CN112358674A - Core-shell nano silicon oxide @ zirconium oxide particle-polypropylene maleic anhydride grafted polypropylene composite material and preparation method thereof - Google Patents

Core-shell nano silicon oxide @ zirconium oxide particle-polypropylene maleic anhydride grafted polypropylene composite material and preparation method thereof Download PDF

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CN112358674A
CN112358674A CN202010707857.2A CN202010707857A CN112358674A CN 112358674 A CN112358674 A CN 112358674A CN 202010707857 A CN202010707857 A CN 202010707857A CN 112358674 A CN112358674 A CN 112358674A
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polypropylene
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刘文凤
张羽欣
程璐
张子琦
李盛涛
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Xian Jiaotong University
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Abstract

The invention provides a core-shell nano SiO2@ZrO2A particle-polypropylene/maleic anhydride grafted polypropylene composite material and a preparation method thereof. Mixing nano SiO2@ZrO2In 50-50% pure polypropylene/maleic anhydride grafted polypropylene, melt blending method is used for different concentrationsDoping, wherein the polypropylene is isotactic polypropylene; the grafting rate of the maleic anhydride grafted polypropylene is 1 percent; the thickness of the silicon oxide shell layer is respectively 3nm, 7nm and 11nm, and the surface of the silicon oxide shell layer is subjected to KH570 silane coupling treatment. The dielectric constant and the breakdown field strength of the nano composite medium obtained by the invention are obviously improved at the same time, when the nano SiO of the invention2@ZrO2When the thickness of the shell layer is 11nm and the doping concentration is 1 wt%, the energy storage density is improved by 52% compared with that of pure PP, and the dielectric loss is kept unchanged compared with that of the pure PP. The technology provides a technical foundation for improving the energy storage density of the thin film capacitor.

Description

Core-shell nano silicon oxide @ zirconium oxide particle-polypropylene maleic anhydride grafted polypropylene composite material and preparation method thereof
Technical Field
The invention belongs to the field of power capacitors, and relates to a high-energy-storage-density core-shell nano SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite material and a preparation method thereof.
Background
As an energy storage device, a power capacitor is widely applied to a power system, and a higher requirement is also put on the energy storage density of materials therein. To meet the requirements in the application, the dielectric material must have a high dielectric constant, as well as low dielectric loss and high breakdown strength.
The currently commonly used organic dielectric material polypropylene (PP) has a relatively high breakdown field strength and a relatively low dielectric loss, but has a relatively low dielectric constant (only 2.2-2.4). In order to increase the dielectric constant of PP, a conventional method is to dope inorganic nanoparticles having a high dielectric constant thereto. For example, the influence of micro-nano-sized Copper Calcium Titanate (CCTO) ceramic powder on the dielectric properties of corresponding composite materials is systematically studied by yankee et al, and it is found that the dielectric constant of the composite material can be improved by utilizing the characteristic of interfacial polarization of inorganic nano-materials, and when the filling volume fraction is 60 vol.%, and the test frequency is 1kHz, the dielectric constant of the composite film shows a tendency of increasing first and then decreasing along with the increase of the size of BT particles; fan et al studied the effect of BT nanoparticles (30-50nm, 50-80nm, 100-150nm) with different particle sizes on the dielectric properties of BT/PVDF composite materials, and found that the dielectric constant of the composite material is greatly improved at low frequency and when the size of the filler nanoparticles is 30-50 nm. However, since the dielectric constant of the inorganic filler is usually greatly different from that of the organic base material, the breakdown performance of the composite material is greatly reduced due to the severe distortion of the electric field, which is quite undesirable.
Some researchers try to keep the structure of the polymer base material unchanged, and coat a layer of inorganic material with medium dielectric constant between the core particles with high dielectric constant and the organic base material to serve as an effective buffer layer, so as to achieve the purposes of homogenizing the internal electric field and effectively improving the energy storage density. In the prior art, alumina is coated outside nano zirconia to form core-shell structure nano particles, and polypropylene is subjected to doping modification.
The core particles of the current research are mostly limited to the preparation and doping of core-shell structures with high dielectric constant nanoparticles (nano barium titanate, nano titanium oxide and the like, the dielectric constant is more than 100 and even more) as cores, so as to achieve the improvement of the dielectric constant of the composite material. Less core-shell doping work is performed with nanoparticles with medium dielectric constant (such as nano zinc oxide and nano zirconium oxide, dielectric constant of 10-100) as cores.
