CN116874745A - Thiophene derivative conjugated polymer containing amphoteric ions and preparation method and application thereof - Google Patents

Thiophene derivative conjugated polymer containing amphoteric ions and preparation method and application thereof Download PDF

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CN116874745A
CN116874745A CN202310892894.9A CN202310892894A CN116874745A CN 116874745 A CN116874745 A CN 116874745A CN 202310892894 A CN202310892894 A CN 202310892894A CN 116874745 A CN116874745 A CN 116874745A
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reaction
conjugated polymer
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欧阳密
孔晨雯
张�诚
张金路
花奇奇
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a conjugated polymer of thiophene derivatives containing amphoteric ions, a preparation method and application thereof, wherein the amphoteric ion side chains are modified on the conjugated polymer, so that not only can the solubility of the polymer in a solvent be improved, but also the ion transmission efficiency can be improved, and the electrochromic performance can be improved; in the invention, thiophene monomer is easy to modify, the reaction selectivity is good, the flow is simple, byproducts are few, and the product generates salt and is easy to separate; the thiophene derivative containing zwitterions with different lengths from a conjugated main chain is sprayed into a film by a chemical polymerization mode, and the polymerizationThe object film can display various color changes under different voltages, and has application value in the electrochromic field;

Description

Thiophene derivative conjugated polymer containing amphoteric ions and preparation method and application thereof
Technical Field
The invention relates to the field of organic synthesis, in particular to a novel thiophene derivative conjugated polymer containing amphoteric ions, and a preparation method and application thereof.
Background
Conjugated thienyl polymers are one of the most widely used organic materials in organic electronics, particularly in field effect transistors, light emitting diodes and electrochromic devices. Among electrochromic materials, thiophene derivatives are commonly used hole transport materials and electrochromic parent materials, wherein the polythiophene conductive polymer has the characteristics of simple synthesis, rich colors and the like, and is one of the most studied electrochromic material systems due to good environmental stability and thermal stability during doping and dedoping.
The 3, 4-ethylenedioxythiophene is also a star molecule in the electrochromic field, not only can obviously oxidize and reduce to change color, but also has a structure which is easy to modify, and the 3, 4-ethylenedioxythiophene unit has stronger power supply capability and good electrochromic property, and can effectively regulate and control the color changing voltage, color changing range and color changing efficiency of the whole conjugated unit, so that the construction of the double-donor conjugated polymer by taking thiophene as a first donor and 3, 4-ethylenedioxythiophene as a second donor is widely studied in the electrochromic field. In which the hanging zwitterion is regarded as a side-chain dipole, imparts solubility in polar solvents for solution processing, and is capable of forming a film. The polar zwitterionic side chains make these polymers hydrophilic and salt responsive, which can effectively improve charge injection and thus ionic conductivity. Therefore, the introduction of the zwitterionic side chains with different lengths from the main chain into the thiophene derivative conjugated polymer not only can provide high solubility in water or organic solvents, but also can improve the response time of the thiophene derivative conjugated polymer in the electrochromic field and influence the material performance.
Disclosure of Invention
In order to overcome the defect that the existing polymer is not ideal in solubility in a solvent, a solution-processable film forming mode is not realized, and the problem of ion transmission efficiency between an electrolyte solution and a film is overcome, the invention provides a novel thiophene derivative conjugated polymer containing amphoteric ions, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a conjugated polymer of thiophene derivatives containing amphoteric ions has a structural formula shown in formula I:
in formula I, x=1 to 8, preferably x=1 or 4;
n＝20～30。
in the present invention, thiophene and 3, 4-ethylenedioxythiophene constitute a conjugated polymer, while the pendant zwitterionic side chains provide a certain solubility, and the conductive polymer film can be prepared by spray coating.
