阅读说明：本技术 聚（n,n-二苯基-4-（2,5-二甲基-1h-吡咯-1-基）苯胺）的应用及制备 (Application and preparation of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) ) 是由 张�诚 许志怡 吕晓静 钱亮 黄从惠 于 2019-07-19 设计创作，主要内容包括：一种聚(N,N-二苯基-4-(2,5-二甲基-1H-吡咯-1-基)苯胺)作为电致变色材料的应用,所述聚(N,N-二苯基-4-(2,5-二甲基-1H-吡咯-1-基)苯胺)如式(I)所示：<Image he="712" wi="552" file="DDA0002135971910000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式(I)中,n代表平均聚合度。以及提供一种聚(N,N-二苯基-4-(2,5-二甲基-1H-吡咯-1-基)苯胺)的制备方法。本发明所述的聚合物具有多色显示、快速的响应时间,较高光学对比度等优异的性能,是潜在的电致变色材料。(Use of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) as an electrochromic material, the poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) being represented by formula (I): in the formula (I), n represents the average degree of polymerization. And a method for preparing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline). The polymer provided by the invention has excellent performances of multicolor display, quick response time, higher optical contrast and the like, and is a potential electrochromic material.)

1. An application of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown as a formula (I) as an electrochromic material;

in the formula (I), n represents the average degree of polymerization.

2. The process for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 1, wherein poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) is produced by an electrochemical polymerization method by adding an electrolytic solvent, an N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline monomer represented by the formula (II), a supporting electrolyte and an electrolytic solvent to an electrolytic solution, adding the electrolytic solution into a three-electrode electrolytic cell, and electrodepositing on a working electrode by a potentiostatic method, a galvanostatic method or a cyclic voltammetry to obtain a polymer film, the film is cleaned and dried to obtain poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown in the formula (I);

3. the method for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) according to claim 2, wherein the initial concentration of the monomer N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline represented by the formula (II) is 10^-4～10^-1mol/L; preferably, the initial concentration is 2X 10^-3mol/L。

4. The process for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 2, characterized in that the supporting electrolyte consists of anions and cations according to the mass ratio of 1:1, the anion is perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroarsenate ion, nitrate ion, sulfonate ion, sulfate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion or phosphate ion; the cation is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, tetra-n-propylammonium ion, or tetra-n-hexylammonium ion.

5. The method for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 2, wherein the electrolytic solvent is N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, toluene, ethanol, methanol, chloroform, dichloromethane, tetrahydrofuran, cyclohexane, pyridine, propylene carbonate, phenylacetonitrile, diethyl ether, acetic acid, formic acid, hydrochloric acid, phosphoric acid or petroleum ether.

6. The method for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 2, wherein the supporting electrolyte is added in an amount of 10% by volume based on the volume of the electrolytic solvent^-3～10^-1mol/L。

7. The method for preparing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 2, wherein in the three-electrode electrolytic cell, the working electrode is gold, platinum, copper, titanium, stainless steel or ITO electrode, the reference electrode is silver-silver ion electrode, silver-silver chloride electrode or saturated calomel electrode, preferably silver-silver chloride electrode, and the counter electrode is platinum, titanium or stainless steel.

8. The process for producing poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline according to claim 2, wherein the electrochemical polymerization is carried out by a potentiostatic method, the voltage is 1.2 to 1.4V, and the polymerization electric quantity is 0.05C to 0.5C.

Technical Field

The invention belongs to the technical field of electrochromic materials, and particularly relates to application of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) as an electrochromic material and a preparation method thereof.

Background

Electrochromism is the phenomenon that the optical properties (reflectivity, transmittance, absorptivity and the like) of a material are subjected to stable and reversible color change under the action of an external electric fieldLike a reversible change in color and transparency in appearance. Materials having electrochromic properties are referred to as electrochromic materials, and devices made with electrochromic materials are referred to as electrochromic devices. Electrochromic materials exhibit reversible color and absorption spectrum changes upon stimulation by an external potential or current. In recent decades, many scientists have been interested in their wide application in the fields of electronic paper, smart windows, camouflage materials, and the like. Deb published since 1969 about WO₃Research on electrochromic materials and devices has been a hot spot for research since the topical reports of electrochromic phenomena. Electrochromic materials are classified into inorganic electrochromic materials and organic electrochromic materials. Compared with electrochromic inorganic oxide and metal complex, organic polymer, especially conductive polymer, as electrochromic material has the advantages of light weight, easy processing, molecular structure design, rich color change, short response time, low cost, etc. In addition to the electrochromic materials commonly studied in the visible region, electrochromic materials in the near infrared (NIR, 750) -3000nm) region have also been developed recently.

The polytriphenylamine and the derivative thereof are one of typical electrochromic materials, and have good application prospects due to the advantages of low oxidation potential, easy protonic acid doping, high color contrast, good environmental stability and the like. However, conventional triphenylamine derivatives are difficult to prepare polymers using electrochemical anodization because triphenylamine TPA is easily oxidized to form radical cations, TPA +; the cation free radical is unstable and is easy to generate tail-to-tail (para) coupling reaction, so that two protons are lost to produce Tetraphenylbenzidine (TPB); TPB is more susceptible to oxidation than TPA, losing 1 electron to TPB +; then loses one more electron to TPB2+, thereby preventing further electrochemical polymerization. Research shows that electron-donating groups are introduced to the para position of triphenylamine groups, single-cation free radicals formed by electrochemical oxidation can be stabilized, and therefore long-chain polymers are formed through electrochemical polymerization. The pyrrole group is a five-membered heterocyclic compound containing one nitrogen heteroatom, is a common electron-donating group with redox activity, and has an oxidation potential of 0.7V. Meanwhile, the N atom of pyrrole and the activity on the alpha position thereof are stronger, and electrons are easily lost to form corresponding free radical ions.