Therefore, those skilled in the art are devoted to provide a new core-shell doping study using a nanoparticle with a medium dielectric constant as a core.
Disclosure of Invention
In view of the above defects in the prior art, the present invention provides a core-shell nano SiO2@ZrO2Polypropylene/maleic anhydride grafted polypropylene composites to add new core-shell doping studies with medium-dielectric constant nanoparticles as core.
In order to realize the purpose, the invention provides a core-shell nano SiO2@ZrO2Polypropylene/maleic anhydride grafted polypropylene composite material, wherein polypropylene in the composite material is isotactic polypropylene, the grafting rate of the maleic anhydride grafted polypropylene is 1-3%, and the core-shell nano SiO is2@ZrO2The doping concentration of the particles in the maleic anhydride grafted polypropylene is 0-5%, and the doping concentration of the particles in the maleic anhydride grafted polypropylene is SiO2The thickness of the shell layer can be adjusted, and the diameter of the nano zirconia particle is 30-50 nm.
The invention also provides a core-shell nano SiO2@ZrO2Preparation method of (E) -polypropylene/maleic anhydride grafted polypropylene composite materialThe method comprises the following steps:
s100, preparing nano ZrO2The particles are fully dispersed in the dispersant after being ground and sieved:
s200, nano ZrO after dispersion2The surface of the particle is coated with SiO2Obtaining the core-shell nano SiO2@ZrO2Drying the particles in vacuum, grinding and sieving;
s300, sieving the core-shell nano SiO2@ZrO2Pickling the particles, drying, grinding and sieving;
s400, subjecting the core-shell nano SiO obtained in the step S300 to2@ZrO2Modifying the particles;
s500, grafting polypropylene and modified core-shell nano SiO by using maleic anhydride2@ZrO2Preparing master batch from the particles;
s600, melting and blending polypropylene, maleic anhydride grafted polypropylene and the master batch to obtain core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
The invention has the technical effects and advantages that:
the core-shell nano SiO obtained by the invention2@ZrO2The breakdown field strength of the particle-polypropylene/maleic anhydride grafted polypropylene composite material is remarkably improved, and simultaneously the low level of dielectric loss is ensured, when the doping concentration of the nano zirconia in PP-50-MAH is 1 wt%, SiO2When the thickness of the shell layer is 11nm, the energy storage density is improved to the maximum extent, and is improved by 52%. The technology provides a technical foundation for improving the energy storage density of the thin film capacitor.
Drawings
FIG. 1 shows core-shell nano SiO prepared by a preferred embodiment of the present invention2@ZrO2A schematic flow chart of the preparation process of the particle-polypropylene/maleic anhydride grafted polypropylene composite material;
FIG. 2 shows KH570 vs. nano SiO2Schematic diagram of the modification action principle of (1);
FIG. 3 shows the core-shell nano SiO prepared by the preferred embodiment of the present invention2@ZrO2Particle-polypropylene/maleic acidThe dielectric constant test result of the anhydride grafted polypropylene composite material;
FIG. 4 is ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results;
FIG. 5 is SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 3 nm;
FIG. 6 is SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 7 nm;
FIG. 7 is SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 11 nm;
FIG. 8 shows the core-shell nano SiO prepared by the preferred embodiment of the present invention2@ZrO2The shell thickness of silicon dioxide in the particle-polypropylene/maleic anhydride grafted polypropylene composite material is related to the content of nano zirconium dioxide.
Detailed Description
The invention provides a core-shell nano SiO2@ZrO2Polypropylene/maleic anhydride grafted polypropylene composite material, wherein polypropylene in the composite material is isotactic polypropylene, the grafting rate of the maleic anhydride grafted polypropylene is 1-3%, and the core-shell nano SiO is2@ZrO2The doping concentration of the particles in the maleic anhydride grafted polypropylene is 0-5%, and the doping concentration of the particles in the maleic anhydride grafted polypropylene is SiO2The thickness of the shell layer can be adjusted, and the diameter of the nano zirconia particle is 30-50 nm.
