A quinone compound and its preparation method and application, a conjugated polymer containing a quinone unit and its preparation method and application, and an organic field-effect transistor device

Abstract

The present invention provides a quinone compound, a preparation method and application thereof, a conjugated polymer containing a quinone unit, a preparation method and application thereof, and an organic field-effect transistor device, and relates to the technical field of functional materials. The quinone compound provided by the present invention has strong intermolecular and intramolecular interactions, and the polymer prepared using such a quinone compound as a monomer has strong interchain interactions, good crystallinity, and excellent charge transfer properties. Moreover, the strong electron-withdrawing ability of the quinone compound can significantly reduce the LUMO energy level of the polymer, which is conducive to the binding and reduction of oxygen. The conjugated polymer containing a quinone unit provided by the present invention is a copolymer of a quinone compound and a conjugated aromatic monomer, and the polymer has strong intermolecular and intramolecular interactions, a low LUMO energy level, good carrier transfer properties, and excellent ORR catalytic activity.

Description

Technical Field

[0001] The present invention relates to the technical field of functional materials, and in particular to a quinone compound, a preparation method and application thereof, a conjugated polymer containing quinone units, a preparation method and application thereof, and an organic field effect transistor device. Background Art

[0002] The oxygen reduction reaction (ORR) is a key process in sustainable, clean energy conversion and storage technologies, such as metal-air batteries. Currently, commercially available ORR catalysts primarily consist of precious metal platinum-based materials. However, their high cost, scarcity, and instability hinder their widespread application. Therefore, the development of highly active, metal-free electrocatalysts is crucial.

[0003] In the electrocatalytic reaction process, the catalytic activity of polymers depends largely on the molecular structure. Recent progress has shown that polymer materials exhibit good electrocatalytic activity and are expected to replace metal catalysts. By modifying the building blocks, the electronic properties of polymers can be adjusted, thereby regulating their catalytic activity. For example, the introduction of five-membered and six-membered heterocycles into the polymer backbone can introduce multiple weak interactions and regulate the electron density of the polymer, thereby regulating the ORR catalytic activity of the polymer. The building blocks of the polymer can be aromatic structures or quinone structures. However, the limiting current density of existing polymer materials composed of aromatic units is lower than that of platinum-based materials, which limits the preparation of high-performance battery devices. Summary of the Invention

[0004] In view of this, the present invention aims to provide a quinone compound, a preparation method and application thereof, a conjugated polymer containing quinone units, a preparation method and application thereof, and an organic field-effect transistor device. The polymer containing quinone units provided by the present invention exhibits strong intermolecular and intramolecular interactions, a low LUMO energy level, good carrier transport properties, and excellent ORR catalytic activity.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a quinone compound having a structure shown in Formula I:

[0007]

[0008] wherein X comprises carbon or nitrogen;

[0009] R1 and R2 independently include C1-C30 alkyl or C1-C20 alkoxy.

[0010] The present invention provides a method for preparing the quinone compound described in the above technical solution, comprising the following steps:

[0011] reacting compound 1 with a strong base to form a salt to obtain a salt of compound 1;

[0012] The salt of compound 1 is subjected to a selective addition reaction with compound 2 to obtain compound 3;

[0013] The compound 3 is subjected to a dehydroxylation reaction and then oxidized to obtain a quinone compound;

[0014]

[0015] The present invention provides the use of the quinoid compound described in the above technical solution or the quinoid compound prepared by the preparation method described in the above technical solution in the preparation of a conjugated polymer containing a quinoid unit.

[0016] The present invention provides a conjugated polymer containing quinone units, having a structure shown in Formula II:

[0017]

[0018] Wherein, n is an integer from 10 to 50;

[0019] X includes carbon or nitrogen;

[0020] R1 and R2 independently include C1-C30 alkyl or C1-C20 alkoxy;

[0021] It is a conjugated aromatic unit.

[0022] Preferably, the conjugated aromatic unit comprises any one of the following structures:

[0023]

[0024] The present invention provides a method for preparing a conjugated polymer containing quinone units according to the above technical solution, comprising the following steps:

[0025] A quinone compound, a bistin salt of an aromatic monomer, an organic phosphine ligand, a palladium catalyst and an organic solvent are mixed to carry out a coupling polymerization reaction to obtain a conjugated polymer containing quinone units;

[0026] The structural formula of the bistin salt of the aromatic monomer is as follows:

[0027] The present invention provides the use of the conjugated polymer containing quinone-type units described in the above technical solution or the conjugated polymer containing quinone-type units prepared by the preparation method described in the above technical solution in an electrocatalytic oxygen reduction reaction or an organic field-effect transistor device.

[0028] The present invention provides an organic field-effect transistor device, comprising a substrate, source / drain electrodes, a charge transport layer, a dielectric layer and a gate electrode stacked in sequence; the material of the charge transport layer is the conjugated polymer containing quinone-type units described in the above technical solution or the conjugated polymer containing quinone-type units prepared by the preparation method described in the above technical solution.

[0029] Preferably, the substrate comprises a silicon wafer, a glass wafer or a quartz wafer;

[0030] The materials of the source / drain electrodes and the gate electrode independently include one or more of gold, aluminum, iron and molybdenum.

