阅读说明：本技术 一种有机自由基聚合物电介质材料及其合成方法 (A kind of organic free radical polyalcohol dielectric substance and its synthetic method ) 是由 张彦峰 张志成 马丽 崔晨晖 陈兴幸 雷恒鑫 谭继东 于 2019-08-15 设计创作，主要内容包括：一种有机自由基聚合物电介质材料及其合成方法,通过将稳定自由基引入到高分子的交联网络结构中,利用一步法流延成膜即可得到部分交联的高分子电介质薄膜,随后通过热处理进一步提高材料的交联度,同时提高了材料的模量与击穿场强；由于体系是一个交联高分子体系,因此该薄膜的模量及耐热性能优异；由于稳定自由基的存在,该电介质薄膜的电学性能优异,具有高的储能密度和放电效率；在整个聚合成膜过程中,反应一步法进行且所使用的试剂廉价,容易获得。(A kind of organic free radical polyalcohol dielectric substance and its synthetic method, by the way that stabilized radical is introduced into polymer crosslinking network structure, partial cross-linked polymer electrolyte membrane can be obtained using one-step method casting film-forming, the degree of cross linking of material is then further increased by heat treatment, while improving the modulus and disruptive field intensity of material；Since system is a cross-linked polymer system, the modulus and Good Heat-resistance of the film；Due to the presence of stabilized radical, the electric property of the thin dielectric film is excellent, has high energy storage density and discharging efficiency；During entire polymerization film formation, reaction one-step method carries out and used reagent is cheap, is easy to get.)

1. a kind of organic free radical polyalcohol dielectric substance, which is characterized in that the structure is as follows

R1 and R2 is selected from one of flowering structure:

2. based on a kind of synthetic method of organic free radical polyalcohol dielectric substance described in claim 1, which is characterized in that The following steps are included:

Step 1: equipped with magneton round-bottomed flask in, be added R2 class monomer 20.5mmol, 100mL containing stabilized radical without 29.0mmol5- norbornene -2- the carboxylic acid and 4-dimethylaminopyridine DMAP, 9.3mmol of water methylene chloride dissolution, in N₂ Under be cooled to 0 DEG C；Then N- (3- dimethylaminopropyl)-N'- carbodiimide hydrochloride 34.9mmol is dissolved in 100mL bis- It is added drop-wise in round-bottomed flask in chloromethanes and under stiring, reaction react 5 minutes at 0 DEG C, at room temperature reaction 48 hours；Most Afterwards, solid is removed by filtration, washs, it is dry, it is concentrated to get the red containing stabilized radical with norbornene functional group Solid；

Step 2: red solid and R1 class monomer that step 1 obtains being mixed according to the degree of polymerization of 100:100-1500 and are completely dissolved In the chloroform of 20mg/mL, Grubbs third generation catalyst G3, G3:R1 class monomer=1 being dissolved in chloroform is added: 100-1500, mol/mol react 10 minutes, then filter the solution, and directly curtain coating preparation electricity is situated between on a glass at room temperature Matter film；

Step 3: the uniform dielectric film that step 2 is obtained is heat-treated at 80-120 DEG C, further increases the crosslinking journey of material Degree.

Technical field

The invention belongs to technical field of polymer materials, in particular to a kind of organic free radical polyalcohol dielectric substance and Its synthetic method.

Background technique

High-voltage pulse capacitor has the characteristics that the alternating current-direct current high pressure characteristics that power density is high, charge/discharge speed is fast, excellent, Occupy irreplaceable position electro-optical equipment, electromagnetic installing are standby etc..With fast development scientific and technological in recent years, as energy supply The impulse capacitor of unit is more and more paid attention to.Existing high-voltage pulse capacitor mainly uses ceramic material, has The advantages such as excellent temperature characterisitic and alternating current-direct current high pressure characteristics.But ceramic capacitor density is big, leads to unit mass capacitor Energy storage density it is low；Ceramic disruptive field intensity is low (< 100MV/m), and ceramic thickness is high between electrode when applying under high pressure, leads to capacitor It is bulky；The sintering process of ceramics makes it be difficult to large area film preparation and flexibility；Ceramic dielectric constant is high, capacitor Device entirety energy storage density is not high, and the ferroelectricity relaxation behavior of ceramics results in serious energy loss.

