WO2022262159A1 - 一种n型共轭聚合物及其制备方法与应用 - Google Patents

一种n型共轭聚合物及其制备方法与应用 Download PDF

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WO2022262159A1
WO2022262159A1 PCT/CN2021/124880 CN2021124880W WO2022262159A1 WO 2022262159 A1 WO2022262159 A1 WO 2022262159A1 CN 2021124880 W CN2021124880 W CN 2021124880W WO 2022262159 A1 WO2022262159 A1 WO 2022262159A1
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formula
conjugated polymer
type conjugated
group
corresponding enol
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French (fr)
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黄飞
唐浩然
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to EP21945739.7A priority Critical patent/EP4357384A4/en
Priority to US18/571,477 priority patent/US20240301132A1/en
Publication of WO2022262159A1 publication Critical patent/WO2022262159A1/zh
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Definitions

  • the invention belongs to the technical field of n-type organic semiconductor materials, and in particular relates to an n-type conjugated polymer and its preparation method and application.
  • conjugated polymers contains a conjugated system composed of delocalized ⁇ electrons, and thus exhibits special optical and electrical properties, which has attracted widespread attention of scientists.
  • the semiconductor materials used in optoelectronic materials and devices not only have the electronic characteristics of metals or semiconductors, but also have the characteristics of low cost, light weight, low temperature processing, and easy large-scale preparation, which meet the requirements of industrialized large-scale production and large-scale promotion. Great business prospects.
  • conjugated polymers have achieved a series of remarkable achievements in the fields of organic solar cells (OPV), organic light-emitting diodes (OLED), organic field-effect transistors (OFETs) and organic thermoelectrics (OTEs).
  • PEDOT:PSS as one of the p-type materials that have been commercially applied, has achieved great success in semiconductor devices due to its high conductivity and printability.
  • n-type organic materials especially organic n-type conjugated polymers with high conductivity, lack corresponding synthesis strategies. Limited by the low electron mobility of n-type organic semiconductor materials, poor air stability, and the need for long insulating alkyl chains to achieve solution processing and other factors, the development of n-type organic semiconductor materials with high conductivity, simple synthesis, low cost, and solution processability Type organic semiconductor materials are currently the focus of research.
  • 3,7-Dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione contains two strong electron-withdrawing functional groups, which can effectively reduce the minimum unoccupied Orbital (LUMO), which is beneficial to improve the electron mobility of the polymer and ensure the stability of the n-type doping of the polymer.
  • LUMO unoccupied Orbital
  • patent application CN108699073 discloses a semiconducting polymer and its synthesis method, the structure of the semiconducting polymer is
  • one of the raw materials used in the preparation of the polymer is tetraketone A It is a kind of intermediate after oxidation reaction. The synthesis of this intermediate requires additional process costs, resulting in uneconomical synthetic routes and difficult commercialization. Simultaneously part of the tetraketone A structure, such as In the prior art, no preparation method is actually disclosed, and it is difficult to obtain a polymer preparation method suitable for commercialization through the published literature.
  • the polymers disclosed above do not involve any n-type conductive properties, or the relevant data are not ideal. Moreover, the disclosed polymer structures all contain alkyl side chains, and the polymer structures and preparation methods that can still realize solution processing without alkyl chains have not been reported.
  • the object of the present invention is to provide an n-type conjugated polymer and a preparation method thereof.
  • the raw materials used in the method of the present invention are aromatic diketones with active methylene groups, and in the presence of an oxidizing agent, the n-type conjugated polymer can be directly obtained through polymerization reaction.
  • the reaction does not require noble metal catalysis, is insensitive to the reaction atmosphere, has simple process and low cost, and is suitable for commercial application.
  • the n-type conjugated polymer obtained by the method of the invention has good solubility in common organic solvents, and can realize solution processing. At the same time, the n-type conjugated polymer can be used in organic photoelectric devices to achieve excellent photoelectric effects.
  • Another object of the present invention is to provide the application of the n-type conjugated polymer prepared by the above method.
  • the n-type conjugated polymer is used in organic photoelectric devices.
  • the n-type conjugated polymer of the present invention is used in organic solar cells as an electron transport layer; or as a thermoelectric material or electromagnetic shielding material.
  • An n-type conjugated polymer is a homopolymer or a copolymer, and the n-type conjugated polymer includes one or more polymerized units, and the polymerized unit is a formula I structure and/or a formula II structure, and/or its corresponding Enol transformation form:
  • the structure of the n-type conjugated polymer is specifically formula I, formula II, the structure composed of formula I and formula II, the structure composed of formula I and formula I, or the structure composed of formula II and formula II, and the structure composed of formula II
  • the structure composed of formula II contains one or more formula I, contains one or more formula II, formula I is the same or different, and formula II is the same or different.