[0031] Preferably, the material of the dielectric layer includes one or more of polymethyl methacrylate, polystyrene and fluorine-containing polymer.

[0032] The quinone compounds provided by the present invention exhibit strong intermolecular and intramolecular interactions. Polymers prepared using these quinone compounds as monomers exhibit strong interchain interactions, good crystallinity, and excellent charge transport properties. Furthermore, the strong electron-withdrawing ability of the quinone compounds can significantly lower the polymer's LUMO energy level, facilitating the binding and reduction of oxygen. These properties provide a new approach for preparing polymer materials with excellent ORR catalytic activity using the quinone compounds provided by the present invention.

[0033] The conjugated polymer containing quinone units provided by the present invention is a copolymer of a quinone compound and a conjugated aromatic monomer. The introduction of the quinone unit not only gives the conjugated polymer containing quinone units strong intermolecular and intramolecular interactions and a low LUMO energy level, but also gives the polymer excellent carrier transport properties, enabling the polymer to catalyze the reduction reaction of oxygen in the absence of carbon nanomaterials and have excellent catalytic activity. As shown in the test results of the embodiment, the conjugated polymer containing quinone units as a catalyst has a limiting current density of up to 7.50 mA / cm 2 , which is higher than the limiting current density of platinum-based materials under the same conditions, providing an effective solution to the current problem of low limiting current density of polymer electrocatalysts.

[0034] The introduction of quinone units not only gives the conjugated polymer containing quinone units strong intermolecular and intramolecular interactions and a low LUMO energy level, but also gives the polymer excellent carrier transport properties. The organic field-effect transistor device using the conjugated polymer containing quinone units provided by the present invention as the charge transport layer shows bipolar transport characteristics, and both electron and hole mobilities can exceed 0.01 cm 2 / V·s. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is the H NMR spectrum of compound 3a;

[0036] Figure 2 is the H NMR spectrum of compound 4a;

[0037] Figure 3 is the H NMR spectrum of compound 3b;

[0038] Figure 4 is the H NMR spectrum of compound 4b;

[0039] Figure 5 The figure is a transfer characteristic curve of an organic field-effect transistor prepared with a conjugated polymer PQ-TZ containing quinone units as a charge transport layer;

[0040] Figure 6 The figure is a transfer characteristic curve of an organic field-effect transistor prepared with a conjugated polymer PNQ-TZ containing quinone units as a charge transport layer;

[0041] Figure 7 The figure is a transfer characteristic curve of an organic field-effect transistor prepared with a conjugated polymer containing quinone units, PNQ-CN, as a charge transport layer;

[0042] Figure 8 The linear scanning curve diagram of the oxygen reduction reaction catalyzed by conjugated polymers PQ-TZ, PNQ-TZ and PNQ-CN containing quinone units as catalysts. DETAILED DESCRIPTION

[0043] The present invention provides a quinone compound having a structure shown in Formula I:

[0044]

[0045] wherein X comprises carbon or nitrogen;

[0046] R1 and R2 independently include C1-C30 alkyl or C1-C20 alkoxy.

[0047] In the present invention, the C1 to C30 alkyl group preferably includes C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl or C30 alkyl; when the number of carbon atoms in the alkyl group is 3 to 20, the alkyl group is preferably a straight-chain alkyl group or a branched-chain alkyl group.

[0048] In the present invention, the C1 to C30 alkoxy group preferably includes a C1 alkoxy group, a C2 alkoxy group, a C3 alkoxy group, a C4 alkoxy group, a C5 alkoxy group, a C6 alkoxy group, a C7 alkoxy group, a C8 alkoxy group, a C9 alkoxy group, a C10 alkoxy group, a C11 alkoxy group, a C12 alkoxy group, a C13 alkoxy group, a C14 alkoxy group, a C15 alkoxy group, a C16 alkoxy group, a C17 alkoxy group, a C18 alkoxy group, a C19 alkoxy group, a C20 alkoxy group, a C21 alkoxy group, a C22 alkoxy group, a C23 alkoxy group, a C24 alkoxy group, a C25 alkoxy group, a C26 alkoxy group, a C27 ​​alkoxy group, a C28 alkoxy group, a C29 alkoxy group or a C30 alkoxy group; when the number of carbon atoms in the alkoxy group is 3 to 20, the alkoxy group is preferably a straight chain alkoxy group or a branched chain alkoxy group.

[0049] In the present invention, R1 and R2 are the same or different.

[0050] In the present invention, when R1 is a C26 branched alkyl group, R2 is a C8 straight chain alkoxy group; the C26 branched alkyl group is preferably Among them, -C 10 H 21 and -C 12 H 25 All are straight-chain alkyl groups.

[0051] The present invention provides a method for preparing the quinone compound described in the above technical solution, comprising the following steps:

[0052] reacting compound 1 with a strong base to form a salt to obtain a salt of compound 1;

[0053] The salt of compound 1 is subjected to a selective addition reaction with compound 2 to obtain compound 3;

[0054] The compound 3 is subjected to a dehydroxylation reaction and then oxidized to obtain a quinone compound;

[0055]

[0056] Wherein, R1 and R2 are the same as R1 and R2 in Formula I.

[0057] In the present invention, the preparation route of the quinone compound is as follows:

[0058]

[0059] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0060] In the present invention, compound 1 is subjected to a salt-forming reaction with a strong base to obtain a salt of compound 1.