Due to the limitation of the current technology and the consideration of practical application cost, the grafting rate of the maleic anhydride grafted polypropylene on the market at present is about 1%, so that the grafting rate of the maleic anhydride grafted polypropylene is 1-3%. The composite material prepared by the process has extremely obvious agglomeration phenomenon of the nano particles under high-concentration nano doping (such as more than 5 percent), and the performance of the composite material is seriously degraded, so the doping concentration range is only selected from low concentrations, namely 0.5 percent, 1 percent, 3 percent and 5 percent. And according to the existing research, if the particle size of the nano particles is too small, the possibility of the nano particles being too smallResulting in increased composite material loss, which may exceed nanometer order of magnitude if too large, and loss of the effect of increasing breakdown field strength, so that the ZrO used2The particle diameter is selected to be moderate and is 30-50 nm.
The core-shell nano SiO obtained by the invention2@ZrO2The breakdown field strength of the particle-polypropylene/maleic anhydride grafted polypropylene composite material is remarkably improved, and simultaneously the low level of dielectric loss is ensured, when the doping concentration of the nano zirconia in PP-50-MAH is 1 wt%, SiO2When the thickness of the shell layer is 11nm, the energy storage density is improved to the maximum extent, and is improved by 52%. The technology provides a technical foundation for improving the energy storage density of the thin film capacitor.
As shown in figure 1, the invention also provides a core-shell nano SiO2@ZrO2A method for preparing a polypropylene/maleic anhydride grafted polypropylene composite material, comprising the steps of:
s100, preparing nano ZrO2The particles are fully dispersed in the dispersant after being ground and sieved:
s200, nano ZrO after dispersion2The surface of the particle is coated with SiO2Obtaining the core-shell nano SiO2@ZrO2Drying the particles in vacuum, grinding and sieving;
s300, sieving the core-shell nano SiO2@ZrO2Pickling the particles, drying, grinding and sieving;
s400, subjecting the core-shell nano SiO obtained in the step S300 to2@ZrO2Modifying the particles;
s500, grafting polypropylene and modified core-shell nano SiO by using maleic anhydride2@ZrO2Preparing master batch from the particles;
s600, melting and blending polypropylene, maleic anhydride grafted polypropylene and the master batch to obtain core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
In a preferred embodiment, step S100 further includes:
sieving the nano ZrO2Adding the particles and absolute ethyl alcohol into a beaker for magnetic stirring, wherein the nano ZrO2The ratio of the particles to the absolute ethyl alcohol is 2g of nano ZrO2The particle proportion of the anhydrous ethanol is 200mL, the magnetic stirring time is 10-20mins, the ultrasonic dispersion is carried out for 40-60mins after the magnetic stirring is finished, the dispersing agent is added into a beaker after the ultrasonic dispersion is finished, and the magnetic stirring is continued for 30-60mins, wherein the dispersing agent is polyvinylpyrrolidone.
In a preferred embodiment, step S200 further includes step 2001:
to be nano ZrO2After the particles are dispersed, adding tetraethoxysilane (TEOS for short) and magnetically stirring for 15-30mins, after the TEOS is fully dispersed, adding 30-50mL of ammonia water to construct an alkaline environment required by hydrolysis reaction, simultaneously dropwise adding deionized water to react with the TEOS, and hydrolyzing to generate SiO2The whole reaction process lasts for 5-6h, and the magnetic stirring is kept to obtain the core-shell nano SiO2@ZrO2A particle solution.
In a preferred embodiment, step S200 further includes step 2002: core-shell nano SiO2@ZrO2Centrifugally cleaning the particle solution, dispersing and cleaning for 10-30mins in a centrifuge by using absolute ethyl alcohol as a cleaning solution, and then ultrasonically dispersing for 10-30mins to enable the core-shell nano SiO to be in a nano-grade state2@ZrO2The particles are washed sufficiently.
In a preferred embodiment, step S200 further includes step 2003: wet core-shell nano SiO obtained after cleaning2@ZrO2The particles are put into an oven for vacuum drying to obtain blocky core-shell nano SiO2@ZrO2Setting the temperature of the oven at 50-70 deg.C for 10-12h, and mixing with the bulk core-shell nano SiO2@ZrO2The particles are ground and sieved to form uniform particles for the next step.
In a preferred embodiment, step S300 further includes: using 0.1mol/L hydrochloric acid solution to react with the dried core-shell nano SiO obtained in the last step2@ZrO2The particles are acid-washed according to the core-shell nano SiO2@ZrO2The ratio of the particles to the hydrochloric acid is 1 g: 100mL, ultrasonic dispersion is carried out for 15-30mins, then centrifugal cleaning, drying, grinding and sieving are carried out.
In a preferred embodiment, step S400 further includes: weighing 2g of the core-shell nano SiO obtained in step S3002@ZrO2Adding the particles into a beaker filled with 200mL of absolute ethyl alcohol, magnetically stirring for 5-10mins, and then performing ultrasonic dispersion for 30-40mins to obtain a solution A; meanwhile, 10mL of silane coupling agent KH570, 40mL of absolute ethanol and 40mL of 0.1mol/L hydrochloric acid solution are measured and added into a three-neck flask, magnetic stirring is carried out at 60-80 ℃ for 30-40mins to obtain solution B, the temperature is set to be 110 ℃ after the solution A and the solution B are mixed, magnetic stirring is carried out for 4-5h, and the nuclear shell nano SiO is finished2@ZrO2Modification reaction of the particles.
In a preferred embodiment, step S500 further includes: adding maleic anhydride grafted polypropylene and the modified core-shell nano SiO obtained in the step S400 into a torque rheometer2@ZrO2Particles, antioxidant 1010 with the mass fraction of 0.1-0.2 percent, are melted and blended for 10-15mins at the temperature of 160-180 ℃ to obtain master batch, wherein the maleic anhydride grafted polypropylene and the nuclear shell nano SiO2@ZrO2The mass ratio of the particles is 5: 1-15: 1.
In a preferred embodiment, step S600 further includes: adding polypropylene, maleic anhydride grafted polypropylene and the master batch into a torque rheometer, adding antioxidant 1010 with the mass fraction of 0.1-0.2% after the torque is stable, and melting at the temperature of 160-180 ℃ for 15-20mins at 35-45r/min to obtain the final product, namely the core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
In a preferred embodiment, the mass ratio of the maleic anhydride grafted polypropylene is 45-50% relative to the total weight of the mixture of the polypropylene and the maleic anhydride grafted polypropylene, and the core-shell nano SiO is2@ZrO2The mass percentage of the particles is controlled between 0.1 and 5 percent.
The invention is further illustrated by the following detailed examples, which are not intended to be limiting.
Preparation of core-shell nano SiO2@ZrO2Particle:
the invention adopts a sol-gel method to prepare the core-shell nano-particlesSiO rice2@ZrO2Particles of in nano ZrO2The surface of the raw material is coated with a layer of SiO2Before the shell layer, ZrO needs to be firstly treated2The raw materials are treated, ground and sieved, and particles with overlarge sizes are removed, so that the relative uniformity of the granules is ensured.
After the pellets were homogenized, 2g of ZrO were weighed2Putting the raw materials and 200mL of absolute ethyl alcohol into a 500mL beaker, adding magnetons, performing magnetic stirring for 10-20mins, and performing ultrasonic dispersion for 30-60mins to ensure ZrO2The raw materials are uniformly dispersed. After the ultrasonic treatment is finished, 8g of PVP (polyvinylpyrrolidone) is added into the beaker, magnetic stirring is carried out for 30-60mins, and the PVP plays a role of a dispersing agent.
To be nano-ZrO2After the particles are dispersed, 42 drops of TEOS (tetraethyl orthosilicate) are added, magnetic stirring is carried out for 15-30mins, and TEOS is used as SiO2By hydrolysis reaction to produce SiO2. However, TEOS hydrolysis produces SiO2An alkaline reaction environment is required. Therefore, after the TEOS is required to be fully dispersed, 40mL of ammonia water is added to construct an alkaline environment required by hydrolysis reaction, and 42 drops of deionized water are added dropwise to react with the TEOS to hydrolyze to generate SiO2The whole reaction process lasts for 5h, and magnetic stirring is required all the time.
The TEOS hydrolysis reaction process is as follows:
Figure RE-GDA0002882796730000061
-SiOH+NH3→-SiO-+NH4 +
-SiO-+-SiOH→-Si-O-Si-+NH3+H2O
after the hydrolysis reaction of TEOS is finished, the core-shell-containing nano SiO is obtained2@ZrO2The ethanol solution of the particles contains unnecessary substances such as ammonia water and PVP in addition to the target core-shell particles, and it is necessary to separate them. In this regard, the solution after reaction is centrifugally washed by a centrifuge, and is dispersedly washed for 10-30mins in the centrifuge by using absolute ethyl alcohol as a washing solution, and the total amount isCleaning for 4 times, wherein ultrasonic dispersion is directly needed for 10-30mins in each cleaning process, so that the particles are fully cleaned.