Other than ceramic capacitor, polymer metal thin film capacitor is able to high speed development, especially polypropylene (PP) Biaxially oriented polypropylene (BOPP) thin-film capacitor is greatly facilitated in the rapid advances of two-way membrane technology and film preparation at home The development of device and high performance.Compared with ceramic capacitor, polymer thin film capacitor is in large area film preparation, capacitor It rolls, capacitor density etc. has overwhelming dominance.But polymer material dielectric constant small (< 15), capacitor energy storage The low (< 3J/cm of density³), the disadvantages of temperature tolerance is insufficient (< 120 DEG C) cause its application in impulse capacitor by many limits System.

In recent years, new polymers and composite dielectric material achieve rapid development.From the angle for improving dielectric constant For, it is the most typical with the research of Kynoar (PVDF) base ferroelectric polymers, pass through electron irradiation or chemical copolymerization Method modified typical ferroelectric poly- (vinylidene-trifluoro-ethylene) (P (VDF-TrFE)) can obtain very typical relaxation Ferroelectric, for dielectric constant up to 100, energy storage density can be up to 20J/cm³.In addition to this, by polymerizeing to PVDF base fluorine The chemical copolymerization of object is modified (with chlorotrifluoroethylene, hexafluoropropene etc.) unidirectional membrane afterwards, it is also possible to obtain Jie of high energy storage density Conductive film.But the ferroelectricity relaxation behavior of this quasi polymer and poor insulation characterisitic cause its energy loss huge (up to 40%), it is difficult to be applied under high electric field.Then, with polystyrene (PS) or polymethacrylates (PXMA) graft modification This quasi polymer studies have shown that under the premise of keeping its high energy storage density characteristic very well, energy loss can be reduced to 20% hereinafter, energy loss is still excessively high, leads to its service life, reliability still compared with BOPP (< 6%@600MV/m) It is all difficult to ensure with long-time stability etc., and such melting point polymer is lower so that it is difficult to use at high temperature.

In order to obtain high energy storage polymeric dielectric resistant to high temperature, scientists start to be explored in engineering plastics, Universal glass transition temperature (the T with higher of such material_g> 200 DEG C), should theoretically have preferable high-temperature insulation characteristic. However, research shows that being far below its T in temperature_gWhen, the high-voltage isulation characteristic of such material just has occurred that obvious deterioration, packet Include disruptive field intensity decline, energy loss be obviously improved, be mostly derived from the polar group of such high molecular material in high temperature and height Directed movement under electric field collective effect.This makes application of such material under high temperature, high electric field not comply with one's wishes.Except this it Outside, in order to improve the temperature-resistance characteristic of polymer, chemical crosslinking and two-dimentional heat-resistant filler (boron nitride nanosheet, mica sheet, oxidation Aluminium etc.) in the polymeric dielectric applied of strategy, but this will lead to the forfeiture of thin polymer film processing technology again, instead It is unfavorable for final electrical property to improve.

Development in recent years is made a general survey of, high energy storage density, high discharging efficiency (low-loss), electricity resistant to high temperature can be met simultaneously Dielectric material not can be implemented simultaneously still, high pressure resistant extremely challenging especially under high temperature for polymer material, and This characteristic is necessary to high energy-storage pulsed capacitor.Therefore, research and development have the polymer dielectric material of " three high " characteristic Have great importance.And physical capacitors theoretical for existing dielectric and based on characteristics such as dipole, interfacial polarizations Dielectric is difficult to realize 30J/cm³Target.Subversiveness dielectric based on novel polarization response and Dielectric Physics theory Macromolecule is urgently researched and developed, to realize the characteristic of " three high ".

Summary of the invention

In order to overcome the drawbacks of the prior art, the purpose of the present invention is to provide a kind of organic free radical polyalcohol dielectrics Material and its synthetic method, since the polymer containing stabilized radical can construct the company of free radical by the self assembly of molecule Continuous channel, which may be implemented the fast transferring transmitting of electronics, to obtain higher conductivity；With being total to for conjugated polymer Jugal frame provides the condition difference that delocalization migrates to free electron, and organic free radical polyalcohol is only in the localized site of high-sequential Electronics is carried, the energy storage that this delicate difference results in the Charge dynamics being exceedingly fast and similar battery of free radical polyalcohol is special Property, and have the characteristics that high energy storage density and low-loss

To achieve the above object, the technical solution of the present invention is as follows:

A kind of organic free radical polyalcohol dielectric substance, the structure are as follows

