CN110903468A - Polythiophene with side chain containing nitroxide free radical, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses polythiophene with a side chain containing nitroxide free radicals and a preparation method and application thereof, wherein 2- (2, 5-di (thiophene-2-yl) thiophene-3-yl) acetic acid and 4-hydroxy-2, 2,6, 6-tetramethylpiperidine nitroxide free radicals are used as reaction raw materials, 4-dimethylaminopyridine is used as a catalyst, dicyclohexylcarbodiimide is used as a dehydrating agent, the reaction raw materials are reacted for 8-12 hours in a dichloromethane solvent at room temperature, and TT-TEMPO is obtained by post-treating reaction liquid after the reaction is finished; adding the obtained TT-TEMPO into sodium perchlorate boron trifluoride ether solution for electropolymerization; and after the electropolymerization is finished, washing the surface of the electrode to obtain a polymer PTT-TEMPO attached to the surface of the electrode. The PTT-TEMPO has catalytic activity similar to TEMPO. The catalyst is used for the reaction of preparing aldehyde by the electrocatalytic oxidation of alcohol, and the result shows that the catalyst has good catalytic oxidation performance.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to polythiophene with a side chain containing nitroxide free radicals, and a preparation method and application thereof.
Background
The conductive polymer is a conductive material formed by chemically or electrochemically doping a polymer containing a long-chain conjugated pi-bond structure. The conductive polymer has the characteristics of metal and semiconductor, and simultaneously retains the advantages of good flexibility, light weight, processability and the like of the high polymer. In addition, the greatest feature is that the conductivity can be varied over a wide range in the insulator-semiconductor-metal state. Conductive polymers have been receiving attention in various fields due to their special structures and excellent physicochemical properties.
Conductive polymers currently under much research include polyaniline, polypyrrole, polythiophene, and the like. Compared with other conducting polymers, polythiophene and its derivatives are one of the most promising conducting polymers due to their higher conductivity, good environmental stability, and easy derivatization. The conductive polymer can be obtained by chemical polymerization, electrochemical polymerization, photochemical polymerization, emulsion polymerization, etc., wherein electrochemical polymerization is a very common method.
The piperidine nitroxide radical is a stable free radical, the most remarkable of which is 2,2,6, 6-tetramethyl piperidine nitroxide radical (TEMPO), which can be used as a green organic small molecule catalyst in various alcohol oxidation reactions, including chemical oxidation and electrochemical oxidation systems. However, when these nitroxides are used as homogeneous catalysts, they are not easily separated from the product after the reaction. If such nitroxide radicals are directly grafted to the conductive polymer, they can be easily separated from the reaction system after the electrochemical oxidation reaction is completed.
Disclosure of Invention
The invention aims to provide polythiophene with a side chain containing nitroxide free radicals, which can be used for electrocatalytic oxidation reaction of alcohol. The invention also aims to provide a preparation method of the polythiophene with the side chain containing the nitroxide free radical and application thereof.
In order to realize the first invention purpose, the adopted technical scheme is as follows:
a polythiophene having nitroxide radicals in the side chains, designated PTT-TEMPO, characterized by the structure:
in the above formula, n is 8 to 200.
In order to achieve the second invention purpose, the adopted technical scheme is as follows:
a method for preparing the polythiophene (PTT-TEMPO) with the side chain containing the nitroxide free radical comprises the following steps:
1) taking 2- (2, 5-di (thiophene-2-yl) thiophene-3-yl) acetic acid (TTAA) and 4-hydroxy-2, 2,6, 6-tetramethylpiperidine nitroxide radical (4-OH-TEMPO) as reaction raw materials, 4-Dimethylaminopyridine (DMAP) as a catalyst, Dicyclohexylcarbodiimide (DCC) as a dehydrating agent, reacting the reaction raw materials in a dichloromethane solvent at room temperature for 8-12 h, and carrying out post-treatment on reaction liquid after the reaction is finished to obtain a thiophene monomer (TT-TEMPO) with a side chain containing the nitroxide radical;
2) performing electropolymerization reaction on an electrochemical workstation, wherein a three-electrode system is adopted, a working electrode is a graphite electrode, an auxiliary electrode is a Pt electrode, and 0.1mol/L silver nitrate acetonitrile solution is used as a reference electrode; adding TT-TEMPO obtained in the step 1) into sodium perchlorate boron trifluoride ether solution, and performing electropolymerization at room temperature;
3) and after the electropolymerization is finished, taking out the working electrode, and respectively washing the surface of the electrode by using deionized water and acetonitrile to obtain the polymer PTT-TEMPO attached to the surface of the electrode.
