placing the mixture in an ultrasonic cleaner, performing ultrasonic treatment for 15min under the condition of the power of 900W, placing the mixture in a probe ultrasonic device, performing ultrasonic treatment for 1h under the condition of the power of 450W to obtain nano titanium dioxide dispersion liquid, adding the graphene oxide into the rest 2/3 of the deionized water, stirring for 12min at the rotation speed of 220r/min at normal temperature, placing the mixture in the probe ultrasonic device, performing ultrasonic treatment for 1h under the condition of the power of 450W to obtain graphene oxide solution, slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 35mL/min, placing the mixture in a water bath at 35 ℃ and performing constant-temperature stirring for 3h at the rotation speed of 330, obtaining mixed dispersion liquid, concentrating the mixed dispersion liquid at 70 ℃ for 3h, cooling at normal temperature to obtain concentrated dispersion liquid, placing the concentrated dispersion liquid in a vacuum filter, carrying out suction filtration under the condition of 700Pa, taking filter cakes, washing with deionized water for 4 times, placing the filter cakes in a-2 ℃ condition, freeze-drying for 22h to obtain graphene oxide coated nano titanium dioxide, respectively weighing 70 parts of polyurethane rubber, 35 parts of nitrile rubber and 2 parts of antioxidant BHT according to parts by weight, placing the polyurethane rubber and the nitrile rubber in a crusher, crushing for 12min, placing the crushed polyurethane rubber and the nitrile rubber in a stirrer, stirring for 8min at normal temperature at 140rmin rotating speed to obtain a rubber mixture, placing the rubber mixture and the antioxidant BHT in a double-screw extruder, and carrying out extrusion treatment at 260 ℃ in a first zone, 260 ℃ in a second zone, 270 ℃ in a third zone, 270 ℃ in a fourth zone, 280 ℃ in a fifth zone, 280 ℃ in a sixth zone, and 280 ℃ in, Extruding and granulating at a rotating speed of 330r/min under the conditions that the temperature of a seven zone is 260 ℃ and the temperature of a die head is 260 ℃, standing at normal temperature for 3 hours to obtain composite rubber particles, respectively putting 90 parts of the composite rubber particles, 22 parts of graphene oxide coated nano titanium dioxide, 22 parts of superconducting carbon black, 2 parts of magnesium stearate and 4 parts of nano zinc oxide powder in a stirrer according to parts by weight, stirring and mixing at a rotating speed of 330r/min for 25 minutes at normal temperature to obtain a conductive filler, mixing the conductive filler, the magnesium stearate, the nano zinc oxide powder and the composite rubber particles, putting the mixture in a double-screw extruder, extruding and granulating at a rotating speed of 390r/min under the conditions that the temperature of a first zone is 270 ℃, the temperature of a second zone is 270 ℃, the temperature of a third zone is 280 ℃, the temperature of a fourth zone is 280 ℃, the temperature of a fifth zone is 280 ℃, the temperature of a sixth zone is 280 ℃, the temperature of a seven, standing for 3h at normal temperature to obtain the polyurethane-based composite nitrile butadiene rubber dielectric elastomer.
