CN117164825A - Conductive polymer with TEMPO-containing side chain, and preparation method and application thereof - Google Patents
Conductive polymer with TEMPO-containing side chain, and preparation method and application thereof Download PDFInfo
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- CN117164825A CN117164825A CN202311136991.1A CN202311136991A CN117164825A CN 117164825 A CN117164825 A CN 117164825A CN 202311136991 A CN202311136991 A CN 202311136991A CN 117164825 A CN117164825 A CN 117164825A
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 34
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 title claims abstract 7
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 26
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 68
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 26
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 26
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- -1 [1,4] dioxin-2-yl Chemical group 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 150000003254 radicals Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 13
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 7
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 28
- 230000003647 oxidation Effects 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 34
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 25
- 239000000047 product Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002484 cyclic voltammetry Methods 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 125000004311 dioxin-2-yl group Chemical group [H]C1=C([H])OC(*)=C([H])O1 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to the technical field of electrochemistry, and discloses a conductive polymer with a side chain containing TEMPO, and a preparation method and application thereof. At present, the preparation of 2, 5-diformylfuran by using 5-hydroxymethyl furfural as a raw material has the problem of difficult recovery of a catalyst and separation of the catalyst from a product. In order to solve the technical problems, the invention realizes heterogeneous electrochemical catalytic oxidation of 5-hydroxymethylfurfural by TEMPO to generate 2, 5-diformylfuran by connecting a small molecular catalyst TEMPO to a conductive polymer and connecting the conductive polymer obtained by connection. The conductive polymer is used as a catalyst for preparing 2, 5-diformylfuran by electrocatalytic oxidation of 5-hydroxymethylfurfural, so that the problem of difficult separation of the catalyst and a product is avoided, and the conductive polymer has the characteristics of high reaction rate and high product yield.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a conductive polymer with a side chain containing TEMPO, and a preparation method and application thereof.
Background
Along with the continuous consumption of fossil resources such as petroleum and the like, renewable biomass resources with rich reserves are developed and utilized to prepare bulk chemicals, fine chemicals and high polymer materials, and the shortage of petroleum resources is supplemented, so that the method has important significance. The biomass resource takes up the largest proportion of carbohydrate, and the 5-Hydroxymethylfurfural (HMF) with wide application market can be prepared by acid-catalyzed dehydration of fructose, glucose, cellulose and other carbohydrate. HMF is one of the biomass-based platform compounds, and is also an important intermediate for synthesizing various fine chemicals and furan-based polymers, and has received wide attention both at home and abroad.
HMF oxidation produces a variety of important platform compounds such as 2, 5-Diformylfuran (DFF), 2, 5-furandicarboxylic acid (FDCA), 5-aldehyde-2-furancarboxylic acid (FFCA), and 5-hydroxymethylfuroic acid (HMFCA), with DFF, FDCA, and HMFCA being important downstream products from selective oxidation of HMF. The 2, 5-diformylfuran is one of the most important derivatives of 5-hydroxymethylfurfural, has wide application in the chemical industry field, and can be used for preparing pesticide intermediates, bactericides, heterocyclic compounds and the like.
At present, the 2, 5-diformylfuran is prepared by oxidizing 5-hydroxymethylfurfural serving as a raw material by using metered oxidants such as manganese dioxide, chromium trioxide, sodium hypochlorite and the like, but the preparation method has serious environmental pollution, longer reaction time, larger consumption of the oxidants and reaction solvents, low product yield, difficult separation and unsuitable large-scale industrial production.
For example, chinese patent CN101987839a discloses a method for preparing 2, 5-diformylfuran by oxidizing 5-hydroxymethylfurfural. Cu (NO) 3 ) 2 And VOSO 4 The compound catalytic system is heated to 80 ℃ in acetonitrile to react for 1.5 hours by using molecular oxygen as an oxygen source, and the yield of the DFF is 98 percent. The reaction condition of the process is mild, and the yield of DFF is high. However, the recovery and recycling of the catalyst of this system is difficult.
