CN110527068B - Organic free radical polymer dielectric material and synthesis method thereof - Google Patents
Organic free radical polymer dielectric material and synthesis method thereof Download PDFInfo
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- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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Abstract
A dielectric material of organic free radical polymer and its synthetic method, through introducing the stable free radical into the cross-linked network structure of macromolecule, utilize one-step method tape casting to form film and can get the dielectric film of macromolecule of partial cross-linking, then further raise the cross-linking degree of the material through the heat treatment, raised modulus and breakdown field intensity of the material at the same time; because the system is a cross-linked polymer system, the modulus and the heat resistance of the film are excellent; due to the existence of stable free radicals, the dielectric film has excellent electrical properties, high energy storage density and high discharge efficiency; in the whole polymerization film-forming process, the reaction is carried out in one step, and the used reagent is cheap and easy to obtain.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an organic free radical polymer dielectric material and a synthesis method thereof.
Background
The high-voltage pulse capacitor has the characteristics of high power density, high charging and discharging speed, excellent alternating current and direct current high-voltage characteristics and the like, and occupies an irreplaceable position in photoelectric equipment, electromagnetic equipment and the like. With the rapid development of technology in recent years, a pulse capacitor as an energy supply unit receives more and more attention. The existing high-voltage pulse capacitor is mainly made of ceramic materials and has the advantages of excellent temperature characteristics, alternating current and direct current high-voltage characteristics and the like. However, the ceramic capacitor has a high density, resulting in a low energy storage density per unit mass of the capacitor; the ceramic breakdown field strength is low (<100MV/m), and the thickness of the ceramic between the electrodes is high when the ceramic is applied under high voltage, so that the capacitor is large in volume; the sintering process of the ceramic makes large-area thin-film preparation and flexibility difficult; the ceramic has a high dielectric constant, the overall energy storage density of the capacitor is not high, and the ferroelectric relaxation properties of the ceramic cause severe energy loss.
Besides ceramic capacitors, polymer metallized film capacitors are developed at a high speed, and particularly, the polypropylene (PP) biaxially oriented film technology and the film preparation are rapidly advanced in China, so that the development and high performance of biaxially oriented polypropylene (BOPP) film capacitors are greatly promoted. Compared with ceramic capacitors, polymer film capacitors have overwhelming advantages in large-area film preparation, capacitor rolling, capacitor density and the like. But the dielectric constant of the polymer material is small (<15) The energy storage density of the capacitor is low (<3J/cm3) Insufficient temperature resistance (C)<120 deg.C) and the like, which causes the application of the pulse capacitor to be limited.
In recent years, new polymers and composite dielectric materials have been rapidly developed. From the perspective of improving the dielectric constant, the research of polyvinylidene fluoride (PVDF) -based ferroelectric polymers is most typical, and a very typical relaxation ferroelectric can be obtained by modifying a typical ferroelectric poly (vinylidene fluoride-trifluoroethylene) (P (VDF-TrFE)) through an electron irradiation or chemical copolymerization method, wherein the dielectric constant of the very typical relaxation ferroelectric can reach 100, and the energy storage density can reach 20J/cm3. In addition, a dielectric film with high energy storage density can be obtained by chemical copolymerization modification (using chlorotrifluoroethylene, hexafluoropropylene and the like) of the PVDF-based fluoropolymer and then drawing the film in a single direction. However, the ferroelectric relaxation property and poor insulation property of these polymers result in huge energy loss (up to 40%), and are difficult to apply under high electric field. Subsequent studies with graft modification of such polymers with Polystyrene (PS) or Polymethacrylate (PXMA) have shown that energy loss can be reduced to below 20% while retaining good high energy storage density properties, but with BOPP ((pxa))<6% @600MV/m), the energy loss is still too high, leading to difficulties in ensuring its service life, reliability and long-term stability, and the low melting point of such polymers makes it difficult to use at high temperatures.
In order to obtain high temperature resistant high energy storage polymer dielectrics, scientists have begun to explore in engineering plastics, which generally have a high glass transition temperature (T)g>200 c) should theoretically have good high temperature insulation properties. However, studies have shown that at temperatures well below their TgIn the meantime, the high-voltage insulation characteristics of the materials are obviously deteriorated, including the reduction of breakdown field strength, the remarkable increase of energy loss and the like, and mainly result from the directional movement of polar groups of the high-molecular materials under the combined action of high temperature and high electric field. This makes the use of such materials at high temperatures and high electric fields undesirable. In addition, in order to improve the temperature resistance of the polymer, chemical crosslinking and two-dimensional heat-resistant filler (boron nitride nanosheet, mica flake, alumina, etc.) strategies are applied to the polymer dielectric, but this will result in the loss of the processability of the polymer film, and is not favorable for the improvement of the final electrical properties.