A preparation method of a conjugated polymer of thiophene derivatives containing amphoteric ions, which is shown in a formula I, comprises the following steps:
(1) 3, 4-ethylenedioxythiophene reacts with bisboronic acid pinacol ester to obtain a compound III (EDOT-2 Bpin);
specifically, the operation method of the step (1) is as follows: at N 2 Under the protection, mixing 3,4 ethylene dioxythiophene and bisboronic acid pinacol ester, adding a catalyst methoxy (cyclooctadiene) iridium dimer and 4, 4-di-tert-butyl-2, 2-bipyridine, and a solvent n-hexane, stirring for 16 hours at normal temperature, filtering, washing a filter cake with n-hexane, and drying under reduced pressure to obtain a compound III;
preferably, the molar ratio of 3,4 ethylene dioxythiophene to pinacol biborate is 1:2;
preferably, the volume mass ratio of the solvent n-hexane to the bisboronic acid pinacol ester is 8:1, mL/g;
(2) The compound II and the compound III are subjected to Suzuki coupling reaction to prepare a product I;
specifically, the operation method of the step (2) is as follows: at N 2 Under the protection, mixing the compound II, the compound III, the catalyst bis (triphenylphosphine) palladium dichloride and a reaction solvent, stirring and heating to 90 ℃ for reflux reaction for 24-30 h, cooling the reaction liquid to room temperature, pouring the reaction liquid into methanol,filtering, sequentially performing Soxhlet extraction on a filter cake by using tetrahydrofuran, methanol and trifluoroethanol, collecting trifluoroethanol extract after extraction, spin-drying, transferring to a dialysis bag, dialyzing with pure water for 2 days, and freeze-drying to obtain a product I;
preferably, the molar ratio of compound II to compound III is 1:1, a step of;
the reaction solvent is toluene, 2M aqueous potassium carbonate solution and 2M aqueous sodium bromide solution with the volume ratio of 2:1:1, a mixture of two or more of the above-mentioned materials;
the monomer for synthesizing the conjugated polymer of the thiophene derivative containing the amphoteric ions is shown in the formula I, and the structural formula is shown in the formula II:
in formula II, x=1 or 4 is preferred.
When x=1, the monomer of formula II is compound VII, which is synthesized as follows:
s1: 3-thiophenecanol is subjected to bromination reaction of N-bromosuccinimide (NBS) to obtain a compound IV (2, 5-dibromo-3-thiophenecanol);
the specific operation method comprises the following steps: mixing 3-thiophenecanol, N-bromosuccinimide and tetrahydrofuran as solvent, stirring at normal temperature for 12h, pouring the reaction liquid into deionized water, extracting with ethyl acetate, concentrating and drying the extract, mixing with crude silica gel (200-300 meshes), purifying by column chromatography, taking fine silica gel (300-400 meshes) as stationary phase, and the volume ratio is 5:1, petroleum ether and ethyl acetate are taken as mobile phases, eluent containing target compounds is collected, solvent is removed by rotary evaporation, and the compound IV is obtained by drying;
preferably, the molar ratio of 3-thiophenemethanol to N-bromosuccinimide is 1:2.5;
preferably, the volume mass ratio of the tetrahydrofuran solvent to the 3-thiophenecanol is 10-20: 1, mL/g;
s2: the compound IV is subjected to substitution reaction by phosphorus tribromide (PBr 3) to obtain a compound V (2, 5-dibromo-3-thiophene methyl bromide);
the specific operation method comprises the following steps: at N 2 Under the protection, mixing the compound IV, phosphorus tribromide and solvent anhydrous dichloromethane, stirring for 30min at 0 ℃, then naturally heating to room temperature, stirring for 12h, pouring the reaction liquid into deionized water, extracting with dichloromethane, concentrating and drying the extract, mixing the extract with crude silica gel, performing column chromatography purification, taking fine silica gel as a stationary phase, and mixing the extract with the fine silica gel at a volume ratio of 9:1, petroleum ether and ethyl acetate are taken as mobile phases, eluent containing target compounds is collected, solvent is removed by rotary evaporation, and the compound V is obtained by drying;