2, 6-tetramethyl piperidine nitroxide radical (TEMPO) is formed into a resonance structure by the movement of contained single electron between nitroxides, so that the TEMPO is a nitroxide radical with high stability. TEMPO is widely used as a high-efficiency stable small-molecule catalyst for the selective oxidation of various hydroxyl functional groups. The TEMPO is used as a catalyst in the reaction for preparing the 2, 5-diformylfuran by using the 5-hydroxymethylfurfural as a raw material, has higher reaction yield, but is used as a homogeneous catalyst, and has the problems of difficult recovery and purification of a product and difficult separation of the catalyst and the product.
Disclosure of Invention
In the prior art, the preparation of 2, 5-diformylfuran by using 5-hydroxymethylfurfural as a raw material has the problem of difficult recovery of a catalyst and separation of the catalyst from a product. In order to solve the technical problems, the invention provides a conductive polymer with a TEMPO-containing side chain, and a preparation method and application thereof. According to the invention, a small molecular catalyst TEMPO is connected to the conductive polymer, and the heterogeneous electrochemical catalytic oxidation of 5-hydroxymethylfurfural by the TEMPO is realized to generate 2, 5-diformylfuran by the conductive polymer obtained through connection. The conductive polymer is used as a catalyst for preparing 2, 5-diformylfuran by electrocatalytic oxidation of 5-hydroxymethylfurfural, so that the problem of difficult separation of the catalyst and a product is avoided, and the conductive polymer has the characteristics of high reaction rate and high product yield.
The specific technical scheme of the invention is as follows:
in one aspect, the present invention provides a conductive polymer having TEMPO in its side chain, which has the structural formula shown below:
wherein n=4 to 100, x=1 to 10, y=1 to 10.
At present, in the process of preparing 2, 5-diformylfuran by taking 5-hydroxymethylfurfural as a raw material, the used catalysts comprise sodium hypochlorite, TEMPO and the like, which are all homogeneous catalysis, and the problem of difficult separation of the catalyst and the product exists; or other catalysts, such as Cu (NO) as proposed in Chinese patent CN101987839A 3 ) 2 And VOSO 4 The composite catalytic system also has the problem of difficult separation of the catalyst in the reaction liquid. The invention uses 3, 4-Ethylenedioxythiophene (EDOT) and 2,2' -dithiazoleAs monomers, pheno (BTh) provides a conductive polymer containing TEMPO in its side chain, which realizes immobilization of TEMPO. The conductive polymer is used as a catalyst in electrochemical catalytic oxidation reaction for preparing 2, 5-diformylfuran from 5-hydroxymethylfurfural, heterogeneous electrocatalysis of TEMPO is realized, the problem of difficult separation of the catalyst and a product can be avoided, and the conductive polymer has the characteristics of quick reaction and high product yield.
In order to realize immobilization of TEMPO, the invention selects 3, 4-Ethylenedioxythiophene (EDOT) and 2,2' -bithiophene (BTh) as monomers to be copolymerized to form the conductive polymer. The 3, 4-ethylenedioxythiophene has low oxidation potential, good molecular symmetry, low sterically hindered condensation ring and wide anodic potential window. The poly 3, 4-ethylenedioxythiophene (PEDOT) obtained by electropolymerization with EDOT as a monomer has the advantage of high conductivity. However, when TEMPO is connected to 3, 4-ethylenedioxythiophene (PEDOT) as a catalyst for preparing 2, 5-diformylfuran from 5-hydroxymethylfurfural, the defect that the stability of the polymer is poor and the yield of the product is low exists. Thus, further, the present invention utilizes the copolymerization of EDOT and BTh to form a copolymer, and TEMPO is immobilized on the copolymer as a catalyst to further increase the yield of the 2, 5-diformylfuran product. EDOT and BTh both act as thiophene derivatives, BTh have a lower initial oxidation potential. The EDOT derivative (EDOT-TEMPO) with the side chain containing the TEMPO group and BTh are copolymerized, so that the oxidation potential can be reduced, peroxidation is avoided, the length of a main chain of the polymer can be increased, the steric hindrance of the side chain is reduced, and the stability of the polymer is further improved.
In another aspect, the present invention provides a method for preparing the above conductive polymer having TEMPO in its side chain, comprising the steps of:
(1) With (4- (2, 3-dihydrothiophene [3, 4-b)][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoic acid (C) 4 -EDOT-COOH) and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide free radical (4-OH-TEMPO) are used as reaction raw materials, and a catalyst and a dehydrating agent are added for reaction to obtain 4- ((4- ((2, 3-dihydro thiophene [3, 4-b)][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical (EDOT-TEMPO);
(2) Adopting a three-electrode system, wherein a working electrode and an auxiliary electrode are Pt electrodes, a reference electrode is Ag/Ag+ electrode, and adding a monomer 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethylpiperidine-1-oxyl free radical (EDOT-TEMPO) and 2,2' -bithiophene (BTh) into a dichloromethane solution containing tetrabutylammonium perchlorate to carry out electropolymerization reaction;
(3) After the electropolymerization reaction is completed, the surface of the working electrode is rinsed and dried to obtain a conductive polymer (P (EDOT-TEMPO/BTh)) film containing TEMPO in the side chain attached to the surface of the working electrode.
The reaction expression of the preparation method provided by the invention is as follows:
as a preferable mode of the above technical scheme of the invention, in the step (1), the ratio of the amount of the substances of the (4- (2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxybutyric acid and the 4-hydroxy-2, 6-tetramethylpiperidine nitroxide is 1:1-1.5.
Preferably, in the above technical scheme of the present invention, in the step (1), the catalyst is 4-dimethylaminopyridine.
More preferably, the ratio of the amounts of the substances of (4- (2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxybutyric acid and 4-dimethylaminopyridine is 1:0.1 to 0.5.
Preferably, in the above technical scheme of the present invention, in the step (1), the dehydrating agent is dicyclohexylcarbodiimide.
More preferably, the ratio of the amounts of the substances of (4- (2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxybutyric acid and dicyclohexylcarbodiimide is 1:1 to 1.5.
As a preferable mode of the above technical scheme of the invention, in the step (1), the reaction time is 8-14 h.
Specifically, in the step (1), after the reaction, the method for obtaining the product 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxyl free radical from the reaction liquid comprises the following steps:
filtering the reaction solution, removing the solvent by rotary evaporation, separating and purifying the crude product by column chromatography, collecting eluent which is a mixed solution of petroleum ether/ethyl acetate=5/1 (v/v), and collecting eluent containing a target compound, and evaporating the eluent to obtain orange yellow solid, namely 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxy free radical (EDOT-TEMPO).
As a preferable mode of the above technical scheme of the invention, in the step (2), the ratio of the amount of substances of the monomer 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidine-1-oxyl free radical (EDOT-TEMPO) and 2,2' -bithiophene (BTh) is 1:0.2-0.8.
In the present invention, EDOT-TEMPO is copolymerized with BTh, and the ratio of the amounts of the substances is preferably 1:0.2 to 0.8. An excessive BTh can result in a copolymer with relatively low structural content of TEMPO and poor catalytic performance; too little BTh results in poor structural stability of the copolymer and thus affects catalytic performance.
As a preferable mode of the above-mentioned invention, in the step (2), the mass concentration of the substance of tetrabutylammonium perchlorate in the methylene chloride solution is 0.1 to 0.15mol/L.
As a preferable mode of the above technical scheme of the invention, in the step (2), the polymerization potential of the electropolymerization reaction is-0.5 to 1.5V, the scanning speed is 50mV/s, and the number of scanning turns is 4 to 10.
As a preferable mode of the above technical scheme of the invention, in the step (3), the surface of the working electrode is rinsed with dichloromethane and acetonitrile, respectively.
The invention provides an application of the conductive polymer and the conductive polymer prepared by the preparation method in catalyzing 5-hydroxymethylfurfural to generate 2, 5-diformylfuran.
The conductive polymer P (EDOT-TEMPO/BTh) provided by the invention has the catalytic activity of TEMPO, and the polymer P (EDOT-TEMPO/BTh) is used for the reaction of preparing 2, 5-diformylfuran by electrocatalytic oxidation of 5-hydroxymethylfurfural, so that the result shows that the conductive polymer has good catalytic oxidation performance.
Compared with the prior art, the invention has the following technical effects:
the invention provides a conductive polymer P (EDOT-TEMPO/BTh), which is used as a catalyst in an electrochemical oxidation reaction for preparing 2, 5-diformylfuran from a biomass compound 5-hydroxymethylfurfural, can realize heterogeneous electrocatalysis of the reaction, avoids the problem of difficult separation of the catalyst and a product, and has the characteristics of quick reaction and high product yield.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of EDOT-TEMPO prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of EDOT-TEMPO prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of polymer P (EDOT-TEMPO/BTh) prepared in example 4 of the present invention;
FIG. 4 is a drawing showing the element Mapping of the polymer P (EDOT-TEMPO/BTh) prepared in example 4 of the present invention;
FIG. 5 is a plot of cyclic voltammetric polymerization for the preparation of Polymer P (EDOT-TEMPO/BTh) according to example 4 of the present invention;
FIG. 6 is a cyclic voltammogram of the stability test of polymer P (EDOT-TEMPO/BTh) prepared in example 4 of the present invention.
Detailed Description
The invention is further described below with reference to examples and figures. 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.
General examples the present invention provides a conductive polymer P (EDOT-TEMPO/BTh) and a method for preparing the same, comprising the steps of:
(1) With (4- (2, 3-dihydrothiophene [3, 4-b)][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoic acid (C) 4 -EDOT-COOH) and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide radical (4-OH-TEMPO) as reaction raw material, adding catalyst and dehydrating agent, and reacting to obtain 4- ((4- ((2, 3-dihydro thiophene [3, 4-b)][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical (EDOT-TEMPO);
(2) Adopts a three-electrode system, the working electrode and the auxiliary electrode are Pt electrodes, and the reference electrode is Ag/Ag + An electrode, in which monomer 4- ((4- ((2, 3-dihydrothiophene [3, 4-b) is added to a dichloromethane solution containing tetrabutylammonium perchlorate][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical (EDOT-TEMPO) and 2,2' -bithiophene (BTh) are electropolymerized;
(3) After the electropolymerization reaction is completed, the surface of the working electrode is rinsed and dried to obtain a conductive polymer (P (EDOT-TEMPO/BTh)) film containing TEMPO in the side chain attached to the surface of the working electrode. The polymer P (EDOT-TEMPO/BTh) has the formula:
wherein n=4 to 100, x=1 to 10, y=1 to 10.
Preferably, in step (1), the catalyst is 4-Dimethylaminopyridine (DMAP).
Preferably, in step (1), the dehydrating agent is Dicyclohexylcarbodiimide (DCC).
Further preferably, in step (1), (4- (2, 3-dihydrothiophene [3, 4-b)][1,4]Dioxin-2-yl) methoxy) -4-oxobutanoic acid (C) 4 -EDOT-COOH), 4-hydroxy-2, 6-tetramethylpiperidine nitroxide radical (4-OH-TEMPO), 4-Dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC) in a ratio of 1:1 to 1.5:0.1 to 0.5:1 to 1.5.
Preferably, in the step (1), the reaction time is 8 to 14 hours.
Specifically, in the step (1), after the reaction, the method for obtaining the product 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxyl free radical from the reaction liquid comprises the following steps:
filtering the reaction solution, removing the solvent by rotary evaporation, separating and purifying the crude product by column chromatography, collecting eluent which is a mixed solution of petroleum ether/ethyl acetate=5/1 (v/v), and collecting eluent containing a target compound, and evaporating the eluent to obtain orange yellow solid, namely 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxy free radical (EDOT-TEMPO).
Preferably, in step (2), the ratio of the amounts of the species of monomer 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical and 2,2' -bisthiophene is from 1:0.2 to 0.8.
Preferably, in the step (2), the mass concentration of the tetrabutylammonium perchlorate in the methylene chloride solution is 0.1 to 0.15mol/L.
Preferably, in the step (2), the electropolymerization has a polymerization potential of-0.5 to 1.5V, a scanning speed of 50mV/s and a number of turns of 4 to 10.
Preferably, in step (3), the working electrode surface is rinsed with dichloromethane and acetonitrile, respectively.
The reaction expression of the preparation method is as follows:
EXAMPLE 1 Synthesis of EDOT-TEMPO
In a 250mL round bottom flask, add 3.26. 3.26g C 4 EDOT-COOH (12.0 mmol), 2.07g 4-OH-TEMPO (12.0 mmol), 0.15g 4-Dimethylaminopyridine (DMAP) (1.2 mmol) and 60mL dichloromethane. 2.97g dicyclohexylcarbodiimide (DCC, 14.4 mmol) was dissolved in 50mL of dichloromethane, added dropwise to the above solution via a 50mL dropping funnel, and the reaction monitored by thin layer chromatography and stirred at 25℃for 18h. After the reaction was completed, the reaction solution was filtered to remove N, N' -Dicyclohexylurea (DCU), then the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate=5/1 (v/v) as a mixed solutionLiquid) to yield 2.86g of orange-yellow solid EDOT-TEMPO in a separation yield of 56%.
The yellow solid obtained in this example was taken for mass spectrometry. The results were: high resolution mass spectrometry results (esi+): m/z, calculated for C 20 H 29 NO 7 S + [M+H] + ：427.1659；found:427.1652。
EDOT-TEMPO has free radicals and cannot be directly characterized by nuclear magnetism. Thus, this example was characterized by nuclear magnetism after reducing EDOT-TEMPO to EDOT-TEMPO with L-ascorbic acid. The nuclear magnetic hydrogen spectrogram and the nuclear magnetic carbon spectrogram are respectively shown in fig. 1 and fig. 2. The nuclear magnetic data are as follows:
1 H NMR(400MHz,CDCl3)δ6.46(s,2H),5.16(s,1H),4.44(s,3H),4.33(d,J＝9.9Hz,1H),4.16(s,1H),2.74(d,J＝14.7Hz,5H),2.00(d,J＝9.6Hz,2H),1.65(s,2H),1.50-1.13(m,12H).
13 C NMR(101MHz,CDCl3)δ169.99,169.69,139.20,139.01,98.54,98.23(d,J＝12.7Hz),69.49,65.30,63.75,60.69,57.29,41.83,30.11,27.33,26.99,18.44。
EXAMPLE 2 Synthesis of EDOT-TEMPO
The main difference between this embodiment and embodiment 1 is that: the amount of 4-OH-TEMPO added was 14.4mmol, DMAP added was 2.4mmol, DCC added was 18.0mmol, and the reaction time was 16h.
The isolation yield of EDOT-TEMPO of this example was 64%.
EXAMPLE 3 Synthesis of EDOT-TEMPO
The main difference between this embodiment and embodiment 1 is that: the amount of 4-OH-TEMPO added was 18mmol, DMAP added was 6.0mmol, DCC added was 12.0mmol, and the reaction time was 14h.
The isolation yield of EDOT-TEMPO of this example was 58%.
Example 4P (EDOT-TEMPO/BTh) preparation
Electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell, a solution of 0.75mmol EDOT-TEMPO, 0.37mmol BTh and 0.1mol/L tetrabutylammonium perchlorate in methylene chloride (15 mL) and sonicated in an ultrasonic cleaner for 5min to completely dissolve the monomers EDOT-TEMPO and BTh. The electrochemical cell is placed in a constant temperature water bath kettle at 25 ℃, and polymer P (EDOT-TEMPO/BTh) is obtained on a working electrode by a cyclic voltammetry, wherein the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 4. After the polymerization was completed, the electrode was taken out, and the electrode surface was rinsed with a dichloromethane solution and an acetonitrile solution. A blue-black polymer P (EDOT-TEMPO/BTh) film was obtained which was adhered to the electrode surface. The polymer P (EDOT-TEMPO/BTh) has the formula:
wherein n=4 to 100, x=1 to 10, y=1 to 10.
The polymer P (EDOT-TEMPO/BTh) of this example is shown in FIG. 3, the element Mapping is shown in FIG. 4, and the cyclic voltammetric polymerization curve is shown in FIG. 5. As can be seen from fig. 5, the oxidation peak current gradually increases with the number of scan turns, indicating that the conductivity of the polymer is better and better.
The polymer P (EDOT-TEMPO/BTh) prepared in this example was subjected to electrochemical stability test, and the cyclic voltammogram thereof is shown in FIG. 6.
As can be seen from FIG. 6, the oxidation peak current at 1 st turn is 2.07mA, the oxidation peak current at 2 nd turn is continuously increased, the oxidation peak current reaches a maximum value of 2.41mA at 10 th turn, and then the oxidation peak current at 10-18 turns is kept unchanged at 2.41mA, and at this time, the oxidation peak current is 116% of the initial value. The oxidation peak current then began to drop, at 100 turns the oxidation peak current was 1.60mA, which was 77% of the initial value, and at 200 turns the oxidation peak current was 1.08mA, which still reached 52% of its initial value. It can be seen that the P (EDOT-TEMPO/BTh) modified electrode has good electrochemical stability in cyclic voltammetry.
