CN108794731B - Application of conjugated polymer containing triarylamine and fluorene units - Google Patents
Application of conjugated polymer containing triarylamine and fluorene units Download PDFInfo
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Abstract
An application of a conjugated polymer containing triarylamine and fluorene units relates to an application of a conjugated polymer containing triarylamine and fluorene units. The invention aims to solve the technical problem that the existing electrochromic material is single in performance. The structural formula of the conjugated polymer containing triarylamine and fluorene units is as follows:
wherein n is a positive integer. The preparation method of the conjugated polymer containing triarylamine and fluorene units comprises the following steps: firstly, synthesizing a triarylamine monomer; secondly, Suzuki reaction. The conjugated polymer containing triarylamine and fluorene units is applied to being used as an explosive detection material. The invention expands the application range of the electrochromic material, and the established fluorene-triarylamine system fully combines the advantages of triarylamine and fluorene units and overcomes the disadvantages of the triarylamine and the fluorene units, thereby having stronger hole transport capability and enhancing the emission efficiency of devices.
Description
Technical Field
The invention relates to application of a conjugated polymer containing triarylamine and fluorene units
Background
With the development of science and technology, the requirements of human beings on materials are higher and higher. The simple electrochromic material is unable to fully meet the increasing demand, and people expect that the electrochromic material has more functions, such as electroluminescent property, resistance memory, sensor function, etc., to achieve the goal of device integration. The triarylamine has a unique conjugated structure and very special electron donating property, can easily form amine positive ion free radicals under the action of an electric field, and has higher hole mobility, so the triarylamine is an excellent electrochromic material. However, most of the reported triarylamine-based electrochromic materials mostly have three benzene rings connected with the center of an N atom. Biphenyl-based aromatic compounds, however, have highly polarized p-electron systems that play an important role in organic light emitting diodes, dyes and pigments, but are rarely used in the field of electrochromism. Polyfluorenes are an active species in the study of conjugated polymers, and are particularly useful in display applications. They are of great interest to researchers in academia and industry, with their good processability, high luminous efficiency and good carrier mobility. However, there are still some problems to be solved. On the one hand, polyfluorenes tend to form excimers and/or aggregates in the solid state. On the other hand, polyfluorenes have ionization potentials as high as 5.8eV, resulting in high drive voltages.
Disclosure of Invention
The invention provides an application of a conjugated polymer containing triarylamine and fluorene units to solve the technical problem of single performance of the existing electrochromic material.
The structural formula of the conjugated polymer containing triarylamine and fluorene units is as follows:
The preparation method of the conjugated polymer containing triarylamine and fluorene units comprises the following steps:
firstly, synthesizing a triarylamine monomer:
① at N2Under the atmosphere, sequentially adding bis (4-tert-butylphenyl) amine, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, uniformly stirring, dropwise adding p-fluoronitrobenzene, heating in an oil bath to 115-120 ℃, continuously reacting at the temperature of 115-120 ℃ until the bis (4-tert-butylphenyl) amine is completely reacted, stopping heating, and adding N2Naturally cooling in the atmosphere, placing the cooled reaction solution into distilled water, adding sodium chloride under the condition of stirring until solid is separated out, standing and settling for 12-14 h, carrying out suction filtration, washing, drying in a vacuum oven at 50 ℃, then recrystallizing in ethanol, carrying out suction filtration, washingWashing, and drying in a vacuum oven at 50 ℃ to obtain a yellow solid; the mass ratio of the bis (4-tert-butylphenyl) amine to the sodium hydride is 1 (1.8-2); the volume ratio of the substance amount of the bis (4-tert-butylphenyl) amine to the anhydrous N, N-dimethylformamide is 1mol (10L-11L); the mass ratio of the bis (4-tert-butylphenyl) amine to the p-fluoronitrobenzene is 1 (1.2-1.5); the volume ratio of the anhydrous N, N-dimethylformamide to the distilled water is 1 (5-5.5);
the reaction formula is as follows:
the method for judging the completion of the reaction of the bis (4-tert-butylphenyl) amine comprises the following steps: the progress of the reaction was judged by thin layer chromatography.