the preferred molar ratio of compound IV to phosphorus tribromide is 1:1, a step of;
preferably, the volume mass ratio of the solvent anhydrous methylene dichloride to the compound IV is 10-20: 1, mL/g;
s3: compound V was substituted with dimethylamine to give compound VI (1- (2, 5-dibromothiophen-3-yl) -N, N-dimethylamine);
the specific operation method comprises the following steps: mixing a compound V with tetrabutylammonium bisulfate, adding dimethylamine and chloroform solvent, carrying out reflux reaction for 2 hours at 60 ℃, pouring the reaction liquid into deionized water, extracting with dichloromethane, concentrating and drying the extract, taking aluminum oxide as a stationary phase, and carrying out volume ratio of 1:1, petroleum ether and methylene dichloride are taken as mobile phases, column chromatography purification is carried out, eluent containing a target compound is collected, solvent is removed by rotary evaporation, and the compound VI is obtained;
preferably, the molar ratio of compound V to tetrabutylammonium bisulfate is 10:1, a step of;
preferably the ratio of dimethylamine to compound V is 5 by volume mass: 2, mL/g;
preferably, the volume mass ratio of the chloroform solvent to the compound V is 15:2, mL/g;
s4: the compound VI and 1, 3-propane sultone undergo a ring opening reaction to obtain a compound VII (3- (((2, 5-dibromothiophene-3-yl) methyl) dimethyl ammonium group) -propane-1-sulfonate);
the specific operation method comprises the following steps: mixing a compound VI, 1, 3-propane sultone and anhydrous acetonitrile serving as a solvent, heating to 80 ℃ for reflux reaction for 1h, cooling to room temperature, filtering, washing a filter cake with the anhydrous acetonitrile, and drying under reduced pressure to obtain a compound VII;
the preferred molar ratio of compound VI to 1, 3-propane sultone is 1:4, a step of;
preferably, the volume mass ratio of the solvent anhydrous acetonitrile to the compound VI is 20:1, mL/g;
when x=4, the monomer of formula II, compound XI, is synthesized as follows:
s1: 3-bromothiophene is subjected to substitution reaction with 1, 4-dibromobutane to obtain a compound VIII (3- (4-bromobutyl) thiophene);
the specific operation method comprises the following steps: at N 2 Under the protection, 3-bromothiophene is dissolved in normal hexane, cooled to minus 50 ℃, n-butyllithium is dripped, tetrahydrofuran is added for dilution after stirring for 10min, stirring is continued for 1h at minus 50 ℃,1, 4-dibromobutane is added, stirring is carried out for 12h at room temperature, then reaction liquid is poured into deionized water, diethyl ether is used for extraction, extract liquid is concentrated and dried, crude silica gel is used for sample stirring, column chromatography purification is carried out, fine silica gel is used as stationary phase, petroleum ether is used as mobile phase, eluent containing target compound is collected, solvent is removed by rotary evaporation and drying are carried out, and compound VIII is obtained;
preferably, the molar ratio of 3-bromothiophene to 1, 4-dibromobutane is 1:1.5;
preferably, the molar ratio of 3-bromothiophene to n-butyllithium is 1:1, a step of;
preferably, the volume mass ratio of the solvent n-hexane to the 3-bromothiophene is 10-20: 1, mL/g;
s2: bromination reaction of the compound VIII with N-bromosuccinimide (NBS) to obtain a compound IX (2, 5-dibromo-3- (4-bromobutyl) thiophene);
the specific operation method comprises the following steps: mixing a compound VIII, N-bromosuccinimide and a solvent DMF (dimethyl formamide), stirring for 12 hours at normal temperature, pouring the reaction solution into deionized water, extracting with ethyl acetate, concentrating and drying the extract, mixing a sample with crude silica gel, performing column chromatography purification, taking fine silica gel as a stationary phase and petroleum ether as a mobile phase, collecting an eluent containing a target compound, removing the solvent by rotary evaporation, and drying to obtain a compound IX;