  • X is independently selected from O, S, Se, Te or NR 1 ;
  • the R 1 is selected from a hydrogen atom, an alkyl group, an alkylene group (R'-C n' H 2n' , R' is a substituent, and C n' H 2n' is an alkylene group), an alkyl derivative, an alkylene group one or more of alkyl derivatives;
  • the alkyl derivative refers to one or more carbons on the alkyl group replaced by one or more of oxygen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, nitro group a replacement;
  • One or more hydrogens on the alkyl derivative are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkyne;
  • n is a positive integer
  • the M is a conjugated part in an n-type conjugated polymer structure, and the structure of the M is selected from one of aromatic rings, aromatic heterocyclic rings, fused aromatic rings, and fused aromatic heterocyclic rings;
  • the aromatic ring refers to a ring structure with a conjugated planar ring system, and the bonding between atoms is covered by a cloud of delocalized ⁇ electrons.
  • benzene ring and its derivatives Such as benzene ring and its derivatives.
  • the aromatic heterocyclic ring refers to a conjugated planar ring system, and the bonding between atoms is covered by a delocalized ⁇ electron cloud; and the atoms constituting the ring contain at least one heteroatom (such as N, O, S, etc.) ring structure.
  • heteroatom such as N, O, S, etc.
  • the fused aromatic ring refers to a structure that has a conjugated planar ring system, and the bonding between atoms is formed by the fusion of two or more aromatic rings covered by a delocalized ⁇ electron cloud (that is, sharing ring edges).
  • a delocalized ⁇ electron cloud that is, sharing ring edges.
  • the fused aromatic heterocyclic ring refers to a conjugated planar ring system, the bonding between atoms is a structure formed by the fusion of two or more aromatic rings covered by a delocalized ⁇ electron cloud, and at least one of the rings is composed of
  • atoms also contain at least one heteroatom (such as N, O, S, etc.). Such as quinoline, indole and their derivatives.
  • the n-type highly conductive conjugated polymer has multiple resonance forms.
  • M as an example of a benzene ring structure, including but not limited to the following resonance forms:
  • the n-type highly conductive conjugated polymer has resonance forms including but not limited to:
  • Wavy lines indicate segments of conjugated polymers.
  • the content of the present invention is expressed in the first resonance form.
  • the structure of M is selected from the following structures:
  • the X 2 -X 4 are independently selected from O, S, Se, Te or NR 1 ;
  • the R 2 -R 5 are independently selected from one or more of hydrogen atom, hydroxyl, nitro, halogen, cyano, nitro, alkyl, and alkyl derivatives;
  • One or more carbons on the alkyl derivative are substituted by one or more of oxygen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, nitro group;
  • One or more hydrogens on the alkyl derivative are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkyne.
  • the dotted line in the aromatic ring Indicates the mutual fusion with adjacent five-membered rings or four-membered rings, that is, the sharing of ring edges.
  • the structure of M is expressed as , the actual structure of the n-type conjugated polymer it represents is:
  • n-type conjugated polymer is a homopolymer or a copolymer
  • the structure of the n-type conjugated polymer is selected from one of the following structures, or its corresponding enol conversion form:
  • the n-type conjugated polymer when the n-type conjugated polymer is a copolymer, the n-type conjugated polymer includes at least two polymerized units;
  • each polymerization unit is independently selected from the following structures:
  • the R 1 is selected from one or more of a hydrogen atom, an alkyl group, and an alkyl derivative
  • One or more carbons on the alkyl derivative are substituted by one or more of oxygen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, nitro group;
  • One or more hydrogens on the alkyl derivative are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkyne;
  • n1-n6 are independently positive integers
  • the M is a conjugated part in the n-type conjugated polymer structure, and the structure of the M is selected from one of aromatic rings, aromatic heterocyclic rings, fused aromatic rings, and fused aromatic heterocyclic rings.
  • R 1 and M are as defined in formula I and formula II above.
  • the preparation method of the n-type conjugated polymer comprises the steps of:
  • reaction monomer reacts under the action of an oxidizing substance to obtain an n-type conjugated polymer.
  • reaction monomer is and / or and/or its corresponding enol conversion form
  • the corresponding enol conversion form is selected from one or more of the following structures:
  • M and X are as defined above for the n-type conjugated polymer.