② at N2Under the atmosphere, sequentially adding absolute ethyl alcohol, palladium carbon and the yellow solid prepared in the step I ① into a three-necked bottle, dropwise adding hydrazine hydrate under the stirring state, heating to 80 ℃, refluxing for 24 hours, stopping heating, immediately performing suction filtration, pouring filtrate into distilled water, adding sodium chloride under the stirring condition until solid is separated out, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain a white solid, wherein the mass fraction of palladium in the palladium carbon is 10%, the mass ratio of the palladium carbon to the absolute ethyl alcohol is 1g (187-190 mL), the mass ratio of the palladium carbon to the yellow solid prepared in the step I ① is 1 (3.3-3.5), and the volume ratio of hydrazine hydrate to the absolute ethyl alcohol is 1 (12-15);
the reaction formula is as follows:
③, under the protection of nitrogen, adding the white solid obtained in the first step ②, sodium tert-butoxide, 4-bromo-4 '-iodobiphenyl, palladium acetate and 1,1' -bis (diphenylphosphine) ferrocene into a two-neck flask filled with dehydrated toluene, shielding the reactants by a tin sheet, introducing nitrogen for reflux reaction for 24 hours at the temperature of 115-120 ℃, extracting and purifying the solution obtained by the reflux reaction by water and saturated saline water in sequence, carrying out rotary evaporation on the obtained extract, drying, and carrying out thin-layer chromatography on the dried product by using a developing agent to obtain a light yellow triarylamine monomer, wherein the developing agent is formed by mixing petroleum ether and dichloromethane according to a volume ratio of 5:1, the volume ratio of the white solid obtained in the first step ② to the sodium tert-butoxide is 1 (3-4), the volume ratio of the white solid obtained in the first step ② to the toluene is 1mol (2.5L-393L), the volume ratio of the white solid obtained in the first step 1 to the 4-biphenyl is 1.2.5-3L), and the volume ratio of the white solid obtained in the biphenyl is 0.2.03-3 to 0.06);
the reaction formula is as follows:
II, Suzuki reaction:
uniformly stirring the light yellow triarylamine monomer prepared in the step one, 9-dioctyl fluorene-2, 7-bis (pinacol borate), tetrakis (triphenylphosphine) palladium and toluene, adding a potassium carbonate solution, stirring for 48 hours at the temperature of 105 ℃ in a nitrogen atmosphere, cooling to room temperature under the protection of nitrogen, separating an organic layer by using a separating funnel, sequentially extracting and purifying by using water and saturated saline solution, pouring the obtained extract into methanol to precipitate a light yellow polymer, performing suction filtration on the light yellow polymer, and finally performing Soxhlet extraction and purification for 48 hours by using methanol to obtain a conjugated polymer containing triarylamine and fluorene units;
the concentration of the potassium carbonate solution is 3 mol/L; the volume ratio of the potassium carbonate solution to the toluene is 1: 1; the mass ratio of the light yellow triarylamine monomer prepared in the first step to the 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester) is 1 (1-1.2); the amount ratio of the light yellow triarylamine monomer prepared in the first step to the tetrakis (triphenylphosphine) palladium is 1 (0.04-0.05); the volume ratio of the substance amount of the light yellow triarylamine monomer prepared in the step one to the toluene is 1mol (40L-45L).
The reaction formula is as follows:
the conjugated polymer containing triarylamine and fluorene units is applied to electrochromic materials, fluorescent sensing materials, hole transport materials, anti-counterfeiting materials, memory resistors, camouflage materials, automobile rearview mirror materials or display materials.
The conjugated polymer containing triarylamine and fluorene units is applied to being used as an explosive detection material.
The invention combines biphenyl structure substituted benzene ring on the central N atom to prepare novel triarylamine monomer to obtain more excellent performance, and provides a basis for designing and synthesizing novel multifunctional organic polymer materials.
The invention copolymerizes fluorene and triarylamine to obtain double functions of electrochromism and electroluminescence; in order to obtain effective hole injection, the biphenyl triarylamine with rich electrons is introduced into a polyfluorene skeleton, so that the ionization potential of the copolymer is reduced, and the introduction of a twisted structure of biphenyl weakens the tendency of forming excimers and/or compact aggregates in a solid state, so that the molecules have better solubility, better electron delocalization range and better chemical stability compared with the molecules containing a common triarylamine structure.
The conjugated polymer containing triarylamine and fluorene units combines biphenyl triarylamine and fluorene structures, has electrochromic, electroluminescent, resistance memory and sensor functions, and can achieve effective integration of devices.
The method for preparing the toluene subjected to water removal in the first step ③ comprises the steps of adding metal sodium into toluene, heating and refluxing, taking benzophenone as an indicator, and collecting the toluene subjected to water removal after turning blue.
The invention has the advantages that:
the invention expands the application range of the electrochromic material, and the established fluorene-triarylamine system fully combines the advantages of triarylamine and fluorene units and overcomes the disadvantages of the triarylamine and the fluorene units, thereby having stronger hole transport capability and enhancing the emission efficiency of devices.
In the field of electrochromism: (1) the color change is obvious, from light yellow to green to dark blue; (2) the response time of the color change is fast; (3) the color change is reversible and the cycling stability is good.
The electroluminescent property of the conjugated polymer containing triarylamine and fluorene units can be adjusted by electrochemical oxidation reduction, and the conjugated polymer has high contrast. In addition, the explosive composition has excellent performance in explosive detection and memory performance. Provides a certain method and thought for designing and synthesizing novel multifunctional organic polymer materials and provides theoretical support for understanding the mechanism of the electrochromic property of the multifunctional organic polymer.
The memory device prepared by the conjugated polymer containing triarylamine and fluorene units can detect the existence of TNT in a TNT chloroform solution with the concentration of 0-100 mug/mL.
The memory device prepared by the conjugated polymer containing triarylamine and fluorene units can detect the existence of picric acid in 0-70 mug/mL picric acid chloroform solution.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment;
FIG. 2 is a cyclic voltammogram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment;
FIG. 3 is an electrochromic diagram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment;
FIG. 4 is an electroluminescence diagram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment;
FIG. 5 is a graph showing the thermogravimetric plot of the conjugated polymer containing triarylamine and fluorene units prepared in this experiment;
FIG. 6 is a graph showing the change in fluorescence intensity of a conjugated polymer solution when the explosive in test two is TNT;
FIG. 7 is a graph showing the change in fluorescence intensity of a conjugated polymer solution when the explosive in test two is picric acid;
fig. 8 is a graph of the resistive memory performance of the memory device fabricated in test three;
FIG. 9 shows an IR spectrum of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment.
Detailed Description
The first embodiment is as follows: the embodiment is a conjugated polymer containing triarylamine and fluorene units, and the structural formula of the conjugated polymer is as follows:
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and n is an integer of 3-10. The rest is the same as the first embodiment.
The third concrete implementation mode: the embodiment is a preparation method of a conjugated polymer containing triarylamine and fluorene units, which comprises the following steps:
firstly, synthesizing a triarylamine monomer:
① at N2Under the atmosphere, sequentially adding bis (4-tert-butylphenyl) amine, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, uniformly stirring, dropwise adding p-fluoronitrobenzene, heating in an oil bath to 115-120 ℃, continuously reacting at the temperature of 115-120 ℃ until the bis (4-tert-butylphenyl) amine is completely reacted, stopping heating, and adding N2Naturally cooling in the atmosphere, placing the cooled reaction solution into distilled water, adding sodium chloride under the stirring condition until solid is separated out, standing and settling for 12-14 h, carrying out suction filtration, washing, drying in a vacuum oven at 50 ℃, then recrystallizing in ethanol, carrying out suction filtration, washing, and drying in a vacuum oven at 50 ℃ to obtain yellow solid; the mass ratio of the bis (4-tert-butylphenyl) amine to the sodium hydride is 1 (1.8-2); the volume ratio of the substance amount of the bis (4-tert-butylphenyl) amine to the anhydrous N, N-dimethylformamide is 1mol (10L-11L); the mass ratio of the bis (4-tert-butylphenyl) amine to the p-fluoronitrobenzene is 1 (1.2-1.5); the anhydrous N, N-dimethylformamide and distilled waterThe volume ratio of (1) to (5-5.5);
the reaction formula is as follows:
② at N2Under the atmosphere, sequentially adding absolute ethyl alcohol, palladium carbon and the yellow solid prepared in the step I ① into a three-necked bottle, dropwise adding hydrazine hydrate under the stirring state, heating to 80 ℃, refluxing for 24 hours, stopping heating, immediately performing suction filtration, pouring filtrate into distilled water, adding sodium chloride under the stirring condition until solid is separated out, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain a white solid, wherein the mass fraction of palladium in the palladium carbon is 10%, the mass ratio of the palladium carbon to the absolute ethyl alcohol is 1g (187-190 mL), the mass ratio of the palladium carbon to the yellow solid prepared in the step I ① is 1 (3.3-3.5), and the volume ratio of hydrazine hydrate to the absolute ethyl alcohol is 1 (12-15);
the reaction formula is as follows:
③, under the protection of nitrogen, adding the white solid obtained in the first step ②, sodium tert-butoxide, 4-bromo-4 '-iodobiphenyl, palladium acetate and 1,1' -bis (diphenylphosphine) ferrocene into a two-neck flask filled with dehydrated toluene, shielding the reactants by a tin sheet, introducing nitrogen for reflux reaction for 24 hours at the temperature of 115-120 ℃, extracting and purifying the solution obtained by the reflux reaction by water and saturated saline water in sequence, carrying out rotary evaporation on the obtained extract, drying, and carrying out thin-layer chromatography on the dried product by using a developing agent to obtain a light yellow triarylamine monomer, wherein the developing agent is formed by mixing petroleum ether and dichloromethane according to a volume ratio of 5:1, the volume ratio of the white solid obtained in the first step ② to the sodium tert-butoxide is 1 (3-4), the volume ratio of the white solid obtained in the first step ② to the toluene is 1mol (2.5L-393L), the volume ratio of the white solid obtained in the first step 1 to the 4-biphenyl is 1.2.5-3L), and the volume ratio of the white solid obtained in the biphenyl is 0.2.03-3 to 0.06);
the reaction formula is as follows:
II, Suzuki reaction:
uniformly stirring the light yellow triarylamine monomer prepared in the step one, 9-dioctyl fluorene-2, 7-bis (pinacol borate), tetrakis (triphenylphosphine) palladium and toluene, adding a potassium carbonate solution, stirring for 48 hours at the temperature of 105 ℃ in a nitrogen atmosphere, cooling to room temperature under the protection of nitrogen, separating an organic layer by using a separating funnel, sequentially extracting and purifying by using water and saturated saline solution, pouring the obtained extract into methanol to precipitate a light yellow polymer, performing suction filtration on the light yellow polymer, and finally performing Soxhlet extraction and purification for 48 hours by using methanol to obtain a conjugated polymer containing triarylamine and fluorene units;
the concentration of the potassium carbonate solution is 3 mol/L; the volume ratio of the potassium carbonate solution to the toluene is 1: 1; the mass ratio of the light yellow triarylamine monomer prepared in the first step to the 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester) is 1 (1-1.2); the amount ratio of the light yellow triarylamine monomer prepared in the first step to the tetrakis (triphenylphosphine) palladium is 1 (0.04-0.05); the volume ratio of the substance amount of the light yellow triarylamine monomer prepared in the step one to the toluene is 1mol (40L-45L).
The reaction formula is as follows:
the fourth concrete implementation mode: the embodiment is an application of the conjugated polymer containing triarylamine and fluorene units in the first embodiment, and is specifically applied to electrochromic materials, fluorescent sensing materials, hole transport materials, anti-counterfeiting materials, memory resistors, camouflage materials, automobile rearview mirror materials or display materials.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: the embodiment is an application of the conjugated polymer containing triarylamine and fluorene units in the first embodiment, and is particularly applied to an explosive detection material.