preferably, the molar ratio of compound VIII to N-bromosuccinimide is 1:2.5;
preferably, the volume mass ratio of the solvent DMF to the compound VIII is 10-20: 1, mL/g;
s3: the compound IX is subjected to substitution reaction with dimethylamine to obtain a compound X (2, 5-dibromo-N, N-dimethyl-3-thiophenebutylamine);
the specific operation method comprises the following steps: mixing the compound IX with dimethylamine, carrying out reflux reaction for 12 hours at 60 ℃, filtering (removing salt), washing with ethyl acetate, concentrating and drying filtrate, mixing with crude silica gel, carrying out column chromatography purification, taking fine silica gel as a stationary phase, and carrying out a volume ratio of 1:1, petroleum ether and ethyl acetate are taken as mobile phases, eluent containing target compounds is collected, solvent is removed by rotary evaporation, and the compound X is obtained by drying;
the molar ratio of compound IX to dimethylamine is preferably 1:2;
s4: the compound X and 1, 3-propane sultone undergo a ring opening reaction to obtain a compound XI (3- ((4- (2, 5-dibromothiophene-3-yl) butyl) dimethyl ammonium group) -propane-1-sulfonate);
the specific operation method comprises the following steps: mixing the compound X, 1, 3-propane sultone and anhydrous acetonitrile serving as a solvent, stirring and heating to 80 ℃ for reflux reaction for 1h, cooling to room temperature, filtering, washing a filter cake with the anhydrous acetonitrile, and drying under reduced pressure to obtain a compound XI;
the preferred molar ratio of compound X to 1, 3-propane sultone is 1:4, a step of;
preferably, the volume mass ratio of the solvent anhydrous acetonitrile to the compound X is 8:1, mL/g;
the conjugated polymer of the thiophene derivative containing the amphoteric ions, which is shown in the formula I, can be used for preparing electrochromic materials in a spraying mode.
The method comprises the following steps: adding a conjugated polymer of thiophene derivatives containing amphoteric ions shown in the formula I into trifluoroethanol serving as a solvent, performing ultrasonic dissolution, filtering with a filter head (nylon 66 0.22 mu m), and performing spray coating on ITO glass to form a film;
preferably, the volume mass ratio of the trifluoroethanol solvent to the compound I is 1:5, mL/mg.
The invention has the following beneficial effects:
(1) The invention modifies the zwitterionic side chain on the conjugated polymer, which not only improves the solubility of the polymer in the solvent, but also improves the ion transmission efficiency and the electrochromic performance.
(2) The conjugated polymer is constructed by EDOT and thiophene, so that the conjugated polymer has stronger electron supply capability and good electrochromic property, and the electrochemical property can be effectively regulated and controlled by connecting the conjugated polymer with a thiophene unit.
(3) In the invention, thiophene monomer is easy to modify, the reaction selectivity is good, the flow is simple, byproducts are few, and the product generates salt and is easy to separate.
(4) The thiophene derivative containing the zwitterions with different lengths from the conjugated main chain is sprayed to form a film in a chemical polymerization mode, and the polymer film can display various color changes under different voltages and has application value in the electrochromic field.
Drawings
FIG. 1 is a cyclic voltammogram of a novel class of zwitterionic based thiophene derivatives PTESB-1 and PTESB-2 of the present invention.
FIG. 2 is a graph of the ultraviolet-visible absorption spectra of a novel class of zwitterionic based thiophene derivatives PTESB-1 and PTESB-2 of the present invention at different voltages.
FIG. 3 is an electrochromic optical contrast plot of a novel zwitterionic based polymer film of thiophene derivative PTESB-1 of the present invention.