[0061] In the present invention, the strong base preferably includes one or more of lithium diisopropylamide (LDA), n-butyl lithium (n-BuLi), and tert-butyl lithium (t-BuLi). In the present invention, the molar ratio of compound 1 to the strong base is preferably 1:2-5, more preferably 1:3-4.

[0062] In the present invention, the salt-forming reaction is preferably carried out in the presence of a first organic solvent. Specifically, compound 1, a strong base and the first organic solvent are mixed to carry out the salt-forming reaction.

[0063] In the present invention, the first organic solvent preferably includes one or more of tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, dichloromethane, and n-hexane; the first organic solvent is preferably an anhydrous organic solvent. In the present invention, the ratio of the amount of compound 1 to the volume of the first organic solvent is preferably 0.01 to 0.2 mol:1 L, more preferably 0.04 to 0.05 mol:1 L.

[0064] In the present invention, the temperature of the salt-forming reaction is preferably -100 to -20°C, more preferably -78°C; the time of the salt-forming reaction is preferably 0.5 to 5 hours, more preferably 1 hour.

[0065] After obtaining the salt of compound 1, the present invention selectively performs an addition reaction on the salt of compound 1 and compound 2 to obtain compound 3.

[0066] In the present invention, the molar ratio of the salt of Compound 1 to Compound 2 is preferably 1:2-10, more preferably 1:2.5-5, and even more preferably 1:2.5-3.

[0067] In the present invention, the selective addition reaction is preferably carried out in the presence of a second organic solvent. Specifically, the salt of compound 1 is mixed with the second organic solvent solution of compound 2 to carry out the selective addition reaction.

[0068] In the present invention, the second organic solvent preferably includes one or more of ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dichloromethane, and n-hexane; the second organic solvent is preferably an anhydrous organic solvent. In the present invention, the ratio of the amount of compound 2 to the volume of the second organic solvent is preferably 0.01 to 0.5 mol:1 L, more preferably 0.1 to 0.45 mol:1 L, and even more preferably 0.3 to 0.4 mol:1 L.

[0069] In the present invention, the temperature of the selective addition reaction is preferably -78 to 25°C, more preferably -78 to 0°C, and further preferably -78 to -50°C; the time of the selective addition reaction is preferably 6 to 24 hours, more preferably 8 to 12 hours.

[0070] After completing the selective addition reaction, the present invention preferably further comprises: subjecting the obtained selective addition reaction system to chloroform extraction, and sequentially washing the obtained organic phase with water, drying over anhydrous MgSO4, removing the solvent under reduced pressure, and separating the organic phase on a silica gel column to obtain compound 3. In the present invention, the eluent used for the silica gel column separation is preferably a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate in the mixed solvent is preferably 5 to 15:1, more preferably 10:1.

[0071] After obtaining compound 3, the present invention performs a dehydroxylation reaction on the compound 3 and then oxidizes it to obtain a quinone compound.

[0072] In the present invention, the dehydroxylation reaction is preferably carried out in the presence of a dehydroxylation agent, an acid and a third organic solvent. Specifically, compound 3, a dehydroxylation agent, an acid and a third organic solvent are mixed to carry out the dehydroxylation reaction.

[0073] In the present invention, the dehydroxylation agent preferably includes one or more of tin dichloride, trimethylsilyl hydride and tributylsilyl hydride; the molar ratio of the compound 3 to the dehydroxylation agent is preferably 1:10-30, more preferably 1:15-20.

[0074] In the present invention, the acid preferably includes one or more of hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluoromethylbenzenesulfonic acid and trifluoroacetic acid; the molar ratio of the compound 3 to the acid is preferably 50-100:1, more preferably 68-75:1.

[0075] In the present invention, the third organic solvent preferably includes one or more of dichloromethane, tetrahydrofuran, cyclohexane, n-hexane, and ethyl acetate. In the present invention, the ratio of the amount of compound 3 to the volume of the third organic solvent is preferably 0.1 to 1 mol:1 L, more preferably 0.15 to 0.4 mol:1 L.

[0076] In the present invention, the temperature of the dehydroxylation reaction is preferably 0 to 50° C., more preferably room temperature; the time of the dehydroxylation reaction is preferably 5 to 60 min, more preferably 20 min.

[0077] After the dehydroxylation reaction is completed, the present invention preferably further comprises: mixing the resulting dehydroxylation reaction system with a base, and extracting with dichloromethane. In the present invention, the base preferably comprises an inorganic base and / or an organic base; the organic base is preferably an organic amine, and the organic amine preferably comprises one or more of triethylamine, piperidine, and pyridine; the inorganic base preferably comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, and lithium hydroxide; the molar ratio of the acid to the base is preferably 1:1 to 3, more preferably 1:2 to 2.3; the base serves to remove the acid from the system.

[0078] In the present invention, the oxidant used for the oxidation preferably includes one or more of 2,3-dichloro-5,6-dicyanobenzoquinone, bromine water, oxygen, and tetrachloro-p-benzoquinone. In the present invention, when the oxidant is oxygen, the pressure of the oxygen is preferably 0.01 to 0.2 MPa, more preferably 0.1 to 0.15 MPa. When the oxidant is not oxygen, the molar ratio of compound 3 to the oxidant is preferably 1:1 to 5, more preferably 1:2 to 3.

[0079] In the present invention, the temperature of the oxidation reaction is preferably 0 to 50° C., more preferably room temperature; the time of the oxidation reaction is preferably 10 to 60 minutes, more preferably 20 to 40 minutes.

[0080] After the oxidation reaction is completed, the present invention preferably further comprises: sequentially washing the resulting oxidation reaction system with water, drying over anhydrous MgSO4, removing the solvent under reduced pressure, and separating the mixture on a silica gel column to obtain a quinone compound. In the present invention, the eluent used for the silica gel column separation is preferably a mixed solvent of petroleum ether and dichloromethane, wherein the volume ratio of petroleum ether to dichloromethane in the mixed solvent is preferably 1 to 4:1, more preferably 2:1.

[0081] The present invention provides the use of the quinoid compound described in the above technical solution or the quinoid compound prepared by the preparation method described in the above technical solution in the preparation of a conjugated polymer containing a quinoid unit.

[0082] The present invention provides a conjugated polymer containing quinone units, having a structure shown in Formula II:

[0083]

[0084] wherein n is an integer of 10 to 50, preferably 10, 15, 20, 25, 30, 35, 40, 45 or 50; X comprises hydrogen or nitrogen; R1 and R2 independently comprise a C1 to C30 alkyl group or a C1 to C20 alkoxy group; R1 and R2 are the same as R1 and R2 in Formula I and are not further described herein; It is a conjugated aromatic unit.

[0085] In the present invention, the conjugated aromatic unit preferably includes any one of the following structures:

[0086]

[0087] In the present invention, when R1 is a C26 branched alkyl group, R2 is a C8 straight chain alkoxy group, for The C26 branched alkyl group is preferably Among them, -C 10 H 21 and -C 12 H25 All are straight-chain alkyl groups.

[0088] The present invention provides a method for preparing a conjugated polymer containing quinone units according to the above technical solution, comprising the following steps: mixing a quinone compound, a bistin salt of an aromatic monomer, an organic phosphine ligand, a palladium catalyst, and an organic solvent (denoted as a fourth organic solvent), and performing a coupling polymerization reaction to obtain a conjugated polymer containing quinone units;

[0089] The structural formula of the bistin salt of the aromatic monomer is as follows:

[0090] In the present invention, the aromatic monomer more preferably includes 5,5'-bis(trimethyltinyl)-2,2'-bithiazole or 5,5'-bis(trimethyltinyl)-3,3'-dicyano-2,2'-bithiophene.

[0091] In the present invention, the molar ratio of the quinone compound to the bistin salt of the aromatic monomer is preferably 0.9 to 1:1, more preferably 1:1.

[0092] In the present invention, the organophosphine ligand preferably includes one or more of tri(o-methylphenyl)phosphine (P(o-tol)3), triphenylphosphine, tributylphosphine, and tricyclohexylphosphine. In the present invention, the molar ratio of the quinone compound to the organophosphine ligand is preferably 1:4-16, more preferably 1:8-10.

[0093] In the present invention, the valence state of palladium in the palladium catalyst is preferably zero or divalent; the palladium catalyst preferably includes one or more of tris(dibenzylacetone)dipalladium (Pd2(dba)3), tetrakistriphenylphosphine palladium (Pd(PPh3)4), palladium acetate (Pd(OAc)2), and 1,1'-bis(diphenylphosphinodiphenylphosphinodichloropalladium) (PdCl2(dppf)). In the present invention, the molar ratio of the quinone compound to the palladium catalyst is preferably 1:1-4, more preferably 1:2-3.

[0094] In the present invention, the fourth organic solvent preferably includes one or more of tetrahydrofuran, toluene, and chlorobenzene; the fourth organic solvent is preferably an anhydrous organic solvent. In the present invention, the ratio of the amount of the quinone compound to the volume of the fourth organic solvent is preferably 10-20 mmol:1 L, more preferably 16.5-18.5 mmol:1 L.

[0095] In the present invention, the temperature of the coupled polymerization reaction is preferably 20 to 140° C., more preferably 80 to 120° C., and further preferably 100 to 110° C.; the time of the coupled polymerization reaction is preferably 24 to 72 hours, more preferably 40 to 48 hours; the coupled polymerization reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably an inert atmosphere, more preferably helium or argon.

[0096] After completing the coupling polymerization reaction, the present invention preferably further comprises: cooling the obtained coupling polymerization reaction system to room temperature, placing it in a first alcohol solvent for sedimentation, dissolving the obtained precipitate in chloroform, removing palladium with sodium diethyldithiocarbamate trihydrate, washing with water, sedimentation, filtering, extracting with acetone, n-hexane and chloroform in sequence, sedimenting in a second alcohol solvent, and drying the obtained solid component to obtain a conjugated polymer containing quinone units. In the present invention, the first alcohol solvent and the second alcohol solvent independently preferably include one or more of methanol, ethanol and isopropanol. In the present invention, the drying temperature is preferably 20 to 80°C, more preferably 25 to 35°C; the drying time is preferably 6 to 24 hours, more preferably 12 to 16 hours.