The invention was verified with the following tests:
test one: the test is a preparation method of a conjugated polymer containing triarylamine and fluorene units, and the specific steps are as follows:
firstly, synthesizing a triarylamine monomer:
① at N2Under the atmosphere, 14.21mmol of bis (4-tert-butylphenyl) amine, 25.58mmol of sodium hydride and 150mL of anhydrous N, N-dimethylformamide are sequentially added into a three-necked bottle, stirred uniformly, 17.06mmol of p-fluoronitrobenzene is added dropwise, then the mixture is heated to 115-120 ℃ in an oil bath, the reaction is continued under the temperature of 115-120 ℃ until the bis (4-tert-butylphenyl) amine finishes the reaction, the heating is stopped, and the reaction is carried out under the condition of N2Naturally cooling in the atmosphere, placing the cooled reaction solution into distilled water, adding sodium chloride under the stirring condition until solid is separated out, standing and settling for 12-14 h, performing suction filtration, washing, drying in a vacuum oven at 50 ℃, then recrystallizing in ethanol, performing suction filtration, washing, and drying in a vacuum oven at 50 ℃ to obtain yellow solid with the yield of 87%;
the reaction formula is as follows:
② at N2Under the atmosphere, sequentially adding 150mL of absolute ethyl alcohol, 0.8g of palladium carbon and 2.7g of yellow solid prepared in the first step ① into a three-necked bottle, dropwise adding 12mL of hydrazine hydrate under the stirring state, heating to 80 ℃, refluxing for 24 hours, stopping heating, immediately performing suction filtration, pouring filtrate into distilled water, adding sodium chloride under the stirring condition until solid is separated out, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain white solid with the yield of 72%, wherein the mass fraction of palladium in the palladium carbon is 10%, and the reaction formula is as follows:
③ into a two-necked flask containing 30mL of toluene with water removed under nitrogen, 4.46g (12mmol) of the white solid obtained in step one ②, 36mmol of sodium tert-butoxide, 24mmol of 4-bromo-4' -iodobiphenyl, 3.6 × 10-1mmol of palladium acetate and 7.2 × 10-1The method comprises the following steps of (1, 1' -bis (diphenylphosphino) ferrocene mmol, shading reactants by a tin sheet, introducing nitrogen for reflux reaction for 24 hours at the temperature of 115-120 ℃, extracting and purifying the solution obtained by the reflux reaction by water and saturated saline water in sequence, carrying out rotary evaporation on the obtained extract, drying, and carrying out thin-layer chromatography separation on the dried product by using a developing agent to obtain a light yellow triarylamine monomer; the developing agent is formed by mixing petroleum ether and dichloromethane according to the volume ratio of 5: 1;
the reaction formula is as follows:
II, Suzuki reaction:
0.3118g (0.3739mmol) of the light yellow triarylamine monomer prepared in step one, 0.3739mmol of 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester) and 1.5 × 10-2mmol of tetrakis (triphenylphosphine) palladium and 15mL of toluene are uniformly stirred, 15mL of potassium carbonate solution is added, the mixture is stirred for 48 hours at the temperature of 105 ℃ under the condition of nitrogen atmosphere, the mixture is cooled to room temperature under the protection of nitrogen, then a separating funnel is used for separating an organic layer, water and saturated saline are sequentially used for extraction and purification, the obtained extract liquid is poured into methanol to separate out a light yellow polymer, the light yellow polymer is subjected to suction filtration, and finally the conjugated polymer containing triarylamine and fluorene units is obtained by soxhlet extraction and purification of methanol for 48 hours; the concentration of the potassium carbonate solution is 3 mol/L.
The reaction formula is as follows:
FIG. 1 shows the hydrogen nuclear magnetic spectrum of the conjugated polymer containing triarylamine and fluorene units prepared in this experiment, and it can be seen from FIG. 11HNMR (400MHz, DMSO-d6, delta, ppm) 7.59-6.89 (hydrogen on benzene ring), 1.97-0.49 (hydrogen on alkyl chain).
FIG. 9 shows the IR spectrum of the conjugated polymer containing triarylamine and fluorene units prepared in this experiment, from which the IR (KBr, upsilon, cm)-1):1265(Ar-N),3032(Ar-H stretch)。
It can be demonstrated by FIGS. 1 and 9 that the conjugated polymer containing triarylamine and fluorene units prepared in this experiment has the following structural formula:
wherein n is a positive integer.
FIG. 2 is a cyclic voltammogram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment, the electrochemical properties of the polymer being determined by Cyclic Voltammetry (CV) measurements, using conditions such that NH is present at a concentration of 0.2mol/L4ClO4CH (A) of3CN solution, applying cyclic reversible voltage on ITO glass plate coated with polymer film. The CV spectra of the polymer are shown in the figure, and two oxidation peaks at 0.84V and 1.16V and two reduction peaks at 0.65V and 1V can be observed.
FIG. 3 is an electrochromic diagram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment, wherein the film of the conjugated polymer is tested and studied in the ultraviolet-visible spectrum under the same test conditions as cyclic voltammetry, 0V to 1.5V, and in the initial state, the polymer film coated on ITO shows a light yellow color, and in the absence of applied voltage, the polymer film has an electron migration of pi-pi of TPA group in the polymer, the strongest absorption peak is at 340nm, and the absorption peaks at 422nm and 936nm gradually increase with the increase of applied voltage, and the polymer film simultaneously changes color from light yellow to yellow green and finally to deep blue.
FIG. 4 is an electroluminescence diagram of a conjugated polymer containing triarylamine and fluorene units prepared in this experiment; as can be seen, the fluorescence intensity reached the highest level before no voltage was applied, and gradually decreased from 0V to 1.5V as the voltage was applied, and finally approached zero.
FIG. 5 is a graph showing the thermogravimetry of the conjugated polymer containing triarylamine and fluorene units prepared in this experiment, and it can be seen from the graph that the polymer begins to lose a large amount of weight at about 350 deg.C, when the temperature is 377 deg.C, the weight loss is 5%, and when the temperature is 410 deg.C, the weight loss is 10%; the weight loss was 20% when the temperature was 453 ℃ and the residual amount of polymer carbon was 41% when the temperature reached 800 ℃.
Dissolving the conjugated polymer containing triarylamine and fluorene units prepared in the test in an organic solvent to obtain a 1mg/mL conjugated polymer solution, and then coating the conjugated polymer solution on conductive glass to prepare an electrochromic material; the organic solvent is N-methyl pyrrolidone.
And (2) test II: dissolving the conjugated polymer containing triarylamine and fluorene units prepared in the test in 4mL of chloroform to obtain a conjugated polymer solution of 5 mug/mL, then dropping a drop of chloroform solution containing explosives with different concentrations into the conjugated polymer solution, and detecting whether the solution contains the explosives or not by using the change of the fluorescence intensity of the solution; the explosive is TNT or picric acid.
FIG. 6 is a graph showing the change of fluorescence intensity of the conjugated polymer solution when the explosive in test two is TNT, wherein the arrow represents the increase of the concentration of TNT (0-100. mu.g/mL) in the chloroform solution containing the explosive, and it can be seen from FIG. 6 that the fluorescence intensity of the conjugated polymer solution gradually decreases with the increase of the concentration of TNT.
FIG. 7 is a graph showing the change in fluorescence intensity of the conjugated polymer solution when the explosive in test two is picric acid, and the arrow indicates the increase in picric acid concentration (0-70. mu.g/mL) in the chloroform solution containing the explosive, and it can be seen from FIG. 7 that the fluorescence intensity of the conjugated polymer solution gradually decreases with the increase in picric acid concentration.
And (3) test III: and dissolving the conjugated polymer containing the triarylamine and fluorene units prepared in the first test in N-methylpyrrolidone to obtain a 1mg/mL solution, coating the solution on ITO conductive glass, drying, and then aluminizing to obtain the Al/polymer/ITO sandwich-type memory device.
Fig. 8 is a diagram of the resistance memory performance of the memory device prepared in the third test, in which the number indicates the number of times of scanning, and it can be seen from fig. 8 that in the first voltage scanning from 0 to +8V, the device is initially in a high-resistance state, a sharp increase in current can be observed in the memory device when the threshold voltage is +1.2V, and the memory device switches from a low conductivity state (OFF) to a high conductivity state (ON), which can be used as a "write" process of the memory device (B in fig. 8). In the subsequent positive scan (second scan), the device is still in the ON state. In the reverse voltage sweep from 0 to-8V (the third sweep), the current drops abruptly when the threshold voltage approaches-2.6V, indicating that the memory device undergoes a transition from the ON state to the original OFF state, which can be referred to as an "erase" (A in FIG. 8). Similarly, the device is in the off state during the fourth scan from-8 to 0V. At a threshold voltage of 1.2V (fifth scan), the erased state can be switched to the memory state again, which means that the memory device is rewritable.
Claims (3)
1. The application of the conjugated polymer containing triarylamine and fluorene units is characterized in that the conjugated polymer containing triarylamine and fluorene units is applied to be used as an explosive detection material;
the structural formula of the conjugated polymer containing triarylamine and fluorene units is as follows:
2. Use of a conjugated polymer comprising triarylamine and fluorene units according to claim 1, wherein n is an integer from 3 to 10.