After the cleaning is finished, wet core-shell nano SiO is obtained2@ZrO2And (3) drying the particles in an oven at 50-70 ℃ for 10-12 h.
After the drying is finished, the granules are integrally formed into blocks, and are required to be ground and sieved to be processed into uniform granules for the next step.
By changing related parameters such as TEOS, deionized water, reaction time and the like, the core-shell nano SiO with different shell thicknesses can be obtained2@ZrO2Particles.
In order to better combine the core-shell nano SiO2@ZrO2The particles are dispersed in a PP/PP-g-MAH matrix, the surface of the particles is required to be modified, the invention adopts a silane coupling agent KH570 to modify the core-shell particles, and SiO is utilized2A large amount of OH existing on the surface and a coupling agent are subjected to dehydration condensation reaction to fix the coupling agent on the surface of the particles, and one end of the coupling agent with higher compatibility with organic matters can be used for improving the dispersibility of the nanoparticles in a polypropylene matrix
The molecular structure of KH570 is simply CH2＝C(CH3)COO(CH2)3Si(OCH3)3With A-SiX3And (4) showing. I.e. A is CH2＝C(CH3)COO(CH2)3-, X is-OCH3. KH570 to nano SiO2The schematic diagram of the modification action of (2) is shown in FIG. 2.
For better KH570 modification treatment, the core-shell nano SiO is treated before the modification process2@ZrO2The particles are subjected to acid washing treatment, and the purpose is to provide a good environment for modification of the coupling agent. Core-shell nano SiO by using 0.1mol/L hydrochloric acid solution2@ZrO2And (3) carrying out acid washing treatment on the particles, carrying out acid washing for 15mins according to the ratio of 1g to 100mL of the nano particles to the hydrochloric acid, then carrying out centrifugal cleaning, drying, grinding and sieving.
2g of pickled SiO were weighed2@ZrO2Particles, adding theretoPutting the mixture into a beaker filled with 200mL of absolute ethyl alcohol, magnetically stirring for 5-10mins, and then performing ultrasonic dispersion for 30-40mins to obtain a solution A; meanwhile, 10mL of silane coupling agent KH570, 40mL of absolute ethyl alcohol and 40mL of 0.1mol/L hydrochloric acid solution are weighed and added into a 500mL three-neck flask, and magnetic stirring is carried out at 60-80 ℃ for 30-40mins to obtain solution B,
and mixing the solution A and the solution B after dispersion is finished, setting the temperature to be 100-110 ℃, and carrying out magnetic stirring for 4-5h to perform modification reaction.
After the modification reaction is finished, centrifugally cleaning, drying, grinding and sieving to obtain the core-shell nano SiO capable of being finally prepared by compounding nano materials2@ZrO2Particles.
Preparing a master batch:
maleic anhydride grafted polypropylene and nano SiO are added into a torque rheometer2@ZrO2And 0.1 percent of antioxidant 1010 by mass percentage, and melt blending at 180 ℃ for 10-15mins to obtain the master batch.
Preparation of core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composite: the polypropylene, the maleic anhydride grafted polypropylene and the master batch are added into the torque rheometer, and 0.04g of antioxidant 1010 (accounting for 0.1 percent of the total mass) is added after the torque rheometer runs stably. Performing melt compounding for 15-20mins at 35-45r/min and 160-180 ℃ to obtain the final product of the core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
In the mixed material, the total mass of polypropylene and maleic anhydride grafted polypropylene is 40g, the weight ratio of the maleic anhydride grafted polypropylene to pure polypropylene is 1: 1, the mass ratio of nano particles is 0, 0.5%, 1%, 3% and 5%, the shell thickness is 3nm, 7nm and 11nm, when the shell thickness is 3nm, TEOS and deionized water are 42 drops, when the shell thickness is 7nm, TEOS and deionized water are 48 drops, when the shell thickness is 11nm, TEOS and deionized water are 96 drops, and the antioxidant is used for preventing the medium from being oxidized in the process of melting and blending.
Preparation of core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene compositeMaterial film: 1) a circular hole having a diameter of 50mm was cut out of a polyimide film having a thickness of about 110 μm to form a die.
2) And (3) putting 0.26g of composite material into each circular hole of the die, preheating for a period of time at 190 ℃ by using a flat vulcanizing machine, exhausting gas, and then carrying out hot press molding under 20MPa to obtain the polypropylene-maleic anhydride grafted polypropylene-nano zirconia composite material film.