Disclosure of Invention

The invention aims to provide application of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) as an electrochromic material and a preparation method thereof.

In order to solve the technical problems, the invention provides the following technical scheme:

an application of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown as a formula (I) as an electrochromic material.

In the formula (I), n represents the average degree of polymerization.

A preparation method of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline), wherein the poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown in the formula (I) is prepared by electrochemically polymerizing N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline monomer shown in the formula (II);

the electrochemical polymerization is carried out according to the following steps:

adding an electrolyte consisting of an N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline monomer shown in a formula (II), a supporting electrolyte and an electrolytic solvent into a three-electrode electrolytic cell, carrying out electrodeposition on a working electrode by adopting a potentiostatic method, a galvanostatic method or a cyclic voltammetry to obtain a polymer film, and cleaning and drying the polymer film to obtain the poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown in the formula (I).

Further, a starting material of the N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline monomer represented by the formula (II)Initial concentration of 10^-4～10^-1mol/L; preferably, the initial concentration is 2X 10^-3mol/L。

Further, the supporting electrolyte is a commonly used supporting electrolyte, such as a commonly composed of an anion and a cation in a molar ratio of 1:1, wherein the anion is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, nitrate, sulfonate, sulfate, formate, acetate, propionate, butyrate, valerate or phosphate; the cation is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, tetra-n-propylammonium ion, or tetra-n-hexylammonium ion. Preferably, the supporting electrolyte is tetrabutylammonium perchlorate and tetrabutylammonium hexafluorophosphate.

Further, the electrolytic solvent is a common solvent, such as N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, toluene, ethanol, methanol, chloroform, dichloromethane, tetrahydrofuran, cyclohexane, pyridine, propylene carbonate, phenylacetonitrile, diethyl ether, acetic acid, formic acid, hydrochloric acid, phosphoric acid or petroleum ether, and preferably the electrolytic solvent is dichloromethane.

Further, the supporting electrolyte is added in an amount of 10 by volume of the electrolytic solvent^-3～10^-1mol/L; preferably, the supporting electrolyte is added in an amount of 10 by volume of the electrolytic solvent^-1mol/L。

Further, in the three-electrode electrolytic cell, the working electrode can be a gold electrode, a platinum electrode, a copper electrode, a titanium electrode, a stainless steel electrode or an ITO electrode, and preferably the ITO electrode; the reference electrode is a silver-silver ion electrode, a silver-silver chloride electrode and a saturated calomel electrode, and preferably a silver-silver chloride electrode; the counter electrode is platinum, titanium, stainless steel, preferably platinum.

Furthermore, electrochemical polymerization is preferably carried out by a potentiostatic method, the voltage range is 1.2-1.4V, and the polymerization electric quantity is 0.05-0.5C.

The preparation method of the N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline monomer shown in the formula (II) can be carried out according to the following steps:

4-diphenylamino aniline shown in a formula (III) and 2, 5-hexanedione shown in a formula (IV) react in an organic solvent at the temperature of 110-150 ℃ under the action of an acidic substance, and a reaction liquid obtained after the reaction is completed is separated and purified to obtain an N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline monomer shown in a formula (II).

Further, the acidic substance is glacial acetic acid.

Further, the organic solvent is toluene.

Furthermore, the ratio of the amounts of the 4-diphenylaminoaniline represented by the formula (III), the 2, 5-hexanedione represented by the formula (IV) and the acidic substance is 1: 1-1.5: 1-10.

Further, the reaction time is 10-24 h.

Further, the reaction solution is separated and purified by the following steps: and after the reaction is finished, filtering the obtained reaction liquid, removing filtrate, leaching and filtering a solid product by using absolute ethyl alcohol, and drying the obtained solid product to obtain the N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline monomer shown in the formula (II).

The poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline) shown in the formula (I) has the characteristics of reversible color change (namely, the color is changed into orange red and further into blue along with the increase of applied voltage, and the color is changed back to the original light color after the voltage is gradually reduced), high optical contrast and quick response time under different voltages.

2, 5-dimethylpyrrole group with electrochemical redox activity is introduced to triphenylamine para position to synthesize N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline, corresponding polymer films are prepared by electrochemical polymerization, and the application of the polymer films in the field of electrochromism is further investigated.

Compared with the prior art, the invention has the advantages that:

(1) preparing a novel poly (triphenylamine) derivative, namely poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrole-1-yl) aniline), by adopting an electrochemical polymerization method;

(2) compared with other conventional electrochromic materials, the electrochromic material prepared by the invention has the advantages of multicolor display, quick response, high color contrast and the like.

Drawings

FIG. 1 shows the cyclic voltammetric polymerization curve of N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline.

FIG. 2 is a scanning electron micrograph of a poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) film. Wherein (a) at a magnification of 10000 ×; (b)30000x magnification; (c) a cross-sectional view.

FIG. 3 shows the spectroelectrochemical curves and color changes of poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) film under different voltages.

FIG. 4 is a graph of response time and contrast for poly (N, N-diphenyl-4- (2, 5-dimethyl-1H-pyrrol-1-yl) aniline) films at different wavelengths.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto.