CN114853987B - Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film - Google Patents
Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film Download PDFInfo
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Abstract
An electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structures is provided, and the molecular formula of the electrochromic copolymer comprises the following structures:wherein A represents sulfur or oxygen, m and n each represent a degree of polymerization and are integers of 8 to 100. The preparation method comprises the following steps: 1) Adding dioxypropylenethiophene, 2', 7' -tetrabromo-9, 9' -spirobifluorene, 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiothiophene, N-dimethylacetamide, potassium carbonate, palladium acetate and pivalic acid into a single-neck flask, pumping air into the single-neck flask by using nitrogen or argon and keeping a ventilation atmosphere, sequentially heating and reacting the mixture, cooling to room temperature, dripping into methanol, and filtering to collect orange-red precipitate; 2) And (3) placing the orange-red precipitate in a fat extractor, sequentially dissolving and washing with methanol, normal hexane and chloroform, concentrating chloroform washing liquid, finally dripping into methanol, and filtering to collect the precipitate, thus obtaining the target product.
Description
The invention relates to the technical field of electrochromic, in particular to an electrochromic copolymer containing dioxythiophene and a 9,9' -spirobifluorene structure, a preparation method thereof and a polymer film.
Background
Electrochromic materials refer to materials with optical property change caused by reversible oxidation-reduction reaction under the action of an external electric field, and have wide application prospects in the fields of intelligent windows, anti-dazzle rearview mirrors, military intelligent camouflage and the like. Generally, the electrochromic material comprises transition metal oxide, viologen micromolecules, conductive polymers and the like, wherein the conductive polymers become research and application hot spots in the current electrochromic field due to the advantages of designable structure, rich color conversion, high contrast, high response speed, high coloring efficiency, good stability and the like. In the past, development of novel conductive polymers excellent in electrochromic properties, particularly showing yellow, orange and red, has been of great significance for research on polymer electrochromic.
To achieve yellow, orange, and red color display, it is desirable that the polymer have a higher band gap, while to increase the stability of the polymer, the band gap increase is caused by steric hindrance effects, rather than electron-induced effects, as much as possible. Thus, electron rich groups should be included in the polymer structure and groups that disrupt the planar conjugation properties. Generally, the electron-rich group is mainly of thiophene structure, while the group breaking plane conjugation has benzene ring, naphthalene ring and the like, and the corresponding polymer generally has higher color-changing potential, so that the color-changing stability is poor.
The spirobifluorene derivative is taken as an organic conjugated unit, the conductive polymer formed by the spirobifluorene derivative shows excellent luminescence performance in the field of organic electroluminescence, the conjugated planeness of the spirobifluorene derivative structure is not strong, the conjugated planeness of the spirobifluorene derivative structure can be interrupted by embedding the spirobifluorene derivative into a conjugated polymer main chain, and meanwhile, the electrochemical oxidation potential of the conductive polymer formed by the spirobifluorene derivative is not high due to the fact that the spirobifluorene derivative has a larger aromatic ring structure, so that the spirobifluorene derivative can be used as an ideal block unit for designing and preparing high band gap electrochromic polymers such as yellow, orange and red. At present, no report of related polymers is available.
Disclosure of Invention
The invention aims to design and prepare electrochromic copolymer and polymer film containing dioxythiophene and 9,9 '-spirobifluorene structure, and the electrochromic copolymer of 9,9' -spirobifluorene, 3, 4-ethylenedioxy (thio) thiophene and 3, 4-dioxypropylenethiophene is prepared mainly by an arylation coupling method.
The technical scheme of the invention is as follows: first, the present invention provides an electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, wherein the molecular formula of the electrochromic copolymer comprises a structure shown as the following formula (1):
in the formula (1), A represents sulfur or oxygen, m and n each represent a degree of polymerization, and are natural numbers, preferably integers of 8 to 100.
The invention also provides a preparation method of the electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, and the synthetic route is shown in the following formula (2):
the method comprises the following specific steps:
1) Preparation of the polymer by arylation coupling: adding dioxypropylenethiophene (M1), 2', 7' -tetrabromo-9, 9' -spirobifluorene (M2), 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiothiophene (M3), N-dimethylacetamide, potassium carbonate, palladium acetate and pivalic acid into a single-neck flask, wherein an air source connecting device and a condenser tube are arranged above the single-neck flask, pumping the single-neck flask, keeping atmosphere protection after ventilation in the single-neck flask, heating the mixture for reacting for a certain time, cooling to room temperature, dripping the reacted mixture solution into methanol for precipitation, and filtering and collecting orange-red precipitate;
2) Purification of the polymer by soxhlet extraction: wrapping the orange-red precipitate obtained in the step 1) by filter paper, placing the filter paper in a fat extractor, firstly adopting methanol for washing, washing the washed precipitate again by normal hexane, then carrying out reverse dissolution washing on the precipitate in chloroform, separating to remove the precipitate, concentrating chloroform washing liquid, finally dripping the chloroform washing liquid into methanol for reprecipitation, and filtering to collect the precipitate, thus obtaining the purified electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure.
In the methanol and n-hexane washing step 2), small molecular impurities in the product are removed from the precipitate in a dissolving way; in the chloroform washing, macromolecular impurities in the product are separated from the chloroform washing liquid by an insoluble manner (the objective copolymer is dissolved in chloroform).
Further, the molar ratio of the dioxypropylenethiophene, 2', 7' -tetrabromo-9, 9' -spirobifluorene and 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiothiophene in the step 1) is 4:1:2.
further, the molar ratio of the dioxypropylenethiophene to the potassium carbonate in the above step 1) is 1: (2-4), the mol ratio of the dioxypropylenethiophene to the pivalic acid is 1: (0.1-0.25), the mol ratio of the dioxypropylidene thiophene to the palladium acetate is 1: (0.002-0.02); the N, N-dimethylacetamide is used as a solvent.
Further, the reaction temperature in the step 1) is 70-100 ℃ and the reaction time is 48-96 hours; the air pumping and exhausting is to replace air in the single-neck flask with nitrogen or argon.
The invention also provides a polymer film which is obtained by diluting the electrochromic copolymer containing the dioxythiophene and the 9,9' -spirobifluorene structure by a solvent and then spraying or knife coating, wherein the thickness of the polymer film is 200-800 nm.
The above polymer films show electrochromic behavior from orange red to transparent: the color contrast reaches more than 40%, the response rate is less than 3 seconds, the color change cycle is 500 times, and no attenuation exists. The electrochromic device has the structure of a conductive substrate, an electrochromic material, an electrolyte, a counter electrode and a conductive substrate.
The polymer films of the present invention are preferably used in electrochromic devices.
The electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure can be formed by diluting a solvent (the solvent is an organic system such as toluene, chloroform, tetrahydrofuran and the like and does not need other components) and then scraping and spraying the solution on the surface of a conductive substrate to form a film, the color conversion range of the electrochromic copolymer is orange red to transparent state shown by a high band gap polymer, the driving voltage is lower than 1V, the optical contrast reaches more than 40 percent, and the electrochromic copolymer is almost attenuated for 500 times in a circulating manner, and the electrochromic copolymer is suitable for the assembly application of electrochromic devices.
The invention has the advantages that: according to the invention, the spirobifluorene derivative unit is introduced into the main chain of dioxythiophene, the coplanarity of the polymer is broken by utilizing the plane distortion characteristic of the spirobifluorene derivative unit, and meanwhile, the obtained copolymer is based on the self large aromatic ring structure and the strong electron donating property of dioxythiophene, so that the preparation of the high-stability orange-red high-band-gap electrochromic polymer is realized.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a nuclear magnetic resonance spectrum of an electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structures prepared in the example of the present invention, wherein (a) is the nuclear magnetic resonance spectrum of P (PRODOT-C20-4 PH-EDTT); (b) P (PRODOT-C20-4 PH-EDOT) nuclear magnetic hydrogen spectrum;
FIG. 2 is a spectral absorption curve of an electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structures prepared in the examples of the present invention dissolved in methylene chloride;
FIG. 3 is a graph showing the UV-visible absorption spectrum of a polymer film prepared according to an embodiment of the present invention at different potentials, wherein (a) is the UV-visible absorption spectrum of P (PRODOT-C20-4 PH-EDTT) at different potentials; (b) An ultraviolet-visible absorption spectrum curve of P (PRODOT-C20-4 PH-EDOT) at different potentials;
FIG. 4 is a cyclic voltammogram of a polymer film prepared in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the thermal stability of polymer films prepared according to examples of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of enabling those skilled in the art to understand the invention better.
Example 1
The preparation method of the electrochromic copolymer containing the dioxythiophene and the 9,9' -spirobifluorene structure comprises the following steps:
(1) Synthesis of 3, 4-ethylenedithiothiophene
0.1mol of 3, 4-dimethoxythiophene, 0.15mol of 1, 2-ethanedithiol and 0.001mol of p-toluenesulfonic acid-hydrate were dissolved in 200mL of toluene, and placed in a 500mL single-neck flask, and a Soxhlet extractor with molecular sieve and a condenser tube were connected. Reflux stirring for reaction for 24 hours, then cooling to room temperature, pouring the reaction liquid into water, separating the liquid, collecting an organic phase, extracting the water phase with 20mL of dichloromethane twice, merging the organic phases, drying with anhydrous magnesium sulfate, loading the mixture on a silica gel column by a wet method, and obtaining a white solid with the yield of 76% by using dichloromethane/n-hexane (1:1) as a leaching agent; the nuclear magnetic hydrogen spectrum 1HNMR (400 MHz, CDCl) of the compound prepared by the step 3 ,δ,ppm):3.24(s,4H),6.99(s,2H)。
(2) Synthesis of 2, 5-dibromo-3, 4-ethylenedithiothiophene
0.1mmol of 3, 4-ethylenedithiothiophene is dissolved in 20mL of chloroform and placed in a double-mouth bottle, the temperature is reduced to 0 ℃ by covering with tinfoil paper, the atmosphere is protected, 0.3mmol of NBS is dissolved in 10mL of DMF, the solution is slowly dripped into the double-mouth bottle, and the reaction is carried out for 8 hours after the dripping is completed and the temperature is raised to room temperature. Spin-evaporating the reaction solution, removing the solvent, dissolving the residue with dichloromethane, loading the residue on a silica gel column by adopting a wet method, and obtaining white solid with the yield of 63% by using dichloromethane/n-hexane (1:2) as a leaching agent; the nuclear magnetic hydrogen spectrum 1HNMR (400 MHz, CDCl) of the compound prepared by the step 3 ,δ,ppm):3.44(s,4H)。
(3) Synthesis of electrochromic polymers
1. Placing 0.2mmol of 2, 5-dibromo 3, 4-ethylenedithiothiophene prepared in the step (2), 0.1mmol of 2,2', 7' -tetrabromo-9, 9' -spirobifluorene, 0.4mmol of icosaalkoxymethyl propylene dioxythiophene (limited, not subjected to other experiments), 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid in a 25mL double-mouth bottle, pumping and ventilating the bottle to inject nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and ventilating the bottle to fill the nitrogen again, heating the bottle to 120 ℃ for reflux reaction for 72 hours, cooling the reaction liquid to room temperature after the reaction is finished, dripping the reaction liquid into cold methanol for precipitation, filtering the precipitate for drying; and then respectively carrying out Soxhlet extraction by methanol, n-hexane (mainly washing to remove impurities in precipitate) and chloroform (the precipitate washed by n-hexane is dissolved in chloroform), wherein the extraction time is 24 hours each time, concentrating chloroform extract to 15mL, dripping into cold methanol to precipitate to obtain black solid, and filtering and drying to obtain the target polymer P (PRODOT-C20-4 PH-EDTT) with the yield of 60%.
2. Placing 0.2mmol of 2, 5-dibromo-3, 4-ethylenedioxythiophene, 0.1mmol of 2,2', 7' -tetrabromo-9, 9' -spirobifluorene, 0.4mmol of dodecyloxymethylpropylenedioxythiophene, 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid into a 25mL double-mouth bottle, pumping and ventilating nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and ventilating nitrogen again, heating to 120 ℃ to reflux for reaction for 72 hours, cooling to room temperature after the reaction is finished, dripping the reaction solution into cold methanol for precipitation, filtering the precipitate and drying; and respectively carrying out Soxhlet extraction with methanol, n-hexane and chloroform for 24 hours, concentrating chloroform extract to 15mL, dripping into cold methanol to precipitate to obtain black solid, and filtering and drying to obtain target polymer P (PRODOT-C20-4 PH-EDOT) with a yield of 66%.
The nuclear magnetic resonance hydrogen spectrum of the obtained target polymer is shown in figure 1, wherein (a) is P (PRODOT-C20-4 PH-EDTT); (b) is P (PRODOT-C20-4 PH-EDOT).
Example 2
Example 1 preparation of a PolymerThe compounds were subjected to solution spectra and electrochemical performance testing. Dissolving polymer in dichloromethane to obtain a concentration of 2×10 -4 mg/mL of the solution, the absorption curves of the solutions are shown in FIG. 2, and the polymer P (PRODOT-C20-4 PH-EDTT) and P (PRODOT-C20-4 PH-EDOT) solutions appear orange-yellow and orange-red, respectively. The solution was tested by UV-visible spectrophotometry with corresponding absorption peaks at 434nm and 488nm, respectively.
Preparing a polymer film: dissolving the polymer in chloroform to prepare a solution of 2mg/ml, filtering out insoluble substances through a filter tip, placing the solution in a spray gun, controlling the air pressure to be 2MPa, spraying on conductive glass, and placing the sprayed solution in a vacuum drying oven for use at 40 ℃ after the film absorbance is about 0.8. A three-electrode system with a polymer film as a working electrode, a platinum wire as a counter electrode and a calibrated silver wire as a reference electrode is adopted, and the supporting electrolyte is as follows: 0.2mol/L of lithium perchlorate propylene carbonate solution.
The polymer film was subjected to spectroelectrochemical performance tests at different voltages. The three-electrode system is adopted, a platinum wire is a counter electrode, a calibrated silver wire is a reference electrode, a polymer film is a working electrode, and a supporting electrolyte is as follows: 0.1mol/L of lithium perchlorate propylene carbonate solution. The spectrum electrochemical spectrograms of the two copolymer films under different applied voltages are shown in figure 3, which shows that the copolymer films have obvious electrochromic properties. Due to the stacking of pi-pi bonds, the polymer film has a certain red shift relative to the spectrum of the solution, and the corresponding absorption peaks are 460nm and 502nm, respectively. They can realize reversible change from color to transparency at lower voltage.
The copolymer was tested for electrochemical stability by cyclic voltammetry (see FIG. 4), wherein the oxidation potential of P (PRODOT-C20-4 PH-EDOT) was 1.2V, and cyclic voltammetry scanning remained stable for multiple times.
The electrochromic polymers were tested for thermal stability (see fig. 5): the thermal decomposition temperature of the polymer is higher than 310 ℃, which indicates that the polymer can be applied to working environments with higher temperature.