[0097] The present invention provides the use of the conjugated polymer containing quinoid units described in the above technical solution or the conjugated polymer containing quinoid units prepared by the preparation method described in the above technical solution in electrocatalytic oxygen reduction reactions or organic field-effect transistor devices. The conjugated polymer containing quinoid units provided by the present invention has excellent charge transport properties, and the prepared organic field-effect transistor device exhibits bipolar transport characteristics, with both electron and hole mobilities exceeding 0.01 cm 2 Because the conjugated polymer containing quinone units provided by the present invention has excellent charge transport capability, the polymer can still efficiently electrocatalyze oxygen reduction reaction in the absence of carbon nanomaterials.

[0098] The present invention also provides an organic field-effect transistor device, comprising a substrate, source / drain electrodes, a charge transport layer, a dielectric layer and a gate electrode stacked in sequence; the material of the charge transport layer is the conjugated polymer containing quinone-type units described in the above technical solution or the conjugated polymer containing quinone-type units prepared by the preparation method described in the above technical solution.

[0099] In the present invention, the substrate preferably includes a silicon wafer, a glass wafer or a quartz wafer; the silicon wafer is preferably a heavily doped n-type silicon wafer.

[0100] In the present invention, the material of the source / drain electrodes preferably includes one or more of gold, aluminum, iron, and molybdenum, more preferably gold, aluminum, iron, or molybdenum, and even more preferably gold. In the present invention, the thickness of the source / drain electrodes is preferably 10 to 60 nm, more preferably 20 to 50 nm, and even more preferably 30 to 40 nm.

[0101] In the present invention, the thickness of the charge transport layer is preferably 20 to 60 nm, more preferably 30 to 50 nm, and even more preferably 30 to 40 nm.

[0102] In the present invention, the material of the dielectric layer preferably includes one or more of polymethyl methacrylate (PMMA), polystyrene, and a fluoropolymer, more preferably polymethyl methacrylate; the fluoropolymer preferably includes Cytop (perfluoro(1-butenyl vinyl ether)polymer). In the present invention, the thickness of the dielectric layer is preferably 200 to 1000 nm, more preferably 300 to 800 nm, and even more preferably 400 to 500 nm; the dielectric constant of the dielectric layer is preferably 3 to 6 nF / cm 2 , more preferably 4 to 5 nF / cm 2 .

[0103] In the present invention, the gate electrode is preferably made of one or more of gold, aluminum, iron, and molybdenum, more preferably gold, aluminum, iron, or molybdenum, and even more preferably aluminum. In the present invention, the gate electrode preferably has a thickness of 50 to 300 nm, more preferably 100 to 250 nm, and even more preferably 150 to 200 nm.

[0104] In the present invention, the channel length of the organic field effect transistor device is preferably 4-6 mm, more preferably 4.5-5.5 mm, and further preferably 5 mm; the channel width of the organic field effect transistor device is preferably 70-100 μm, more preferably 80-90 μm.

[0105] In the present invention, the preparation method of the organic field-effect transistor device preferably includes the following steps: first depositing source / drain electrodes, first coating a conjugated polymer solution containing quinone units, annealing, second coating a dielectric layer material solution, and second depositing a gate electrode on the surface of a substrate to obtain an organic field-effect transistor device.

[0106] The present invention has no particular limitation on the conditions for the first deposition, as long as the source / drain electrodes having a thickness of 10 to 60 nm can be obtained.

[0107] In the present invention, the concentration of the conjugated polymer solution containing quinone-type units is preferably 3 to 10 mg / mL, more preferably 5 to 8 mg / mL; the solvent in the conjugated polymer solution containing quinone-type units preferably includes one or more of o-dichlorobenzene, chloroform, chlorobenzene, and tetrachloroethane, more preferably o-dichlorobenzene. In the present invention, the first coating method is preferably spin coating, the spin coating speed is preferably 1000 to 5000 r / min, more preferably 2000 to 3000 r / min; the spin coating time is preferably 20 to 120 s, more preferably 45 to 100 s.

[0108] In the present invention, the annealing temperature is preferably 80-300°C, more preferably 100-200°C; the annealing time is preferably 5-30 minutes, more preferably 10-15 minutes; the purpose of the annealing is to remove residual solvent and improve the stacking order of material molecules.

[0109] In the present invention, the concentration of the dielectric layer material solution is preferably 60-110 mg / mL, more preferably 70-85 mg / mL. The solvent in the dielectric layer material solution preferably includes one or more of n-butyl acetate, ethyl acetate, and propyl acetate, more preferably n-butyl acetate. In the present invention, the second coating method is preferably spin coating, the spin coating speed is preferably 1000-4000 r / min, more preferably 1500-2500 r / min, and the spin coating time is preferably 80-160 s, more preferably 100-120 s.

[0110] After completing the second coating, the present invention preferably further comprises drying the obtained wet dielectric layer. The drying temperature is preferably 70-150° C., more preferably 80-100° C.; the drying time is preferably 20-60 min, more preferably 40-50 min.

[0111] The present invention has no particular limitation on the conditions of the second deposition, as long as a gate electrode with a thickness of 50 to 300 nm can be obtained.

[0112] The organic field-effect transistor device provided by the present invention uses a conjugated polymer containing quinone units as a charge transport layer. The polymer has excellent charge transport performance. The organic field-effect transistor device shows bipolar transport characteristics, and both electron and hole mobilities can exceed 0.01 cm 2 / V·s.

[0113] To further illustrate the present invention, the following detailed description of quinone compounds, preparation methods and applications thereof, conjugated polymers containing quinone units, preparation methods and applications thereof, and organic field-effect transistor devices is provided with reference to the following examples. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0114] Example 1

[0115]

[0116] Compound 1a (1.65 mmol) was dissolved in anhydrous THF (40 mL), and lithium diisopropylamide (LDA, 2M, 2.47 mL) was added dropwise at -78 ° C. The reaction system was stirred at -78 ° C for 1 h, and then a THF solution (10 mL) of compound 2a (4.12 mmol) was slowly added. After reacting for 12 h, the mixture was extracted with chloroform, and the resulting organic phase was washed with water, dried over anhydrous MgSO4, and the solvent was removed under reduced pressure and separated with a silica gel column (petroleum ether: ethyl acetate volume ratio = 10:1) to obtain compound 3a (light yellow solid, 1.59 g, yield 60%). The H NMR spectrum of compound 3a is shown as follows Figure 1 As shown, 1 HNMR(400MHz,CD2Cl2)δ7.11(d,J=3.7Hz,4H),6.97(s,2H),4.17(t,J=6.3Hz,4H),3.68-3. 56(m,2H),3.49-3.38(m,2H),1.62-1.49(m,12H),1.32-1.00(m,102H),0.86-0.68(m,18H).

[0117] Compound 3a (0.685 mmol) and stannous chloride (13.70 mol) were dissolved in anhydrous dichloromethane (40 mL), and trifluoromethanesulfonic acid (0.01 mmol) was added. After stirring at room temperature for 20 min, triethylamine (0.02 mmol) was added and extracted with dichloromethane. The extract was oxidized in air for 40 min under stirring at room temperature, then washed with water, dried over anhydrous MgSO4, and the solvent was removed under reduced pressure and separated on a silica gel column (petroleum ether: dichloromethane volume ratio = 2:1) to obtain compound 4a (dark purple solid, 638 mg, yield 59%). The H NMR spectrum of compound 4a is shown as follows: Figure 2 As shown, 1 H NMR (400MHz, CDCl3) δ7.70(d,J=8.2Hz,2H),7.03(d,J=8.2Hz,2H),6.79(s,2H),4.71(t,J=6.8Hz,4 H),3.62(t,J=7.2Hz,4H),2.04-1.94(m,4H),1.53(s,9H),1.50-1.14(m,103H),0.81-0.76(m,18H). 13C NMR (100MHz, CDCl3) δ173.77,167.32,155.53,141.60,126.46,123.86,1 21.19,120.71,111.29,110.84,77.32,77.00,76.68,73.74,40.32,37.21 ,33.55,31.92,30.87,30.15,29.72,29.67,29.46,29.37,28.70,27.24,2 6.70,25.96,25.08,22.69,19.67,14.17,14.12.HRMS(MALDI-TOF):Calcd for C 90 H 146 Br2N4O4S2:1568.9152[M] + ;found:1568.9100.

[0118] Example 2

[0119]

[0120] Compound 1a (2.36 mmol) was dissolved in anhydrous THF (80 mL), and lithium diisopropylamide (LDA, 2M, 4.94 mL) was added dropwise at -78 ° C. The reaction system was stirred at -78 ° C for 1 h, and then a THF solution (20 mL) of 2b (5.42 mmol) was slowly added. After reacting for 12 h, the mixture was extracted with chloroform, and the resulting organic phase was washed with water, dried over anhydrous MgSO4, and the solvent was removed under reduced pressure and separated with a silica gel column (petroleum ether: ethyl acetate volume ratio = 10:1) to obtain compound 3b (light yellow solid, 2.3 g, yield 61%). The H NMR spectrum of compound 3b is shown as follows Figure 3 As shown, 1 HNMR (400MHz, CDCl3) δ7.45 (dd, J=7.6, 6.1Hz, 2H), 7.18 (dd, J=7.6, 3.5Hz, 2H), 4.30 (td, J=6.5, 2.7Hz, 4H), 3.79 (t, J = 7.3Hz, 4H), 1.79-1.50 (m, 12H), 1.45-1.12 (m, 102H), 0.95-0.79 (m, 18H).

[0121] Compound 3b (0.808 mmol) and stannous chloride (13.70 mol) were dissolved in anhydrous dichloromethane (45 mL), and trifluoromethanesulfonic acid (0.011 mmol) was added. After stirring at room temperature for 20 min, triethylamine (0.025 mmol) was added and the mixture was extracted with dichloromethane. The extract was oxidized in air for 40 min under stirring at room temperature, then washed with water, dried over anhydrous MgSO4, and the solvent was removed under reduced pressure and separated on a silica gel column (petroleum ether: dichloromethane volume ratio = 2:1) to obtain compound 4b (dark purple solid, 800 mg, yield 63%). The H NMR spectrum of compound 4b is shown in FIG. Figure 4 As shown, 1 HNMR (400MHz, CDCl3) δ7.75(d,J=7.8Hz,2H),6.98(d,J=7.8Hz,2H),4.69(t,J=6.7Hz,4H),3.78(t,J=7.2H z,4H),2.04-1.94(m,4H),1.73-1.61(m,4H),1.59-1.46(m,4H),1.42-1.08(m,102H),0.88-0.74(m,18H). 13 C NMR (100MHz, CDCl3) δ173.77,167.32,155.53,141.60,126.46,123.86,1 21.19,120.71,111.29,110.84,77.32,77.00,76.68,73.74,40.32,37.21 ,33.55,31.92,30.87,30.15,29.72,29.67,29.46,29.37,28.70,27.24,2 6.70,25.96,25.08,22.69,19.67,14.17,14.12.HRMS(MALDI-TOF):Calcd for C 88 H 144 Br2N6O4S2:1570.9057[M] + ;found:1570.9106.