Example 5 preparation of P (EDOT-TEMPO/BTh)
The main difference between the reaction steps and example 4 is: the amount of the monomer EDOT-TEMPO added was 1.5mmol and that of BTh added was 0.3mmol. The specific reaction steps in this example are as follows:
electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell, a solution of 1.5mmol EDOT-TEMPO, 0.3mmol BTh and 0.1mol/L tetrabutylammonium perchlorate in methylene chloride (15 mL) and sonicated in an ultrasonic cleaner for 5min to completely dissolve the monomers EDOT-TEMPO and BTh. The electrochemical cell is placed in a constant temperature water bath kettle at 25 ℃, and polymer P (EDOT-TEMPO/BTh) is obtained on a working electrode by a cyclic voltammetry, wherein the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 4. After the polymerization is completed, the electrode is taken out, and the surface of the electrode is washed by dichloromethane solution and acetonitrile solution respectively. A blue-black P (EDOT-TEMPO/BTh) polymer film was obtained which was attached to the electrode surface.
Example 6P (EDOT-TEMPO/BTh) preparation
The main difference between the reaction steps and example 4 is: the amount of the monomer EDOT-TEMPO added was 1.5mmol and that of BTh added was 1.2mmol. The specific reaction steps in this example are as follows:
electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell with a solution of 1.5mmol EDOT-TEMPO, 1.2mmol BTh and 0.1mol/L tetrabutylammonium perchlorate in methylene chloride (15 mL) and sonicated in an ultrasonic cleaner for 5min to completely dissolve the monomers EDOT-TEMPO and BTh. The electrochemical cell is placed in a constant temperature water bath kettle at 25 ℃, and polymer P (EDOT-TEMPO/BTh) is obtained on a working electrode by a cyclic voltammetry, wherein the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 4. After the polymerization is completed, the electrodes are taken out and respectively usedThe electrode surface was rinsed with methylene chloride solution and acetonitrile solution. A blue-black P (EDOT-TEMPO/BTh) polymer film was obtained which was attached to the electrode surface.
Example 7P (EDOT-TEMPO/BTh) preparation
The main difference between the reaction steps and example 4 is: the concentration of the methylene dichloride solution of tetrabutylammonium perchlorate is 0.15mol/L, and the scanning circle number is 10. The specific reaction steps in this example are as follows:
electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell, a solution of 0.75mmol EDOT-TEMPO, 0.37mmol BTh and 0.15mol/L tetrabutylammonium perchlorate in methylene chloride (15 mL) and sonicated in an ultrasonic cleaner for 5min to completely dissolve the monomers EDOT-TEMPO and BTh. The electrochemical cell is placed in a constant temperature water bath kettle at 25 ℃, and polymer P (EDOT-TEMPO/BTh) is obtained on a working electrode by a cyclic voltammetry, wherein the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 10. After the polymerization was completed, the electrode was taken out, and the electrode surface was rinsed with a dichloromethane solution and an acetonitrile solution. A blue-black P (EDOT-TEMPO/BTh) polymer film was obtained which was attached to the electrode surface.
Comparative example 1
The main difference from example 4 is that: polymer P (EDOT-TEMPO) was prepared by homopolymerization of the monomer EDOT-TEMPO without addition of BTh. The preparation method comprises the following specific steps:
electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell with 1.12mmol EDOT-TEMPO and 0.1mol/L tetrabutylammonium perchlorate in methylene chloride (15 mL) and sonicated in an ultrasonic cleaner for 5min to completely dissolve the monomer EDOT-TEMPO. Placing the electrochemical cell in a constant-temperature water bath kettle at 25 ℃ and circulatingThe polymer P (EDOT-TEMPO) is obtained on the working electrode by a cyclic voltammetry, the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 4. After the polymerization was completed, the electrode was taken out, and the electrode surface was rinsed with a dichloromethane solution and an acetonitrile solution. A dark blue polymer P (EDOT-TEMPO) film was obtained which was attached to the electrode surface.