Wherein, the preheating time at 190 ℃ can be set to be between 280 and 320s, such as 300s, the exhaust frequency can be set to be 10-15 times, 9-11s each time, such as 10 times for each time, 10 s; the hot press molding time at 20MPa can be set to 280-320s, for example, 300s, the diameter of the film sample is 50mm, and the thickness is about 120 μm.
Sample Performance testing
For core-shell nano SiO2@ZrO2And (3) carrying out performance test on the particle-polypropylene/maleic anhydride grafted polypropylene composite material film, and respectively testing the breakdown performance and the dielectric performance of the sample.
Breakdown test A DC breakdown test was carried out on the film in silicone oil at a rate of 500V/s using a hemispherical electrode having a diameter of 12.7mm in accordance with ASTM-D149 and ASTM-D3755. At least 30 effective breakdown points are obtained from each sample, Weibull statistical analysis is carried out on the at least 30 breakdown field strength data, and a scale parameter of Weibull distribution, namely the breakdown field strength when the breakdown probability is 63.2%, is selected as a characteristic breakdown field strength for judgment.
The dielectric test was conducted on a thin film sample by first spraying gold (gold ion sputtering) on the surface of the sample, and the electrode diameter was 30 mm. At room temperature (25 deg.C), 0.1Hz-105And testing in the Hz frequency range to obtain the dielectric constant and the dielectric loss of the sample.
FIG. 3 shows core-shell nano SiO prepared according to a preferred embodiment of the present invention2@ZrO2The dielectric constant test result of the particle-polypropylene/maleic anhydride grafted polypropylene composite material shows that the dielectric constant of the composite material film is firstly reduced and then increased along with the increase of the doping concentration of the nano particles under the influence of transverse contrast doping concentrationThis is because the high dielectric nanoparticle doping introduces thermionic polarization, so that the dielectric constant of the composite material is increased compared to the base material at high doping concentrations. And a low content of ZrO2The nanometer filler has small contribution to the dielectric constant of the composite material, but can inhibit the polarization of the molecular chain of the base material and reduce the free volume in the material, so that the dielectric constant of the composite material is slightly reduced.
The dielectric constant of the composite material shows monotonous decrease instead with the increase of the shell thickness due to the influence of the lateral contrast of the shell thickness, which is caused by the SiO serving as the shell2Material dielectric constant ratio core particle ZrO2Much lower, so the thicker the shell (incorporated SiO)2More), the dielectric constant of the material may exhibit a weak tendency to decrease. But the overall change is not large, and the change is still concentrated between 2.5 and 3.
TABLE 1 core-shell nano SiO prepared by a preferred embodiment of the invention2@ZrO2DC breakdown field strength of particle-polypropylene/maleic anhydride grafted polypropylene composite material
Figure RE-GDA0002882796730000091
Influence of transverse contrast of doping concentration along with core-shell nano SiO2@ZrO2Particles or ZrO2The breakdown field strength of the composite material shows the trend of rising first and then falling after the doping concentration of the nano particles is increased, and the highest value appears at low concentration (about 1%). This is because the introduction of a small amount of nanoparticles will form an interaction region between the particles and the organic matrix, and when an electric field is applied to the material, electron traps in the interaction region will capture carriers. However, the surface energy of the nano particles is high, agglomeration easily occurs under high-concentration doping, and the agglomerated nano particles can not play a role in adjusting the breakdown field strength but can become defects in the material, so that the breakdown field strength of the material is rapidly reduced.
Longitudinal contrast of SiO2The influence of the introduced shell layer can be found to have SiO2Sodium of shell layerZrO of rice-doped composite material without shell2The overall breakdown field strength of the nano-doped composite material is further improved because of ZrO2The dielectric constant (about 22) of the filler is greatly different from that of a polypropylene matrix (about 2.2), and the direct introduction of the high-dielectric nano filler can cause uneven local electric field distribution in the material, so that the breakdown performance is deteriorated. And SiO introduced2The dielectric constant (about 3.9) is between the two, and the function of buffering local electric field is realized, so that the ZrO ceramic material is compared with the original ZrO ceramic material2The breakdown performance of the nano-doped composite material is further improved.