3. The use of a conjugated polymer comprising triarylamine and fluorene units according to claim 1, wherein the process for the preparation of the conjugated polymer comprising triarylamine and fluorene units comprises the following steps:
firstly, synthesizing a triarylamine monomer:
① at N2Under the atmosphere, sequentially adding bis (4-tert-butylphenyl) amine, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked bottle, uniformly stirring, dropwise adding p-fluoronitrobenzene, heating in an oil bath to 115-120 ℃, continuously reacting at the temperature of 115-120 ℃ until the bis (4-tert-butylphenyl) amine is completely reacted, stopping heating, and adding N2Naturally cooling in the atmosphere, placing the cooled reaction solution into distilled water, adding sodium chloride under the stirring condition until solid is separated out, standing and settling for 12-14 h, carrying out suction filtration, washing, drying in a vacuum oven at 50 ℃, then recrystallizing in ethanol, carrying out suction filtration, washing, and drying in a vacuum oven at 50 ℃ to obtain yellow solid; the mass ratio of the bis (4-tert-butylphenyl) amine to the sodium hydride is 1 (1.8-2); the volume ratio of the substance amount of the bis (4-tert-butylphenyl) amine to the anhydrous N, N-dimethylformamide is 1mol (10L-11L); the mass ratio of the bis (4-tert-butylphenyl) amine to the p-fluoronitrobenzene is 1 (1.2-1.5); the volume ratio of the anhydrous N, N-dimethylformamide to the distilled water is 1 (5-5.5);
② at N2Under the atmosphere, sequentially adding absolute ethyl alcohol, palladium carbon and the yellow solid prepared in the step I ① into a three-necked bottle, dropwise adding hydrazine hydrate under the stirring state, heating to 80 ℃, refluxing for 24 hours, stopping heating, immediately performing suction filtration, pouring filtrate into distilled water, adding sodium chloride under the stirring condition until solid is separated out, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain a white solid, wherein the mass fraction of palladium in the palladium carbon is 10%, the mass ratio of the palladium carbon to the absolute ethyl alcohol is 1g (187-190 mL), the mass ratio of the palladium carbon to the yellow solid prepared in the step I ① is 1 (3.3-3.5), and the volume ratio of hydrazine hydrate to the absolute ethyl alcohol is 1 (12-15);
③, under the protection of nitrogen, adding the white solid obtained in the first step ②, sodium tert-butoxide, 4-bromo-4 '-iodobiphenyl, palladium acetate and 1,1' -bis (diphenylphosphine) ferrocene into a two-neck flask filled with dehydrated toluene, shielding the reactants by a tin sheet, introducing nitrogen for reflux reaction for 24 hours at the temperature of 115-120 ℃, extracting and purifying the solution obtained by the reflux reaction by water and saturated saline water in sequence, carrying out rotary evaporation on the obtained extract, drying, and carrying out thin-layer chromatography on the dried product by using a developing agent to obtain a light yellow triarylamine monomer, wherein the developing agent is formed by mixing petroleum ether and dichloromethane according to a volume ratio of 5:1, the volume ratio of the white solid obtained in the first step ② to the sodium tert-butoxide is 1 (3-4), the volume ratio of the white solid obtained in the first step ② to the toluene is 1mol (2.5L-393L), the volume ratio of the white solid obtained in the first step 1 to the 4-biphenyl is 1.2.5-3L), and the volume ratio of the white solid obtained in the biphenyl is 0.2.03-3 to 0.06);
II, Suzuki reaction:
uniformly stirring the light yellow triarylamine monomer prepared in the step one, 9-dioctyl fluorene-2, 7-bis (pinacol borate), tetrakis (triphenylphosphine) palladium and toluene, adding a potassium carbonate solution, stirring for 48 hours at the temperature of 105 ℃ in a nitrogen atmosphere, cooling to room temperature under the protection of nitrogen, separating an organic layer by using a separating funnel, sequentially extracting and purifying by using water and saturated saline solution, pouring the obtained extract into methanol to precipitate a light yellow polymer, performing suction filtration on the light yellow polymer, and finally performing Soxhlet extraction and purification for 48 hours by using methanol to obtain a conjugated polymer containing triarylamine and fluorene units;
the concentration of the potassium carbonate solution is 3 mol/L; the volume ratio of the potassium carbonate solution to the toluene is 1: 1; the mass ratio of the light yellow triarylamine monomer prepared in the first step to the 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester) is 1 (1-1.2); the amount ratio of the light yellow triarylamine monomer prepared in the first step to the tetrakis (triphenylphosphine) palladium is 1 (0.04-0.05); the volume ratio of the substance amount of the light yellow triarylamine monomer prepared in the step one to the toluene is 1mol (40L-45L).
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