FIG. 4 is an electrochromic optical contrast plot of a novel zwitterionic based polymer film of thiophene derivative PTESB-2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1: (1) 3-thiophenecanol (2 g,17.5 mmol) and N-bromosuccinimide (7.8 g,43.8 mmol) were sequentially added to a 100mL two-necked round bottom flask, tetrahydrofuran (20 mL) was added as a reaction solvent, stirring at room temperature was carried out for 12 hours, after the reaction was completed, the solution after the completion of the reaction was poured into 200mL deionized water, extracted 5 times with 400mL ethyl acetate, the extract was concentrated, dried over anhydrous sodium sulfate, stirred with crude silica gel, purified by column chromatography with fine silica gel as a stationary phase and ethyl acetate and petroleum ether as mobile phases, the eluent containing the objective compound was collected, the solvent was removed by rotary evaporation and dried to obtain pure TSB1-1,2, 5-dibromo-3-thiophenecanol with a yield of 90%.
(2) 2, 5-dibromo-3-thiophenmethanol (2 g,7.3 mmol) and anhydrous dichloro (20 mL) are added into a 100mL reaction tube under the protection of N2 at a low temperature of 0 ℃, phosphorus tribromide (0.7 mL,7.3 mmol) is slowly added, stirring is carried out for 30min, then stirring is carried out for 12h at room temperature, after the reaction is finished, the solution with complete reaction is poured into 200mL deionized water, 400mL dichloromethane is used for extraction for 5 times, the extract is concentrated and dried with anhydrous sodium sulfate for water removal, crude silica gel is used for sample mixing, column chromatography purification is carried out, ethyl acetate and petroleum ether are used as mobile phases, eluent containing target compounds is collected, solvent is removed by rotary evaporation and drying is carried out, and the pure product TSB1-2, 5-dibromo-3-thiophen methyl bromide is obtained, and the yield is 94%.
(3) 2, 5-dibromo-3-thiophenemethyl bromide (2 g,5.93 mmol) and tetrabutylammonium bisulfate (0.2 g,0.593 mmol) were sequentially added to a 100mL two-necked round bottom flask, dimethylamine (5 mL) and chloroform (15 mL) were added as reaction solvents, heated under reflux at 60 ℃ for 2 hours, after the completion of the reaction, the solution was poured into 200mL deionized water, extracted 5 times with 400mL methylene chloride, the extract was concentrated and dried with anhydrous sodium sulfate to remove water, alumina was used as a stationary phase, methylene chloride and petroleum ether were used as mobile phases, the eluent containing the target compound was collected, the solvent was removed by rotary evaporation and dried to obtain pure TSB1-3,1- (2, 5-dibromothiophen-3-yl) -N, N-dimethylamine with a yield of 90%.
(4) 1- (2, 5-Dibromothiophen-3-yl) -N, N-dimethyl methylamine (1 g,3.34 mmol) and 1, 3-propane sultone (1.64 g,13.4 mmol) were sequentially added into a 100mL two-port round bottom flask, anhydrous acetonitrile (20 mL) was added as a reaction solvent, stirred, heated under reflux at 80 ℃ for 1 hour, after the reaction was completed, the reaction was cooled to room temperature, the mixture was filtered, repeatedly washed with acetonitrile and dried under reduced pressure to obtain pure product TSB1-4,3- (((2, 5-dibromothiophen-3 yl) methyl) dimethylammonium) -propane-1-sulfonate in 98% yield.