[0122] Example 3

[0123] Copolymerization of quinone monomer compound 4a and bithiazole monomer (PQ-TZ)

[0124]

[0125] Under argon protection, compound 4a (65.5 μmol) and 5,5'-bis(trimethyltin)-2,2'-bithiazole (compound 5, 65.5 μmol), Pd2(dba)3 (2 mol%), P(o-tol)3 (8 mol%), and anhydrous toluene (4.0 mL) were added to a Schlenk tube and heated to 110°C for 48 h. The reaction solution was cooled to room temperature and poured into methanol. The collected precipitate was dissolved in chloroform (60 mL) and palladium was removed with sodium diethyldithiocarbamate trihydrate. The solution was washed with water, settled, and filtered. The solution was extracted with acetone, n-hexane, and chloroform in a Soxhlet extractor, settled in methanol, and the resulting solid component was dried to constant weight to obtain a conjugated polymer containing quinone units, PQ-TZ (black solid, 97.1 mg, yield 92%). The structural characterization data of PQ-TZ are as follows: elemental analysis, theoretical value (C 96 H 150 N6O4S4) n : C 72.95, H 9.57, N 5.32, S 8.11; Found: C 71.48, H 9.23, N 5.1, S 7.57; Gel Permeation Chromatography (GPC): M n =16.1 kDa,

[0126] Example 4

[0127] Copolymerization of quinone monomer compound 4b and bithiazole monomer (PNQ-TZ)

[0128]

[0129] Under argon protection, compound 4b (84.5 μmol) and 5,5'-bis(trimethyltin)-2,2'-bithiazole (compound 5, 84.5 μmol), Pd2(dba)3 (2 mol%), P(o-tol)3 (8 mol%) and anhydrous toluene (4.5 mL) were added to a Schlenk tube and heated to 110°C for 48 hours. The reaction solution was cooled to room temperature and poured into methanol. The collected precipitate was dissolved in chloroform (60 mL) and palladium was removed with sodium diethyldithiocarbamate trihydrate. The solution was washed with water, settled, and filtered. The solution was extracted with acetone, n-hexane, and chloroform in a Soxhlet extractor, settled in methanol, and the resulting solid component was dried to constant weight to obtain a conjugated polymer containing quinone units, PNQ-TZ (black solid, 126.5 mg, yield 95%). The structural characterization data of PNQ-TZ are as follows: elemental analysis, theoretical value (C 94 H 148 N8O4S4) n: C 71.34, H 9.43, N 7.08, S 8.10; Found: C 71.19, H 9.18, N6.92, S 7.87; Gel Permeation Chromatography (GPC): M n =10.1kDa,

[0130] Example 5

[0131] Copolymerization of quinone monomer compound 4b and cyanobithiophene monomer (PNQ-CN)

[0132]

[0133] Under argon, compound 4b (63.5 μmol), 5,5'-bis(trimethyltinyl)-3,3'-dicyano-2,2'-bithiophene (compound 6, 63.5 μmol), Pd2(dba)3 (2 mol%), P(o-tol)3 (8 mol%), and anhydrous toluene (4.0 mL) were added to a Schlenk tube and heated to 110°C for 48 h. The reaction solution was cooled to room temperature and poured into methanol. The collected precipitate was dissolved in chloroform (60 mL) and palladium was removed with sodium diethyldithiocarbamate trihydrate. The product was washed with water, allowed to settle, and filtered. The product was extracted in a Soxhlet extractor with acetone, n-hexane, and chloroform, followed by settling in methanol. The resulting solid component was dried to constant weight to obtain a conjugated polymer containing quinone units, PNQ-CN (black solid, 100.2 mg, 93% yield). The structural characterization data of PNQ-CN are as follows: elemental analysis, theoretical value (C 98 H 148 N8O4S4) n : C 72.19, H 9.15, N 6.87, S 7.86; Found: C 72.36, H 9.15, N 6.52S 7.59; Gel Permeation Chromatography (GPC): M n =14.0kDa,D=1.59.

[0134] Test Example 1

[0135] The performance of organic field-effect transistor devices prepared with conjugated polymers PQ-TZ, PNQ-TZ or PNQ-CN containing quinone units as charge transport layers is studied. The device comprises a heavily doped n-type silicon wafer, source / drain electrodes, a charge transport layer, a dielectric layer and a gate electrode stacked in sequence.