TABLE 2 core-shell nano-SiO prepared by a preferred embodiment of the invention2@ZrO2Energy storage density of particle-polypropylene/maleic anhydride grafted polypropylene composite material
Figure RE-GDA0002882796730000101
By the formula
Figure RE-GDA0002882796730000102
The energy storage density corresponding to the composite material can be calculated, wherein E is the breakdown field strength epsilon0Is a vacuum dielectric constant (8.854X 10)-12F/m)，εrIs the relative dielectric constant of the composite material. The dielectric constant of the composite material obtained by the invention is not changed greatly, so the integral change trend of the energy storage density is basically the same as the breakdown field intensity.
FIG. 4 is ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, FIG. 5 is SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 3nm, and fig. 6 shows SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 7nm, and fig. 7 shows SiO2@ZrO2-polypropylene/maleic anhydride grafted polypropylene composite dielectric loss test results, wherein the shell thickness is 11 nm; generally, the introduction of nanometersImpurities must be introduced into the composite material after the particles, and the overall loss of the composite material is greatly increased compared with that of the base material. The dielectric loss of the composite material is tested at the frequency of 0.1-10000 Hz, and the loss of the material is found to be increased compared with the base material, but the amplification is not large, and the loss is still kept at 10 basically-3And meets the actual industrial requirements.
FIG. 8 shows the core-shell nano SiO prepared by the preferred embodiment of the present invention2@ZrO2The shell thickness of silicon dioxide in the particle-polypropylene/maleic anhydride grafted polypropylene composite material is related to the content of nano zirconium dioxide. According to the results of the existing research, when the concentration of the nano filler is higher (more than 5%) in the composite material prepared by the melt blending method, the agglomeration phenomenon of particles is obvious, and the performance is seriously degraded, so that the higher concentration doping is not required to be tried continuously, and the invention only selects four concentrations of 0.5%, 1%, 3% and 5%. If the thickness of the shell layer is too thick, the particle size of the nano particles is too large and exceeds the nano-order of magnitude, the special effect of the nano particles on improving the breakdown field intensity is lost, and the nano particles are changed into impurities, so that only three groups of shell layer thicknesses of 3nm, 7nm and 11nm are selected to coat on the basis that the diameter of the nano particles is 50 nm.
The results show that in the maleic anhydride grafted polypropylene base, SiO2@ZrO2The energy storage density of the composite material is obviously improved when the thickness of the silicon oxide shell layer is 3nm, 7nm and 11nm under different doping concentrations of 0%, 0.5%, 1%, 3% and 5% of the doping content of the nano particles. In particular, when the thickness of the shell layer is 11nm and the doping concentration is 1%, the energy storage density is increased by 52% compared with that of pure polypropylene, wherein, an applicant uses the pure PP material to measure the breakdown field strength of the pure PP: 345.6kV/mm, energy storage density: 1.35J/cm3Dielectric loss is substantially maintained at 10-3The order of magnitude is basically the same as that of pure polypropylene, and better results are obtained.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. Core-shell nano SiO2@ZrO2Polypropylene/maleic anhydride grafted polypropylene composite material, wherein polypropylene in the composite material is isotactic polypropylene, the grafting rate of the maleic anhydride grafted polypropylene is 1-3%, and the core-shell nano SiO is2@ZrO2The doping concentration of the particles in the maleic anhydride grafted polypropylene is 0-5%, and the doping concentration of the particles in the maleic anhydride grafted polypropylene is SiO2The thickness of the shell layer can be adjusted, and the diameter of the nano zirconia particle is 30-50 nm.
2. A method of making the composite material of claim 1, comprising the steps of:
s100, preparing nano ZrO2The particles are fully dispersed in the dispersant after being ground and sieved:
s200, nano ZrO after dispersion2The surface of the particle is coated with SiO2Obtaining the core-shell nano SiO2@ZrO2Drying the particles in vacuum, grinding and sieving;
s300, sieving the core-shell nano SiO2@ZrO2Pickling the particles, drying, grinding and sieving;
s400, subjecting the core-shell nano SiO obtained in the step S300 to2@ZrO2Modifying the particles;
s500, grafting polypropylene and modified core-shell nano SiO by using maleic anhydride2@ZrO2Preparing master batch from the particles;
s600, mixing polypropylene and maleic acidThe anhydride grafted polypropylene and the master batch are melted and blended to obtain the core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
3. The method of claim 2, wherein step S100 further comprises, preferably:
sieving the nano ZrO2Adding the particles and absolute ethyl alcohol into a beaker for magnetic stirring, wherein the nano ZrO2The ratio of the particles to the absolute ethyl alcohol is 2g of nano ZrO2The particle proportion of the anhydrous ethanol is 200mL, the magnetic stirring time is 10-20mins, the ultrasonic dispersion is carried out for 40-60mins after the magnetic stirring is finished, the dispersing agent is added into a beaker after the ultrasonic dispersion is finished, and the magnetic stirring is continued for 30-60mins, wherein the dispersing agent is polyvinylpyrrolidone.