In recent years, dielectric materials that can satisfy high energy storage density, high discharge efficiency (low loss) and high temperature resistance at the same time cannot be realized at the same time, and for polymer materials, high temperature resistance is particularly challenging, and this characteristic is essential for high energy storage pulse capacitors. Therefore, it is of great significance to develop polymer dielectric materials with "three-high" characteristics. The dielectric of the physical capacitor based on the characteristics of dipole, interface polarization and the like and the existing dielectric theory are difficult to realize 30J/cm3The object of (1). Subversive dielectric macromolecules based on novel polarization response and dielectric physics theory are in urgent need of research and development to realize the characteristics of three-high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an organic free radical polymer dielectric material and a synthesis method thereof, wherein a polymer containing stable free radicals can construct a continuous channel of free radicals through self-assembly of molecules, and the channel can realize rapid migration and transfer of electrons, so that higher conductivity is obtained; different from the condition that the conjugated skeleton of the conjugated polymer provides delocalized migration for free electrons, the organic free radical polymer only bears electrons at highly ordered local sites, and the subtle difference causes the extremely fast charging kinetics of the free radical polymer and the energy storage characteristics of similar batteries, and has the characteristics of high energy storage density and low loss
In order to achieve the purpose, the technical scheme of the invention is as follows:
an organic free radical polymer dielectric material, the structure is as follows
R1 and R2 are selected from one of the following structures:
R1:
R2:
the method for synthesizing the organic radical polymer dielectric material comprises the following steps:
and step 3: and (3) carrying out heat treatment on the uniform dielectric film obtained in the step (2) at the temperature of 80-120 ℃, and further improving the crosslinking degree of the material.
Compared with the prior art, the novel organic free radical polymer dielectric material provided by the invention has the following beneficial effects:
according to the synthesis method of the organic free radical polymer dielectric material, as shown in the formula, stable free radicals are introduced into a macromolecular cross-linking network structure, a partially cross-linked macromolecular dielectric film can be obtained by utilizing a one-step casting film forming method, and then the cross-linking degree of the material is further improved through heat treatment, and meanwhile, the modulus of the material is improved, so that the breakdown field strength is improved. Because the system is a cross-linked polymer system, the modulus and the heat resistance of the film are relatively high; and because of the existence of stable free radicals, the dielectric film has excellent electrical properties, low dielectric constant and loss properties, high energy storage density and heat resistance, high discharge efficiency and high breakdown field strength, and in the whole polymerization film-forming process, the reaction one-step method is carried out, and the used reagents are cheap and easy to obtain.
Drawings
FIG. 1 is a synthetic structural formula of a dielectric polymer material containing radicals of example 1 of the present invention.
FIG. 2 is a DSC vs. stress-strain curve of the free radical containing dielectric polymer material of example 1 of the present invention.
FIG. 3 is a schematic diagram of the electric field response and energy storage mechanism of the free radical containing dielectric polymer material of example 1 of the present invention.
FIG. 4 shows the dielectric constant and loss of the free radical containing dielectric polymer material of example 1 of the present invention.
Fig. 5 is a plot of dielectric constant versus loss versus temperature for the free radical containing dielectric polymer material of example 1 of the present invention (a) and a plot of dielectric constant versus loss versus frequency for different temperatures (b).
FIG. 6 is a graph of the breakdown field strength and its Weibull distribution of the free radical containing dielectric polymer material of example 1 of the present invention, and the variation of the dielectric constant with electric field under a bias electric field.
Fig. 7 is a ferroelectric hysteresis loop of the free radical containing dielectric polymer material of example 1 of the present invention.
Fig. 8 is a graph showing the energy storage density and the releasable efficiency of the dielectric polymer material containing radicals of example 1 of the present invention.
Fig. 9 is a ferroelectric hysteresis loop of the free radical containing dielectric polymer material of example 2 of the present invention.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings, and it will be apparent to those skilled in the art from this detailed description that the present invention can be practiced. Features from different embodiments may be combined to yield new embodiments, or certain features may be substituted for certain embodiments to yield yet further preferred embodiments, without departing from the principles of the present invention.