R1 and R2 is selected from one of flowering structure:

R1:

R2:

Based on a kind of above-mentioned synthetic method of organic free radical polyalcohol dielectric substance, comprising the following steps:

Step 1: in the round-bottomed flask equipped with magneton, R2 class monomer 20.5mmol of the addition containing stabilized radical, The 29.0mmol 5- norbornene -2- carboxylic acid and 4-dimethylaminopyridine DMAP of 100mL anhydrous methylene chloride dissolution, 9.3mmol, in N₂Under be cooled to 0 DEG C；Then by N- (3- dimethylaminopropyl)-N'- carbodiimide hydrochloride 34.9mmol It is dissolved in 100mL methylene chloride and is added drop-wise in round-bottomed flask under stiring, reaction reacts 5 minutes at 0 DEG C, at room temperature Reaction 48 hours；Finally, solid is removed by filtration, wash, it is dry, it is concentrated to get and contains stabilization with norbornene functional group The red solid of free radical；

Step 2: the red solid and R1 class monomer that step 1 is obtained mix complete according to the degree of polymerization of 100:100-1500 Be dissolved in the chloroform of 20mg/mL, add Grubbs third generation catalyst G3, the G3:R1 class monomer that is dissolved in chloroform= 1:100-1500, mol/mol react 10 minutes, then filter the solution, and directly curtain coating preparation is electric on a glass at room temperature Dielectric film；

Step 3: the uniform dielectric film that step 2 is obtained is heat-treated at 80-120 DEG C, further increases the friendship of material Connection degree.

Compared with prior art, a kind of novel organic free radical polyalcohol dielectric substance synthesis provided by the invention has Beneficial effect is:

The synthetic method of organic free radical polyalcohol dielectric substance provided by the invention, as shown in above formula, by will be steady Determine free radical to be introduced into polymer crosslinking network structure, partial cross-linked high score can be obtained using one-step method casting film-forming Sub- thin dielectric film, then further increases the degree of cross linking of material by heat treatment, while improving the modulus of material, results in The raising of disruptive field intensity.Since system is a cross-linked polymer system, the modulus and heat resistance of the film are relatively high； And due to the presence of stabilized radical, the electric property of the thin dielectric film is excellent, the property with low dielectric constant and loss Matter has high energy storage density and heat resistance, and discharging efficiency is high, high disruptive field intensity is reacted during entire polymerization film formation One-step method carries out and used reagent is cheap, is easy to get.

Detailed description of the invention

Fig. 1 is the composite structure formula of the di-electric polymer material containing free radical of the embodiment of the present invention 1.

Fig. 2 is the DSC and stress-strain diagram of the di-electric polymer material containing free radical of the embodiment of the present invention 1.

Fig. 3 is the electric field response and energy storage mechnism of the di-electric polymer material containing free radical of the embodiment of the present invention 1 Schematic diagram.

Fig. 4 is dielectric constant and the loss of the di-electric polymer material containing free radical of the embodiment of the present invention 1.

Fig. 5 is the dielectric constant of the di-electric polymer material containing free radical of the embodiment of the present invention 1 and is lost not The curve (a) that is varied with temperature under same frequency and at different temperatures curve (b) varying with frequency.

Fig. 6 is disruptive field intensity and the Qi Wei boolean of the di-electric polymer material containing free radical of the embodiment of the present invention 1 It is distributed, and the dielectric constant under bias field is with the change curve of electric field.

Fig. 7 is the ferroelectric hysteresis loop of the di-electric polymer material containing free radical of the embodiment of the present invention 1.

Fig. 8 is the energy storage density of the di-electric polymer material containing free radical of the embodiment of the present invention 1 and releasably imitates Rate.

Fig. 9 is the ferroelectric hysteresis loop of the di-electric polymer material containing free radical of the embodiment of the present invention 2.

Specific embodiment

Hereinafter, specific embodiments of the present invention will be described in detail with reference to attached drawing, it is detailed according to these Description, one of ordinary skill in the art can implement the present invention it can be clearly understood that the present invention.Without prejudice to the principle of the invention In the case where, the feature in each different embodiment can be combined to obtain new embodiment, or be substituted certain Certain features in embodiment obtain other preferred implementation embodiments.

The invention will be further described for following embodiment, and purpose, which is only that, more fully understands the purpose of the present invention, Rather than it limits the scope of the invention.