4. The method of claim 2, wherein step S200 further comprises step 2001:
to be nano ZrO2After the particles are dispersed, adding TEOS, magnetically stirring for 15-30mins, after the TEOS is fully dispersed, adding 30-50mL of ammonia water to construct an alkaline environment required by hydrolysis reaction, simultaneously dropwise adding deionized water, reacting with the TEOS, and hydrolyzing to generate SiO2The whole reaction process lasts for 5-6h, and the magnetic stirring is kept to obtain the core-shell nano SiO2@ZrO2A particle solution.
5. The method of claim 2, wherein step S200 further comprises step 2002: core-shell nano SiO2@ZrO2Centrifugally cleaning the particle solution, using absolute ethyl alcohol as a cleaning solution, centrifugally dispersing in a centrifuge for 10-30mins to separate particles from the solution, and then ultrasonically dispersing for 10-30mins to enable the core-shell nano SiO to be in a nano-grade state2@ZrO2The particles are dispersed in the cleaning solution and this is repeated 3-4 times until the surface of the particles is free of residue in the reaction solution.
6. The method of claim 2, wherein step S200 further comprises step 2003: wet core-shell nano powder obtained after cleaningSiO rice2@ZrO2The particles are put into an oven for vacuum drying to obtain blocky core-shell nano SiO2@ZrO2Setting the temperature of the oven at 50-70 deg.C for 10-12h, and mixing with the bulk core-shell nano SiO2@ZrO2The particles are ground and sieved to form uniform particles for the next step.
7. The method of claim 2, wherein step S300 further comprises: using 0.1mol/L hydrochloric acid solution to react with the dried core-shell nano SiO obtained in the last step2@ZrO2The particles are acid-washed according to the core-shell nano SiO2@ZrO2The ratio of the particles to the hydrochloric acid is 1 g: 100mL, ultrasonic dispersion is carried out for 15-30mins, then centrifugal cleaning, drying, grinding and sieving are carried out.
8. The method of claim 2, wherein step S400 further comprises: weighing 2g of the core-shell nano SiO obtained in step S3002@ZrO2Adding the particles into a beaker filled with 200mL of absolute ethyl alcohol, magnetically stirring for 5-10mins, and then performing ultrasonic dispersion for 30-40mins to obtain a solution A; meanwhile, 10mL of silane coupling agent KH570, 40mL of absolute ethanol and 40mL of 0.1mol/L hydrochloric acid solution are measured and added into a three-neck flask, magnetic stirring is carried out at 60-80 ℃ for 30-40mins to obtain solution B, the temperature is set to be 110 ℃ after the solution A and the solution B are mixed, magnetic stirring is carried out for 4-5h, and the nuclear shell nano SiO is finished2@ZrO2Modification reaction of the particles.
9. The method of claim 2, wherein step S500 further comprises: adding maleic anhydride grafted polypropylene and the modified core-shell nano SiO obtained in the step S400 into a torque rheometer2@ZrO2Particles, antioxidant 1010 with the mass fraction of 0.1-0.2 percent, are melted and blended for 10-15mins at the temperature of 160-180 ℃ to obtain master batch, wherein the maleic anhydride grafted polypropylene and the nuclear shell nano SiO2@ZrO2The mass ratio of the particles is 5: 1-15: 1.
10. As claimed in claim2, wherein step S600 further comprises: adding polypropylene, maleic anhydride grafted polypropylene and the master batch into a torque rheometer, adding antioxidant 1010 with the mass fraction of 0.1-0.2% after the torque is stable, and melting at the temperature of 160-180 ℃ for 15-20mins at 35-45r/min to obtain the final product, namely the core-shell nano SiO2@ZrO2Particle-polypropylene/maleic anhydride grafted polypropylene composites.
CN202010707857.2A 2020-07-21 2020-07-21 Core-shell nano silicon oxide @ zirconium oxide particle-polypropylene maleic anhydride grafted polypropylene composite material and preparation method thereof Pending CN112358674A (en)

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