Comparative example 2
The main difference from example 4 is that: the monomer EDOT-TEMPO (4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical) was replaced with 4- (((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) carbonyl) -2, 6-tetramethylpiperidin-1-oxyl radical (comparative monomer). The structural formula of the 4- (((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) carbonyl) -2, 6-tetramethylpiperidine-1-oxyl radical is as follows:
the preparation method comprises the following specific steps:
electrochemical polymerization was performed on the substrate Pt electrode by cyclic voltammetry using a three electrode system on the CHI600e electrochemical workstation. The working electrode is a platinum sheet electrode, the auxiliary electrode is a platinum sheet electrode, and the reference electrode is Ag/Ag + Electrode (0.1 mol/LAgNO) 3 /CH 3 CN solution) was added to a 25mL undivided electrochemical cell, a dichloromethane solution (15 mL) of 0.75mmol of the comparative monomer, 0.37mmol of BTh and 0.1mol/L tetrabutylammonium perchlorate, and the mixture was sonicated in a sonicator for 5min to completely dissolve the monomer. The electrochemical cell is placed in a constant temperature water bath kettle at 25 ℃, and a polymer is obtained on a working electrode by a cyclic voltammetry, wherein the potential range is-0.5V-1.5V, the scanning speed is 50mV/s, and the scanning turns are 4. After the polymerization was completed, the electrode was taken out, and the electrode surface was rinsed with a dichloromethane solution and an acetonitrile solution. A blue-violet polymer film attached to the electrode surface was obtained.
Comparative example 3
The main difference from example 4 is that: the amounts of the monomers EDOT-TEMPO and BTh were 0.75mmol and 0.07mmol, respectively.
Comparative example 4
The main difference from example 4 is that: the amounts of the monomers EDOT-TEMPO and BTh were 0.75mmol and 0.75mmol, respectively.
Catalytic Performance test P (EDOT-TEMPO/BTh) electrocatalytic 5-hydroxymethylfurfural oxidation
The catalytic performance test method comprises the following steps: the electrocatalytic oxidation reaction was carried out on the electrochemical workstation CHI600e, using a three-electrode system, the Pt electrodes with polymer films attached to the surfaces obtained in examples 4 to 7 and comparative examples 1 to 4 were working electrodes, pt electrode was auxiliary electrode, ag/Ag, respectively + Electrode (0.1 mol/L AgNO) 3 /CH 3 CN) is a reference electrode. 15mL of 0.1mol/L NaClO was prepared 4 /CH 3 CN solution, adding 5-hydroxymethylfurfural (0.5 mmol) and 2, 6-dimethylpyridine (0.5 mmol) into a 25mL undivided electrochemical cell, completely dissolving reactants by ultrasonic treatment in an ultrasonic cleaner for 5min, placing the electrochemical cell into a constant-temperature water bath kettle at 25 ℃, carrying out constant current electrolysis at 2mA, and detecting the content of 2, 5-diformylfuran in the reaction solution by gas chromatography after 8h of electrolysis.
The yields of 2, 5-diformylfuran obtained by electrocatalytic oxidation of 5-hydroxymethylfurfural were shown in Table 1 using the Pt electrodes with polymer films attached to the surfaces obtained in examples 4 to 7 and comparative examples 1 to 4, respectively, as working electrodes.
TABLE 1
| Group of | Yield/% |
| Example 4 | 94 |
| Example 5 | 87 |
| Example 6 | 82 |
| Example 7 | 90 |
| Comparative example 1 | 71 |
| Comparative example 2 | 73 |
| Comparative example 3 | 79 |
| Comparative example 4 | 63 |
As can be seen from table 1:
(1) from the data of examples 4 to 7, it can be seen that the conductive polymer P (EDOT-TEMPO/BTh) provided by the invention is used as a catalyst in electrochemical catalytic oxidation reaction for preparing 2, 5-diformylfuran from 5-hydroxymethylfurfural serving as a biomass platform compound, and has the characteristics of rapid reaction and high product yield in heterogeneous electrocatalysis.