Example 3
Respectively weighing 80 parts of graphene oxide, 40 parts of nano titanium dioxide and 360 parts of deionized water according to parts by weight, adding the nano titanium dioxide into 1/3 of the deionized water, stirring for 40min at the rotating speed of 1000r/min at normal temperature, placing the mixture in an ultrasonic cleaner, carrying out ultrasonic treatment for 20min under the condition of the power of 1000W, placing the mixture in a probe ultrasonic device, carrying out ultrasonic treatment for 2h under the condition of the power of 500W to obtain nano titanium dioxide dispersion liquid, adding the graphene oxide into the rest 2/3 of the deionized water, stirring for 15min at the rotating speed of 240r/min at normal temperature, placing the mixture in the probe ultrasonic device, carrying out ultrasonic treatment for 2h under the condition of the power of 500W to obtain graphene oxide solution, slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 40mL/min, placing the mixture in a water bath at 40 ℃ and carrying out constant-temperature stirring for 4h at the, obtaining mixed dispersion liquid, concentrating the mixed dispersion liquid at 80 ℃ for 4h, cooling at normal temperature to obtain concentrated dispersion liquid, placing the concentrated dispersion liquid in a vacuum filter, carrying out suction filtration under the condition of 800Pa, taking filter cakes, washing the filter cakes with deionized water for 5 times, placing the filter cakes in a 0 ℃ condition, freeze-drying for 24h to obtain graphene oxide coated nano titanium dioxide, respectively weighing 80 parts of polyurethane rubber, 40 parts of nitrile rubber and 3 parts of antioxidant BHT according to parts by weight, placing the polyurethane rubber and the nitrile rubber in a crusher, crushing for 15min, placing the crushed materials in a stirrer, stirring for 10min at normal temperature at 160rmin rotation speed to obtain a rubber mixture, placing the rubber mixture and the antioxidant BHT in a double-screw extruder, and carrying out the steps of firstly heating at 260 ℃, secondly heating at 260 ℃, thirdly heating at 270 ℃, fourthly heating at 270 ℃, fifthly heating at 280 ℃, sixty heating at 280 ℃, seventy heating at 260 ℃ and the like, Extruding and granulating at a die head temperature of 260 ℃ at a rotating speed of 360r/min, standing at normal temperature for 4h to obtain composite rubber particles, respectively putting 100 parts of the composite rubber particles, 25 parts of graphene oxide coated nano titanium dioxide, 25 parts of superconducting carbon black, 3 parts of magnesium stearate and 5 parts of nano zinc oxide powder in parts by weight in a stirrer, stirring and mixing at a rotating speed of 360r/min at normal temperature for 30min to obtain a conductive filler, mixing the conductive filler, the magnesium stearate, the nano zinc oxide powder and the composite rubber particles, putting the mixture in a double-screw extruder, extruding and granulating at a rotating speed of 400r/min under conditions of a first-zone temperature of 270 ℃, a second-zone temperature of 270 ℃, a third-zone temperature of 280 ℃, a fourth-zone temperature of 280 ℃, a fifth-zone temperature of 280 ℃, a sixth-zone temperature of 280 ℃, a seventh-zone temperature of 270 ℃ and a die head temperature of 260 ℃, standing for 4h at normal temperature to obtain the polyurethane-based composite nitrile butadiene rubber dielectric elastomer.
Comparative example: polyurethane-based composite nitrile rubber dielectric elastomer manufactured by Dongguan company.
The polyurethane-based composite nitrile-butadiene rubber dielectric elastomer prepared in the examples and the comparative examples is detected as follows:
Mechanical properties: mechanical tensile testing of the elastomeric films was performed using an Instron3343 universal electronic tensile tester from Instron corporation, usa. The elastomer film was cut into 50mm × 10mm strips, and the strips were stretched at a speed of 50mm/min under conditions of 20% air humidity and 25 ℃ until the strips broke.
the dielectric property is that an Aglient4294A impedance meter of Agilent company in America is adopted, carbon electrodes are coated on the upper side and the lower side of the elastomer membrane, and the frequency range is 1kHz ~ 1 MHz.
The specific test results are shown in table 1.
table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | comparative example |
| Tensile strength/MPa | 0.41 | 0.40 | 0.43 | 0.32 |
| Elongation at break% | 318 | 310 | 326 | 183 |
| Dielectric constant | 21.53 | 22.61 | 23.05 | 9.33 |
| Dielectric loss | 0.2 | 0.19 | 0.17 | 0.5 |
As can be seen from Table 1, the dielectric elastomer material prepared by the invention has good mechanical properties and dielectric properties.
Claims (10)
1. A preparation method of a polyurethane-based composite nitrile rubber dielectric elastomer is characterized by comprising the following specific preparation steps:
(1) placing the graphene oxide coated nano titanium dioxide and the superconducting carbon black in a stirrer, and stirring and mixing at the rotating speed of 300-360 r/min for 20-30 min at normal temperature to obtain a conductive filler;
(2) And mixing the conductive filler, magnesium stearate, nano zinc oxide powder and composite rubber particles, putting the mixture into a double-screw extruder, extruding and granulating at the rotating speed of 380-400 r/min, and standing at normal temperature for 2-4 hours to obtain the polyurethane-based composite nitrile rubber dielectric elastomer.