Example 2: according to the S2, a novel zwitterionic based thiophene derivative PTESB-2 is synthesized, as shown in S2:
(1) Under the protection of N2, setting a low-temperature reaction bath to be minus 50 ℃, dissolving 3-bromothiophene (2 g,12.3 mmol) in 18mL of N-hexane, dropwise adding 4.92mL of N-butyllithium (2.5M), stirring for 10min, adding 3mL of tetrahydrofuran to precipitate lithium salt, stirring for 1h at the temperature, adding 5.3g of 1, 4-dibromobutane, stirring for 12h at room temperature, pouring the solution after the reaction is completed into 200mL of deionized water, extracting for 5 times by 400mL of diethyl ether, concentrating the extract, drying for dewatering by anhydrous sodium sulfate, mixing a crude silica gel sample, performing column chromatography purification by taking fine silica gel as a stationary phase and petroleum ether as a mobile phase, collecting eluent containing a target compound, removing the solvent by rotary evaporation and drying to obtain a pure product TSB2-1,3- (4-bromobutyl) thiophene, wherein the yield is 56%.
(2) 3- (4-bromobutyl) thiophene (1.73 g,7.90 mmol) and N-bromosuccinimide (3.52 g,19.7 mmol) are sequentially added into a 100mL two-port round bottom flask, DMF (20 mL) is added as a reaction solvent, stirring is performed at normal temperature, after the reaction is finished, the solution which is completely reacted is poured into 200mL deionized water, extraction is performed for 5 times by 400mL ethyl acetate, the extract is concentrated, anhydrous sodium sulfate is used for drying and dewatering, crude silica gel is used for sample stirring, column chromatography purification is performed, fine silica gel is used as a stationary phase, petroleum ether is used as a mobile phase, eluent containing a target compound is collected, solvent is removed by rotary evaporation and drying is performed, and the pure product TSB2-2, 5-dibromo-3- (4-bromobutyl) -thiophene is obtained, and the yield is 94%.
(3) 2, 5-dibromo-3- (4-bromobutyl) -thiophene (1 g,1 mol) and dimethylamine (20 mL) are added into a 100mL two-port round bottom flask, heating reflux is carried out at 60 ℃ for 12 hours, after the reaction is finished, salt is removed by filtration, the solution is washed for multiple times by ethyl acetate, crude oil is obtained after the solvent is removed, anhydrous sodium sulfate is used for drying and removing water, crude silica gel is used for sample mixing, column chromatography purification is carried out, fine silica gel is used as a stationary phase, petroleum ether and ethyl acetate are used as mobile phases, eluent containing target compounds is collected, solvent is removed by rotary evaporation and drying is carried out, and the pure product TSB2-3,2, 5-dibromo-N, N-dimethyl-3-thiophen butylamine is obtained, and the yield is 74%.
(4) 2, 5-dibromo-N, N-dimethyl-3-thiophenebutylamine (1 g,2.65 mmol) and 1, 3-propane sultone (1.64 g,13.4 mmol) are sequentially added into a 100mL two-port round bottom flask, anhydrous acetonitrile (8 mL) is added as a reaction solvent, stirring is carried out, heating reflux is carried out at 80 ℃ for 1 hour, after the reaction is finished, the reaction is cooled to room temperature, the mixture is filtered, and repeatedly washed by acetonitrile and dried under reduced pressure, thus obtaining the pure product TSB2-4,3- ((4- (2, 5-dibromothiophen-3 yl) butyl) dimethyl ammonium) -propane-1-sulfonate with the yield of 98 percent.
Example 3: under the protection of N2, 3,4 ethylene dioxythiophene (0.284 g,2 mmol) and bisboronic acid pinacol ester (1.02 g,4 mmol), 25mg of catalyst methoxy (cyclooctadiene) iridium dimer and 10mg of 4, 4-di-tert-butyl-2, 2-bipyridine are added, N-hexane (8 mL) is added as a reaction solvent, stirring is carried out for 16 hours at normal temperature, after the reaction is finished, the mixture is filtered, and repeatedly washed by N-hexane, and the pure product is obtained after boronation, and the yield is 85 percent.
Example 4: thiophene monomer compound II containing a zwitterionic side chain, X=1 (426 mg,1 mmol) or X=4 (463mg, 1 mmol) and boronated EDOT (390 mg,1 mmol), bis (triphenylphosphine) palladium dichloride (20 mg) were sequentially added into a single-port round-bottom flask, toluene (2 mL) was added under N2 protection, 1mL of each of 2M aqueous potassium carbonate and sodium bromide solution was used as a reaction solvent, stirring was carried out, reflux was carried out at 90℃for 24 hours, after completion of the reaction, the solution was poured into 200mL of methanol, filtered, soxhlet extraction was carried out sequentially in the order of tetrahydrofuran, methanol and trifluoroethanol, after completion of the extraction, the solution was transferred into a dialysis bag and dialyzed with pure water for 2 days, and pure products PTESB-1 and PTESB-2 were obtained after freeze drying, with a yield of 80%.
Application examples
5mg of the zwitterionic based on the thiophene derivative PTESB-1 or PTESB-2 was dissolved in 1mL of trifluoroethanol solvent, and after ultrasonic dissolution and filtration by a filter head, the film was formed by spray coating on ITO glass (0.9X4 cm).
The ITO glass is used as a working electrode, the platinum sheet is used as a counter electrode, the Ag/AgCl is used as a reference electrode, and the ultraviolet-visible spectrum and electrochromic performance of the polymer film are tested, so that the color of the polymer film is light coffee in a neutral state, blue in an oxidation state, and the polymer film has good electrochromic performance.
[ Performance test ]
1. Cyclic voltammetry performance test
2.128g (0.2 mol/L) of lithium perchlorate was added to a 100mL volumetric flask, and the volume was determined using chromatographic grade acetonitrile as a blank supporting electrolyte solution. The cyclic voltammetry performance of the polymer film at 0-1.2V is tested by taking the thiophene derivative conjugated polymers PTESB-1 and PTESB-2 film containing amphoteric ions prepared in the embodiment 4 as working electrodes, platinum sheets as counter electrodes and Ag/AgCl as reference electrodes, and the test result is shown in figure 1.
As can be seen from fig. 1, the polymer exhibits a distinct redox peak, which indicates that the polymer has good redox activity and that the redox behavior is reversible.
2. Ultraviolet-visible absorption spectrum test
2.128g (0.2 mol/L) of lithium perchlorate was added to a 100mL volumetric flask, and the volume was determined using chromatographic grade acetonitrile as a blank supporting electrolyte solution. The film of the thiophene derivative conjugated polymers PTESB-1 and PTESB-2 containing the amphoteric ions, which are prepared in the embodiment 4, are used as working electrodes, a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, and the ultraviolet-visible absorption spectra of the polymer film under different voltages are tested, and the test results are shown in figure 2.
As can be seen from the uv-vis absorption spectrum of fig. 2, the polymer film was light-colored in the neutral state and blue in the oxidized state, with a significant color change.
3. Electrochromic Performance test
2.128g (0.2 mol/L) of lithium perchlorate was added to a 100mL volumetric flask, and the volume was determined using chromatographic grade acetonitrile as a blank supporting electrolyte solution. The optical contrast patterns of the thiophene derivative conjugated polymers PTESB-1 and PTESB-2 containing the amphoteric ions, which are prepared in the embodiment 4, are tested by taking the films of the thiophene derivative conjugated polymers PTESB-1 and PTESB-2 containing the amphoteric ions as working electrodes, taking a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, and the test results are shown in figures 3 and 4.
As can be seen from the optical contrast ratios of FIGS. 3 and 4, the color time of the PTESB-1 film at 687nm is 1.32s, the color fading time is 0.25s, and the optical contrast ratio can reach 20%; the PTESB-2 film has a coloring time of 1.6s at 754nm and a fading time of 0.93s, and has an optical contrast of 24% and good electrochromic performance.

Claims (8)

1. A conjugated polymer of thiophene derivatives containing amphoteric ions has a structural formula shown in formula I:
in the formula I, X=1 to 8;
n＝20～30。
2. the preparation method of the conjugated polymer of the thiophene derivative containing the amphoteric ions shown in the formula I is characterized by comprising the following steps:
(1) 3, 4-ethylenedioxythiophene reacts with bisboronic acid pinacol ester to obtain a compound III;
(2) The compound II and the compound III are subjected to Suzuki coupling reaction to prepare a product I;
3. the method for preparing the conjugated polymer of the thiophene derivative containing the zwitterions, which is shown in the formula I in the claim 2, wherein the operation method in the step (1) is as follows: at N 2 Under the protection, mixing 3,4 ethylene dioxythiophene and bisboronic acid pinacol ester, adding a catalyst methoxy (cyclooctadiene) iridium dimer and 4, 4-di-tert-butyl-2, 2-bipyridine, and a solvent n-hexane, stirring for 16 hours at normal temperature, filtering, washing a filter cake with n-hexane, and drying under reduced pressure to obtain a compound III;
wherein, the mole ratio of 3,4 ethylene dioxythiophene to bisboronic acid pinacol ester is 1:2.
4. the method for preparing the conjugated polymer of the thiophene derivative containing the zwitterions, which is shown in the formula I in the claim 2, wherein the operation method in the step (2) is as follows: at N 2 Under the protection, mixing a compound II, a compound III, a catalyst bis (triphenylphosphine) palladium dichloride and a reaction solvent, stirring and heating to 90 ℃ for reflux reaction for 24-30 h, cooling the reaction liquid to room temperature, pouring the reaction liquid into methanol, filtering, sequentially carrying out Soxhlet extraction on a filter cake by using tetrahydrofuran, methanol and trifluoroethanol, collecting the trifluoroethanol extract after the extraction is finished, spin-drying, transferring to a dialysis bag, dialyzing with pure water for 2 days, and freeze-drying to obtain a product I;
wherein, the mol ratio of the compound II to the compound III is 1:1, a step of;
the reaction solvent is toluene, 2M aqueous potassium carbonate solution and 2M aqueous sodium bromide solution with the volume ratio of 2:1: 1.
5. The application of a thiophene derivative conjugated polymer containing amphoteric ions in the preparation of electrochromic materials is shown in a formula I.
6. The application according to claim 5, wherein the method of application is: adding a conjugated polymer of thiophene derivatives containing amphoteric ions shown in the formula I into trifluoroethanol serving as a solvent, performing ultrasonic dissolution and filtering by a filter head, and then performing spraying processing on ITO glass to form a film.
7. The monomer for synthesizing the conjugated polymer of the thiophene derivative containing the amphoteric ions is shown in the formula I, and the structural formula is shown in the formula II:
in formula II, x=1 or 4.
8. A preparation method of a monomer shown in a formula II is characterized in that:
when x=1, the monomer of formula II is compound VII, which is synthesized as follows:
s1: 3-thiophenecanol is subjected to bromination reaction of N-bromosuccinimide to obtain a compound IV;
s2: the compound IV is subjected to substitution reaction by phosphorus tribromide to obtain a compound V;
s3: the compound V is subjected to dimethylamine substitution reaction to obtain a compound VI;
s4: the compound VI is subjected to ring-opening reaction with 1, 3-propane sultone to obtain a compound VII;
when x=4, the monomer of formula II, compound XI, is synthesized as follows:
s1: 3-bromothiophene is subjected to substitution reaction with 1, 4-dibromobutane to obtain a compound VIII;
s2: the compound VIII is subjected to bromination reaction with N-bromosuccinimide to obtain a compound IX;
s3: compound IX is subjected to substitution reaction with dimethylamine to obtain compound X;
s4: the compound X is subjected to ring opening reaction with 1, 3-propane sultone to obtain a compound XI;
CN202310892894.9A 2023-07-20 2023-07-20 Thiophene derivative conjugated polymer containing amphoteric ions and preparation method and application thereof Pending CN116874745A (en)

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