(2) As can be seen from comparative analysis of comparative examples 1-2 and example 4, the conductive polymer prepared by taking EDOT-TEMPO and BTh provided by the invention as monomers has a good catalytic effect on electrochemical catalytic oxidation reaction of preparing 2, 5-diformylfuran from 5-hydroxymethylfurfural. In comparative example 1, PEDOT-TEMPO obtained by electropolymerization using EDOT-TEMPO as a monomer has the advantage of high conductivity, but the catalytic performance is still poor. In example 4, BTh was added for copolymerization to form a copolymerization product, the catalytic performance of which was greatly improved. The great advantage of adding BTh to copolymerize with a EDOT derivative having TEMPO groups in the side chain (EDOT-TEMPO) is demonstrated. The reason for this is further analyzed that BTh is copolymerized, so that not only can the oxidation potential be reduced, peroxidation be avoided, but also the length of the main chain of the polymer can be increased, the steric hindrance of the side chain can be reduced, and the stability of the polymer can be further improved. Comparative example 2 illustrates that 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxobutanoyl) oxy) -2, 6-tetramethylpiperidin-1-oxyl radical is more advantageous as a provider of TEMPO structure than the comparative monomer 4- (((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) carbonyl) -2, 6-tetramethylpiperidin-1-oxyl radical.
(3) As can be seen from comparative analysis of comparative examples 3 to 4 with example 4, the addition of BTh to EDOT-TEMPO forms a copolymerization product, BTh, which has a large influence on the catalytic performance of the copolymerization product P (EDOT-TEMPO/BTh). EDOT-TEMPO is copolymerized with BTh in the amount of 1:0.2-0.8. An excessive BTh can result in a copolymer with relatively low structural content of TEMPO and poor catalytic performance; too little BTh results in poor structural stability of the copolymer and thus affects catalytic performance.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A conductive polymer having TEMPO in its side chain, characterized in that: has the structural formula shown as follows:
wherein n=4 to 100, x=1 to 10, y=1 to 10.
2. A process for producing a TEMPO-containing conductive polymer according to claim 1 wherein: the method comprises the following steps:
(1) Taking (4- (2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxybutyric acid and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide free radical as reaction raw materials, adding a catalyst and a dehydrating agent, and reacting to obtain 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxy free radical;
(2) Adopting a three-electrode system, wherein a working electrode and an auxiliary electrode are Pt electrodes, a reference electrode is an Ag/Ag+ electrode, and monomer 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethylpiperidine-1-oxy free radical and 2,2' -bithiophene are added into dichloromethane solution containing tetrabutylammonium perchlorate to carry out electropolymerization reaction;
(3) After the electropolymerization reaction is finished, the surface of the working electrode is washed and dried, and the conductive polymer film with TEMPO attached to the side chain of the surface of the working electrode is obtained.
3. The method of manufacturing as claimed in claim 2, wherein: in the step (1), the mass ratio of the (4- (2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxybutyric acid and the 4-hydroxy-2, 6-tetramethylpiperidine nitroxide free radical is 1:1-1.5.
4. The method of manufacturing as claimed in claim 2, wherein: in the step (1), the catalyst is 4-dimethylaminopyridine.
5. The method of manufacturing as claimed in claim 2, wherein: in the step (1), the dehydrating agent is dicyclohexylcarbodiimide.
6. The method of manufacturing as claimed in claim 2, wherein: in the step (1), the reaction time is 14-18 h.
7. The method of manufacturing as claimed in claim 2, wherein: in the step (2), the ratio of the amounts of the substances of the monomer 4- ((4- ((2, 3-dihydrothiophene [3,4-b ] [1,4] dioxin-2-yl) methoxy) -4-oxo-butyryl) oxy) -2, 6-tetramethyl piperidine-1-oxyl free radical and 2,2' -bithiophene is 1:0.2-0.8.
8. The method of manufacturing as claimed in claim 2, wherein: in the step (2), the mass concentration of the tetrabutylammonium perchlorate in the dichloromethane solution is 0.1 to 0.15mol/L.
9. The method of manufacturing as claimed in claim 2, wherein: in the step (2), the polymerization potential of the electropolymerization reaction is-0.5-1.5V, the scanning speed is 50mV/s, and the number of scanning turns is 4-10.
10. Use of a conductive polymer according to claim 1 or a conductive polymer prepared by a method according to any one of claims 2 to 8 for catalyzing the production of 2, 5-diformylfuran from 5-hydroxymethylfurfural.
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