The reaction expression is as follows:
the ratio of the amount of TTAA to the amount of 4-OH-TEMPO, DMAP and DCC in the step (1) is 100: 100-120: 20-50: 100 to 120.
The method for post-treating the reaction solution in the step (1) comprises the following steps: after the reaction is finished, filtering the reaction solution, evaporating the filtrate under reduced pressure to remove the solvent, and then performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 5 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the monomer TT-TEMPO.
In the sodium perchlorate boron trifluoride diethyl etherate solution in the step (2), the mass concentration of sodium perchlorate in boron trifluoride diethyl etherate is recommended to be 0.05-0.1 mol/L.
And (3) polymerizing TT-TEMPO in boron trifluoride ether solution, wherein the mass concentration of TT-TEMPO in boron trifluoride ether is recommended to be 0.05-0.1 mol/L.
And (3) recommending 8-12 circles for the number of scanning circles in the step (2).
The PTT-TEMPO has catalytic activity similar to TEMPO. The catalyst is used for the reaction of preparing aldehyde by the electrocatalytic oxidation of alcohol, and the result shows that the catalyst has good catalytic oxidation performance.
Drawings
FIG. 1 is an infrared spectrum of TT-TEMPO and PTT-TEMPO of the present invention, where curve a is TT-TEMPO and curve b is PTT-TEMPO.
FIG. 2 is a scanning electron micrograph of PTT-TEMPO according to the present invention.
Detailed Description
The present invention is further illustrated by the following specific embodiments, but the scope of the invention is not limited thereto.
Example 1 Synthesis of TT-TEMPO
In a 100mL round-bottomed flask, 5mmol of TTAA, 5mmol of 4-OH-TEMPO, 2mmol of DMAP, 50mL of dichloromethane and 5mmol of DCC were sequentially added, and the reaction was stirred at room temperature for 12 hours. Filtering the reaction solution, evaporating the filtrate under reduced pressure to remove the solvent, and then performing column chromatography separation, wherein the volume ratio of ethyl acetate/petroleum ether is 1: 5 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the monomer TT-TEMPO. The isolation yield was 80%.
Because free radicals exist in TT-TEMPO molecules and cannot be directly characterized by nuclear magnetism, after the TT-TEMPO molecules are reduced by isoascorbic acid,further characterization was performed by NMR and MS.1H NMR(500M,CDCl3)δ:7.33-7.01(m,7H),5.08(s,1H),3.70(s,2H),1.91(d,J＝10.0Hz,2H),1.58(t,J＝11.2Hz,2H),1.19(d,J＝8.8Hz,12H).13C NMR(125M,CDCl3)δ:168.8,135.3,134.4,133.3,130.5,129.2,126.4,126.3,125.3,125.0,124.8,123.3,122.4,66.1,57.8,42.2,33.7,30.3.MS(ESI),m/z,462.1217[M+H]+。
Example 2 Synthesis of TT-TEMPO
The reaction procedure is as in example 1, except that the amount of 4-OH-TEMPO is changed to 6mmol, the amount of DMAP is changed to 1mmol, the reaction is carried out for 12 hours, and the separation yield of TT-TEMPO is 72%.
Example 3 Synthesis of TT-TEMPO
The reaction procedure is as in example 1, except that the amount of 4-OH-TEMPO was changed to 6mmol, the amount of DCC was changed to 6mmol, the reaction was carried out for 8 hours, and the isolation yield of TT-TEMPO was 83%.
Example 4 preparation of PTT-TEMPO
The electropolymerization reaction is carried out on an electrochemical workstation, a three-electrode system is adopted, a working electrode is a graphite electrode, an auxiliary electrode is a Pt electrode, and 0.1mol/L silver nitrate acetonitrile solution is used as a reference electrode. A25 mL beaker was charged with a 0.067mol/L sodium perchlorate in boron trifluoride ether (15mL) and 1mmol TT-TEMPO, and electropolymerization was carried out at room temperature. And (3) the polymerization potential is 0-1.1V, the scanning speed is 25mV/s, after scanning for 10 circles, the working electrode is taken out, and the surface of the electrode is respectively washed by deionized water and acetonitrile to obtain the polymer PTT-TEMPO attached to the surface of the electrode.
Example 5 preparation of PTT-TEMPO
The reaction procedure was the same as in example 4, except that the concentration of boron trifluoride etherate solution of sodium perchlorate was changed to 0.1mol/L, the amount of TT-TEMPO was changed to 1.5mmol, and the number of scanning cycles was changed to 12 cycles, to prepare the polymer PTT-TEMPO attached to the electrode surface.