From the above examples, it can be seen that the copolymer film prepared by the present invention can realize the conversion from color to transparency, and has the characteristics of low driving potential, high coloring efficiency, good stability, etc., and the prepared copolymer film can be applied in the fields of electrochromic display, self-adaptive camouflage, etc.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (8)
1. An electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structures, which is characterized by comprising the following structures in the molecular formula:
wherein A represents sulfur or oxygen, m and n both represent polymerization degree, m and n both are integers of 8-100;
the electrochromic copolymer containing the dioxythiophene and the 9,9 '-spirobifluorene structure is polymerized by dioxypropylthiophene (M1), 2',7 '-tetrabromo-9, 9' -spirobifluorene (M2), 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiothiophene (M3).
2. A process for the preparation of electrochromic copolymers containing dioxythiophene and 9,9' -spirobifluorene structures according to claim 1, characterized in that it comprises the following steps:
1) Preparation of the polymer by arylation coupling: adding dioxypropylenethiophene (M1), 2', 7' -tetrabromo-9, 9' -spirobifluorene (M2), 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiothiophene (M3), N-dimethylacetamide, potassium carbonate, palladium acetate and pivalic acid into a single-neck flask, wherein an air source connecting device and a condenser tube are arranged above the single-neck flask, pumping the single-neck flask, keeping atmosphere protection after ventilation in the single-neck flask, heating the mixture for reacting for a certain time, cooling to room temperature, dripping the reacted mixture solution into methanol for precipitation, and filtering and collecting orange-red precipitate;
2) Purification of the polymer by soxhlet extraction: wrapping the orange-red precipitate obtained in the step 1) by filter paper, placing the filter paper in a fat extractor, firstly adopting methanol for washing, washing the washed precipitate again by normal hexane, then carrying out reverse dissolution washing on the precipitate in chloroform, separating to remove the precipitate, concentrating chloroform washing liquid, finally dripping the chloroform washing liquid into methanol for reprecipitation, and filtering to collect the precipitate, thus obtaining the purified electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure.
3. The process according to claim 2, wherein the molar ratio of the dioxypropylenethiophene, 2', 7' -tetrabromo-9, 9' -spirobifluorene and 3, 4-dibromoethylenedioxythiophene or 3, 4-dibromoethylenedithiophene in step 1) is 4:1:2.
4. the method according to claim 2, wherein the molar ratio of the dioxypropylenethiophene to the potassium carbonate in the step 1) is 1: (2-4), the mol ratio of the dioxypropylenethiophene to the pivalic acid is 1: (0.1-0.25), the mol ratio of the dioxypropylidene thiophene to the palladium acetate is 1: (0.002-0.02); the N, N-dimethylacetamide is used as a solvent.
5. The method according to claim 2, wherein the reaction temperature in step 1) is 70 to 100 ℃ and the reaction time is 48 to 96 hours; the air pumping and exhausting is to replace air in the single-neck flask with nitrogen or argon.
6. A polymer film, wherein the polymer film is obtained by diluting the electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure according to claim 1 with a solvent and then spraying or knife coating, and the thickness of the polymer film is 200-800 nm.
7. The polymer film of claim 6, wherein the polymer film exhibits an electrochromic behavior from orange red to clear: the color contrast reaches more than 40%, the response rate is less than 3 seconds, the color change cycle is 500 times, and no attenuation exists.
8. The polymer film of claim 6, wherein the polymer film is used in an electrochromic device.
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| Conjugated Polymer Nanoparticles Based Fluorescent Electronic Nose for the Identification of Volatile Compounds;Peng Zhao et al;《Anal. Chem.》;第90卷(第7期);第4815-4822页 * |
| Fluorescent electronic tongue supported with water-borne polyurethane for the discrimination of nitroaromatics in aqueous solution;Tao Yang et al;《J. Mater. Chem. C》;第8卷;第2500-2506页 * |
| Production of Nanostructured Conjugated Polymers by Electropolymerization of Tailored Tetrahedral Precursors;Ali Yassin et al;《ChemElectroChem》;第1卷;第1219-1225页 * |
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