2. The method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer according to claim 1, wherein the weight parts of the composite rubber particles, the graphene oxide coated nano titanium dioxide, the superconducting carbon black, the magnesium stearate and the nano zinc oxide powder are 80-100 parts of the composite rubber particles, 20-25 parts of the graphene oxide coated nano titanium dioxide, 20-25 parts of the superconducting carbon black, 1-3 parts of the magnesium stearate and 4-5 parts of the nano zinc oxide powder.
3. The method for preparing a polyurethane-based composite nitrile rubber dielectric elastomer as claimed in claim 1, wherein the temperatures of the zones of the twin-screw extruder in the step (2) are 270 ℃ for the first zone, 270 ℃ for the second zone, 280 ℃ for the third zone, 280 ℃ for the fourth zone, 280 ℃ for the fifth zone, 280 ℃ for the sixth zone, 270 ℃ for the seventh zone, and 260 ℃ for the die.
4. The method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer as claimed in claim 1, wherein the specific preparation steps of the composite rubber particles in step (2) are as follows:
(1) Placing the polyurethane rubber and the nitrile rubber into a grinder to be ground for 10-15 min, then placing the ground materials into a stirrer to be stirred for 5-10 min at normal temperature at a rotating speed of 120-160 rmin to obtain a rubber mixture;
(2) And (3) placing the rubber mixture and the antioxidant BHT in a double-screw extruder, extruding and granulating at the rotating speed of 300-360 r/min, and standing at normal temperature for 2-4 hours to obtain the composite rubber particles.
5. The method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer as claimed in claim 4, wherein the weight parts of the polyurethane rubber, the nitrile rubber and the antioxidant BHT are 60-80 parts of polyurethane rubber, 30-40 parts of nitrile rubber and 1-3 parts of antioxidant BHT.
6. The method for preparing a polyurethane-based composite nitrile rubber dielectric elastomer as claimed in claim 4, wherein the temperatures of the zones of the twin-screw extruder in the step (2) are 260 ℃ for the first zone, 260 ℃ for the second zone, 270 ℃ for the third zone, 270 ℃ for the fourth zone, 280 ℃ for the fifth zone, 280 ℃ for the sixth zone, 260 ℃ for the seventh zone and 260 ℃ for the die.
7. The preparation method of the polyurethane-based composite nitrile rubber dielectric elastomer according to claim 1, wherein the specific preparation steps of the graphene oxide coated nano titanium dioxide in the step (1) are as follows:
(1) Adding nano titanium dioxide into 1/3 deionized water, stirring at the normal temperature at the rotating speed of 800-1000 r/min for 20-40 min, placing the mixture in an ultrasonic cleaning machine for ultrasonic treatment for 10-20 min, and then placing the mixture in a probe ultrasonic device for ultrasonic treatment for 1-2 h to obtain nano titanium dioxide dispersion liquid;
(2) adding graphene oxide into the rest 2/3 of deionized water, stirring at the rotating speed of 200-240 r/min for 10-15 min at normal temperature, and then placing the mixture in a probe ultrasonic device for ultrasonic treatment for 1-2 h to obtain a graphene oxide solution;
(3) Slowly adding the nano titanium dioxide dispersion liquid into the graphene oxide solution at the flow rate of 30-40 mL/min, and stirring for 2-4 hours at the constant temperature of 300-360 r/min under the water bath condition of 30-40 ℃ to obtain a mixed dispersion liquid;
(4) Concentrating the mixed dispersion liquid at 60-80 ℃ for 2-4 h, and cooling at normal temperature to obtain a concentrated dispersion liquid;
(5) and placing the concentrated dispersion liquid into a vacuum suction filter, carrying out suction filtration under the condition of 600-800 Pa, taking the filter cake, washing the filter cake with deionized water for 3-5 times, and placing the filter cake at the temperature of-4-0 ℃ for freeze drying for 20-24 hours to obtain the graphene oxide coated nano titanium dioxide.
8. The method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer as claimed in claim 7, wherein the graphene oxide, the nano titanium dioxide and the deionized water are 60-80 parts by weight, 30-40 parts by weight and 270-360 parts by weight.
9. the method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer according to claim 7, wherein the power of the ultrasonic cleaning machine in the step (1) is 800-1000W, and the power of the probe ultrasonic device is 400-500W.
10. the method for preparing the polyurethane-based composite nitrile rubber dielectric elastomer according to claim 7, wherein the power of the probe ultrasonic device in the step (2) is 400-500W.
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