[0136] Using a heavily doped n-type silicon wafer as a substrate, a 40nm thick layer of gold is deposited to form the source / drain electrodes. PQ-TZ, PNQ-TZ, or PNQ-CN is dissolved in dichlorobenzene to obtain a 6mg / mL solution of a conjugated polymer containing quinone units. The conjugated polymer solution containing quinone units is spin-coated on the surface of the source / drain electrodes at a speed of 2000r / min and then dried to form a charge transport layer. The spin-coating time is 45s and the charge transport layer thickness is 30nm. The device is then annealed at 150°C for 15min. A PMMA n-butyl acetate solution (PMMA concentration is 80mg / mL) is then spin-coated at 2000r / min for 120s to form a dielectric layer with a thickness of 600nm. The layer is dried at 95°C for 45min. Finally, aluminum is deposited to a thickness of 100nm to form the gate electrode. The channel length and width of the device prepared by the present invention are 80μm and 5600μm, and the dielectric constant of the dielectric layer is 4.6nF / cm 2 ,The device is measured in air using a Keithley 4200 semiconductor tester. Figure 5 、 Figure 6 and Figure 7 The transfer characteristic curves of organic field-effect transistor devices based on PQ-TZ, PNQ-TZ, and PNQ-CN were tested in air. The hole / electron mobility of PQ-TZ, PNQ-TZ, or PNQ-CN was calculated to be 0.017 / 0.010 cm-3, respectively. 2 / V·s, 0.016 / 0.024cm 2 / V·s and 0.028 / 0.017cm 2 / V·s.

[0137] Test Example 2

[0138] Conjugated polymers containing quinone units PQ-TZ, PNQ-TZ or PNQ-CN as catalysts for electrocatalytic oxygen reduction reaction

[0139] The oxygen reduction reaction (ORR) catalytic activities of PQ-TZ, PNQ-TZ, and PNQ-CN were measured in a three-electrode, single-chamber cell equipped with a Pt wire counter electrode and an Ag / AgCl reference electrode at room temperature. 8 μL of a 6 mg / mL chloroform solution of a conjugated polymer containing quinone units was drop-coated onto the electrode. Linear sweep voltammetry was then performed at a scan rate of 10 mV / s in an oxygen-saturated KOH (KOH concentration, 0.1 mol / L) electrolyte solution. The tests were performed at different electrode rotation rates (400 rpm, 800 rpm, 1200 rpm, 1600 rpm, 2000 rpm, and 2500 rpm). Figure 8The linear scan curves of oxygen reduction reaction catalyzed by PQ-TZ, PNQ-TZ and PNQ-CN are shown. The half-wave potentials of PQ-TZ, PNQ-TZ and PNQ-CN are calculated to be 0.69 V, 0.74 V and 0.71 V (relative to reversible hydrogen electrode), and the limiting current density is 4.97 mA / cm 2 , 7.50mA / cm 2 and 6.18 mA / cm 2 .

[0140] Although the above embodiments provide a detailed description of the present invention, they are only part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on the embodiments of the present invention without creative work, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A quinone compound having the structure shown in Formula I: in, X is selected from carbon or nitrogen; R1 and R2 are independently selected from C1-C30 alkyl or C1-C20 alkoxy.

2. The method for preparing the quinone compound according to claim 1, comprising the following steps: reacting compound 1 with a strong base to form a salt to obtain a salt of compound 1; The salt of compound 1 is subjected to a selective addition reaction with compound 2 to obtain compound 3; The compound 3 is subjected to a dehydroxylation reaction and then oxidized to obtain a quinone compound; 3. Use of the quinoid compound according to claim 1 or the quinoid compound prepared by the preparation method according to claim 2 in the preparation of a conjugated polymer containing a quinoid unit.

4. A conjugated polymer containing quinone units having the structure shown in Formula II: in, n is an integer from 10 to 50; X is selected from carbon or nitrogen; R1 and R2 are independently selected from C1-C30 alkyl or C1-C20 alkoxy; It is a conjugated aromatic unit.

5. The conjugated polymer containing quinone units according to claim 4, characterized in that The conjugated aromatic unit is selected from any one of the following structures:

6. The method for preparing the conjugated polymer containing quinone units according to claim 4 or 5, comprising the following steps: A quinone compound, a bistin salt of an aromatic monomer, an organic phosphine ligand, a palladium catalyst and an organic solvent are mixed to carry out a coupling polymerization reaction to obtain a conjugated polymer containing quinone units; The structural formula of the bistin salt of the aromatic monomer is as follows:

7. Use of the conjugated polymer containing quinone units according to claim 4 or 5, or the conjugated polymer containing quinone units obtained by the preparation method according to claim 6, in an electrocatalytic oxygen reduction reaction or an organic field-effect transistor device.

8. An organic field effect transistor device comprising a substrate, a source / drain electrode, a charge transfer layer, a dielectric layer and a gate electrode stacked in sequence; characterized in that: The material of the charge transport layer is the conjugated polymer containing quinone-type units according to claim 4 or 5 or the conjugated polymer containing quinone-type units prepared by the preparation method according to claim 6.

9. The organic field effect transistor device according to claim 8, characterized in that: The substrate is selected from a silicon wafer, a glass wafer or a quartz wafer; The materials of the source / drain electrodes and the gate electrode are independently selected from one or more of gold, aluminum, iron and molybdenum.

10. The organic field effect transistor device according to claim 8, characterized in that: The material of the dielectric layer is selected from one or more of polymethyl methacrylate, polystyrene and fluorine-containing polymer.

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