The invention will be further illustrated by the following examples, which are intended only for the purpose of a better understanding of the invention and do not limit the scope of the invention.
Example one
The structure of an organic radical polymer dielectric material described in this example is as follows
R1 and R2 are selected from one of the following structures:
R1:
R2:
referring to fig. 1 to 8, the present embodiment provides a method for designing and synthesizing a dielectric material, the method including the steps of:
and step 3: and (3) carrying out heat treatment on the uniform dielectric film obtained in the step (2) at the temperature of 80-120 ℃, and further improving the crosslinking degree of the material.
The polymer-like thin film obtained in the embodiment is subjected to test characterization of electrical properties under a low electric field and a high electric field respectively, wherein the test characterization comprises a dielectric spectrum/temperature spectrum, breakdown field intensity, a D-E loop, energy storage density, loss and the like.
Referring to FIG. 2, DSC tests show that the material has no glass transition temperature within the range of-50 to 110 ℃, and a stress-strain curve shows that the modulus of the material can reach 1.9GPa, which is 2 to 3 times of that of BOPP. The material is shown to have excellent heat resistance and mechanical strength equivalent to that of BOPP.
Referring to fig. 3, the energy storage mechanism of the radical dielectric polymer material is shown in the figure, when no electric field is applied, the radicals in the material are not arranged, and after the electric field is applied, the radicals are arranged in a directional manner to store energy.
Referring to fig. 4, the material is tested to obtain different dielectric constants when the content of free radicals is different, a series of materials are prepared in the range of 6% -34% of the molar ratio of the free radicals to the polymer, the dielectric constant is 2.7-3.6, the dielectric constant is kept unchanged under high frequency and low frequency, the materials are ideal linear dielectric materials, and the theory that the dielectric constant is in direct proportion is obtained by comparing the relation between the dielectric constant and the content of the free radicals, and the theory is identical with the theoretical design. The dielectric loss of the material in the designed free radical content range is less than 0.007 at 1000Hz and substantially less than 0.01 in the range of 1-1MHz, and the dielectric material is a low-loss linear dielectric material.
Referring to fig. 5, in a BDS test system, the curves of the dielectric constant and the loss with temperature at different frequencies and the curves with frequency at different temperatures are tested, and it is found that the dielectric constant and the loss of the material have no dielectric property mutation caused by obvious phase change in the range of-40 to 110 ℃. At 0.01-1Hz, the material has a large increase in dielectric constant at high temperatures, probably due primarily to Grubb's catalyst residues.
Referring to fig. 6, the breakdown field strength test shows that the breakdown field strength of the material can reach 700MV/m at room temperature, and the dielectric constant of the material has a remarkable increase under the condition of voltage application. The breakdown of four materials with different compositions is between 650-850MV/m, and the Weibull distribution is narrower, which shows that the consistency of the materials is good. Meanwhile, we measured the dielectric constant of the material under a bias electric field, and found that the dielectric constant of the material under an applied electric field tends to increase, that is, the dielectric constant of the material under a high electric field may be much higher than that measured by the BDS under a low electric field.
Referring to FIG. 7, the ferroelectric test system tests at normal temperature, the material is judged to be a typical linear dielectric material from the hysteresis loop, the result is consistent with the conclusion that the dielectric test obtains the linear dielectric, and the maximum energy storage density of the material can reach 20J/cm at the position of Weibull distribution with 63.2% breakdown probability through calculation3The maximum breakdown field strength of the material can reach 34J/cm3With BOPP and without freenessCompared with stored energy, the dicyclopentadiene polymer has greatly improved energy storage.
Referring to FIG. 8, to determine the contribution of free radicals to the storage density, dicyclopentadiene homopolymer (PDCPD) without any free radicals was synthesized and its electrical properties were determined as follows in comparison to the D-E loop and storage density, discharge efficiency of the free radical copolymer: compared with BOPP, the PDCPD has high electric hysteresis loop slope, high breakdown field intensity and energy storage density which is about 2 times of that of the BOPP. The introduction of free radicals further improves the dielectric constant, the slope of a D-E loop and the energy storage density, the energy storage density of the free radical copolymer is 30-40% higher than that of PDCPD, meanwhile, the breakdown field strength reaches more than 700MV/m, and the energy storage density can reach 20J/cm3The above. The discharge efficiency is over 90 percent, and the discharge efficiency is not obviously reduced along with the electric field.