Example 6 electrocatalytic Properties of PTT-TEMPO
The PTT-TEMPO on the surface of the graphite electrode prepared in example 4 was coated with 30. mu.L of Nafion ethanol solution (volume ratio of Nafion to ethanol: 1: 9), and dried for use. The electrocatalytic oxidation reaction is carried out on an electrochemical workstation, a three-electrode system is adopted, the working electrode is the PTT-TEMPO/C prepared above, the auxiliary electrode is a Pt electrode, and 0.1mol/L silver nitrate acetonitrile solution is used as a reference electrode. Adding 15mL of 0.5mmol of benzyl alcohol, 1mmol of 2, 6-dimethylpyridine and 0.1mol/L sodium perchlorate acetonitrile solution into a 25mL beaker, electrolyzing at a constant potential of 1.6V at room temperature, detecting the electrolyte by gas chromatography after 7h of electrolysis, wherein the conversion rate of the benzyl alcohol is 97 percent, and the selectivity of the product benzaldehyde is 98 percent.
Example 7 electrocatalytic Properties of PTT-TEMPO
The PTT-TEMPO on the surface of the graphite electrode prepared in example 5, which was marked as PTT-TEMPO/C, was coated with 30. mu.L of a Nafion ethanol solution (Nafion/ethanol volume ratio: 1: 9) and dried for use. The procedure of the experiment for testing the electrocatalytic properties is the same as that of example 6, the conversion rate of the benzyl alcohol is 92%, and the selectivity of the product benzaldehyde is 99%.
Claims (7)
1. A polythiophene having nitroxide radicals in the side chains, designated PTT-TEMPO, characterized by the structure:
in the above formula, n is 8 to 200.
2. A method for producing a polythiophene (PTT-TEMPO) having a nitroxide radical in a side chain according to claim 1, comprising: the method comprises the following steps:
1) taking 2- (2, 5-di (thiophene-2-yl) thiophene-3-yl) acetic acid (TTAA) and 4-hydroxy-2, 2,6, 6-tetramethylpiperidine nitroxide radical (4-OH-TEMPO) as reaction raw materials, 4-Dimethylaminopyridine (DMAP) as a catalyst, Dicyclohexylcarbodiimide (DCC) as a dehydrating agent, reacting the reaction raw materials in a dichloromethane solvent at room temperature for 8-12 h, and carrying out post-treatment on reaction liquid after the reaction is finished to obtain a thiophene monomer (TT-TEMPO) with a side chain containing the nitroxide radical;
2) performing electropolymerization reaction on an electrochemical workstation, wherein a three-electrode system is adopted, a working electrode is a graphite electrode, an auxiliary electrode is a Pt electrode, and 0.1mol/L silver nitrate acetonitrile solution is used as a reference electrode; adding TT-TEMPO obtained in the step 1) into sodium perchlorate boron trifluoride ether solution, and performing electropolymerization at room temperature;
3) and after the electropolymerization is finished, taking out the working electrode, and respectively washing the surface of the electrode by using deionized water and acetonitrile to obtain the polymer PTT-TEMPO attached to the surface of the electrode.
3. The method of claim 2, wherein: the ratio of the amount of TTAA to the amount of 4-OH-TEMPO, DMAP and DCC in the step (1) is 100: 100-120: 20-50: 100 to 120.
4. The method of claim 2, wherein: the method for post-treating the reaction solution in the step (1) comprises the following steps: after the reaction is finished, filtering the reaction solution, evaporating the filtrate under reduced pressure to remove the solvent, and then performing column chromatography separation, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 5 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the monomer TT-TEMPO.
5. The method of claim 2, wherein: in the sodium perchlorate boron trifluoride diethyl etherate solution in the step (2), the mass concentration of sodium perchlorate in boron trifluoride diethyl etherate is recommended to be 0.05-0.1 mol/L.
6. The method of claim 2, wherein: and (3) polymerizing TT-TEMPO in boron trifluoride ether solution, wherein the mass concentration of TT-TEMPO in boron trifluoride ether is recommended to be 0.05-0.1 mol/L.
7. The polythiophene according to claim 1, wherein the side chain thereof contains nitroxide radical, which is used as a catalyst in the reaction of preparing aldehyde by electrocatalytic oxidation of alcohol.
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| CN115093549A (en) * | 2022-08-04 | 2022-09-23 | 浙江吉泰新材料股份有限公司 | Polythiophene with side chain containing ABNO, and preparation method and application thereof |
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| CN102598401A (en) * | 2009-07-31 | 2012-07-18 | 松下电器产业株式会社 | Photoelectric element |
| WO2012105857A1 (en) * | 2011-02-04 | 2012-08-09 | University Of Otago | Gel actuator |
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| CN115093549A (en) * | 2022-08-04 | 2022-09-23 | 浙江吉泰新材料股份有限公司 | Polythiophene with side chain containing ABNO, and preparation method and application thereof |
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