Example two
The structure of an organic radical polymer dielectric material described in this example is as follows
R2:
The embodiment provides a design synthesis method of a dielectric material, which comprises the following steps:
The polymer-like thin film obtained in the embodiment is respectively subjected to test representation of electrical properties under a high electric field, a ferroelectric test system is used for testing at normal temperature, the material is judged to be a linear dielectric material from a ferroelectric hysteresis loop, the maximum energy storage density of the material is obtained by calculation and is greatly improved compared with BOPP at the position where Weibull distribution is 63.2% of breakdown probability, and a free radical is introduced into the polymer structure to obtain an excellent dielectric energy storage material. (see FIG. 9)
According to the method for synthesizing the organic free radical polymer dielectric material, stable free radicals are introduced into a macromolecular cross-linked network structure, a partially cross-linked macromolecular dielectric film can be obtained by utilizing a one-step casting film forming method, and then the cross-linking degree of the material is further improved through heat treatment, and meanwhile, the modulus of the material is improved, so that the breakdown field strength is improved. Because the system is a cross-linked polymer system, the modulus and the heat resistance of the film are relatively high. And due to the existence of stable free radicals, the dielectric film has excellent electrical properties, high energy storage density and high discharge efficiency. In the whole polymerization film-forming process, the reaction is carried out by one step method, the used reagent is cheap and is easy to obtain
Although the present invention has been described above with reference to specific embodiments, it will be appreciated by those skilled in the art that many modifications are possible in the arrangement and details of the invention disclosed within the principle and scope of the invention. The scope of the invention is to be determined by the appended claims, and all changes that come within the meaning and range of equivalency of the technical features are intended to be embraced therein.
Claims (2)
1. An organic radical polymer dielectric material, characterized in that the structure is as follows:
the organic radical dielectric material is obtained by the following method:
the method comprises the following steps:
step 1. in a round-bottomed flask containing magnetons, 20.5mmol of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl monomer containing a stable free radical, 29.0mmol of 5-norbornene-2-carboxylic acid and 9.3mmol of 4-dimethylaminopyridine DMAP dissolved in 100mL of anhydrous dichloromethane were charged in a N-solution2Cooling to 0 deg.c; then 34.9mmol of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride was dissolved in 100mL of dichloromethane and added dropwise to the round-bottom flask with stirring, reacted at 0 ℃ for 5 minutes and at room temperature for 48 hours; finally, filtering to remove the solid, washing, drying and concentrating to obtain red solid containing stable free radicals and having norbornene functional groups;
step 2, mixing the red solid obtained in the step 1 and dicyclopentadiene monomer according to the polymerization degree of 100:100-1500, completely dissolving the mixture in 20mg/mL chloroform, adding Grubbs third-generation catalyst G3 dissolved in chloroform, G3: dicyclopentadiene monomer 1:100-1500 mol/mol, reacting for 10 minutes, filtering the solution, and preparing a dielectric film by casting directly on a glass plate at room temperature;
and step 3: and (3) carrying out heat treatment on the uniform dielectric film obtained in the step (2) at the temperature of 80-120 ℃, and further improving the crosslinking degree of the material.
2. The method of claim 1, comprising the steps of:
step 1. in a round-bottomed flask containing magnetons, 20.5mmol of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-N-oxyl monomer containing a stable free radical, 29.0mmol of 5-norbornene-2-carboxylic acid and 9.3mmol of 4-dimethylaminopyridine DMAP dissolved in 100mL of anhydrous dichloromethane were charged in a N-solution2Cooling to 0 deg.c; then 34.9mmol of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride were dissolved in 100mL of dichloromethane anddropwise adding the mixture into a round-bottom flask under stirring, reacting at 0 ℃ for 5 minutes, and reacting at room temperature for 48 hours; finally, filtering to remove the solid, washing, drying and concentrating to obtain red solid containing stable free radicals and having norbornene functional groups;
step 2, mixing the red solid obtained in the step 1 and dicyclopentadiene monomer according to the polymerization degree of 100:100-1500, completely dissolving the mixture in 20mg/mL chloroform, adding Grubbs third-generation catalyst G3 dissolved in chloroform, G3: dicyclopentadiene monomer 1:100-1500 mol/mol, reacting for 10 minutes, filtering the solution, and preparing a dielectric film by casting directly on a glass plate at room temperature;
and step 3: and (3) carrying out heat treatment on the uniform dielectric film obtained in the step (2) at the temperature of 80-120 ℃, and further improving the crosslinking degree of the material.
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