  • the reactive monomer is a compound of the same structure
  • the reactive monomers are compounds of different structures; that is, the reactive monomers are two or more of the compounds of formula I' or two or more of the compounds of II', or their corresponding enol formulas Transformation form; Or reaction monomer is formula I' compound and II' compound, and/or its corresponding enol transformation form;
  • the preparation method of the n-type conjugated polymer can also be:
  • step 2) Using a solvent as a reaction medium, different polymer units in step 1) undergo further copolymerization reaction under the action of an oxidizing substance to obtain an n-type conjugated polymer.
  • the different polymerized units are preferably two or more of the following structures, and/or their corresponding enol conversion forms:
  • the copolymer can be a binary copolymer or a multiple copolymer, and different polymer units can be polymerized with each other to form a new long-chain copolymer.
  • the structure of the copolymer can be but not limited to one of the following structures:
  • the oxidizing substance is selected from one or more mixtures of organic oxidizing substances and inorganic oxidizing substances.
  • the oxidizing substance is oxygen, peroxide, metal halide, persulfate, perborate, hypohalite, halide, quinone compound, perbenzoic acid compound more than one of .
  • the above-mentioned oxidizing substances can be but not limited to: such as oxygen, hydrogen peroxide, sodium peroxide, potassium peroxide, calcium peroxide, zinc peroxide, copper peroxide, iron nitrate, zinc nitrate, nickel nitrate, Aluminum nitrate, magnesium nitrate, ammonium nitrate, ferric fluoride, ferric chloride, ferric bromide, ferric iodide, sodium perchlorate, potassium perchlorate, sodium perbromate, potassium perbromate, sodium periodate, potassium periodate , potassium perchlorate, sodium perchlorate, potassium perbromate, sodium perbromate, magnesium perchlorate, sodium persulfate, potassium persulfate, magnesium persulfate, zinc persulfate, iron persulfate, copper persulfate, calcium persulfate, Potassium perborate, zinc perborate, magnesium perborate, calcium perborate, sodium hypofluorite, potassium
  • the solvent is selected from solvent 1, or solvent 2, or a mixture of solvent 1 and solvent 2;
  • the solvent 1 is selected from water, nitrile solvents, aromatic solvents, alicyclic hydrocarbon solvents, alicyclic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, sulfone solvents, One or more mixtures of ketone solvents and amide solvents;
  • the solvent 2 is a deuterated solvent of the solvent 1.
  • the above-mentioned solvent 1 is preferably a polar solvent, which can be but not limited to: tetrahydrofuran, methyl tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propionic acid Propyl, Butyl Propionate, Methyl Methacrylate, Ethyl Methacrylate, Propyl Methacrylate, Toluene, Xylene, Trimethylbenzene, Chlorobenzene, Dichlorobenzene, Trichlorobenzene, Methanol, Ethanol, Propylene Alcohol, ethylene glycol, isobutanol, propylene glycol, acetonitrile, formic acid, acetic acid, propionic acid, trifluoroacetic acid, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dimethylacetamide,
  • the above-mentioned solvent 2 is a deuterated solvent corresponding to the above-mentioned solvent 1.
  • the solvent 2 can be but not limited to: deuterated chloroform, deuterated chlorobenzene, deuterated ethanol, etc.
  • the solvent is selected from solvent 1.
  • the n-type conjugated polymer is used in the electron transport layer.
  • the electron transport layer includes the above n-type conjugated polymer.
  • thermoelectric material includes the above-mentioned n-type conjugated polymer.
  • the electromagnetic shielding material includes the above-mentioned n-type conjugated polymer.
  • the present invention has the following advantages and beneficial effects:
  • the n-type conjugated polymer raw material obtained in the present invention is an aromatic diketone substance with active methylene groups, which can be directly obtained by polymerization reaction in the presence of oxidizing substances.
  • the reaction does not require noble metal catalysis, is insensitive to the reaction atmosphere, has a simple process and low cost, and is suitable for large-scale commercial application; the obtained product has excellent solubility and is suitable for solution-processed organic photoelectric devices.
  • the n-type conjugated polymer obtained in the present invention is used in organic solar cells and can be used as an electron transport layer. Compared with the traditional electron transport layer ZnO, it has a more excellent electron transport ability, thereby obtaining a more excellent photoelectricity conversion efficiency.
  • the n-type conjugated polymer obtained in the present invention can be used as a thermoelectric material. Without using additional dopants, the electrical conductivity can reach up to 1060 S/cm, and when applied to thermoelectric materials, more than 130 ⁇ Wm -1 K can be obtained -2 power factor.
  • the n-type conjugated polymer obtained in the present invention can be used as an electromagnetic shielding material, can shield more than 96% of electromagnetic waves at a thickness of 2 mm, and has a corresponding function of broadband.
  • Fig. 1 are respectively the n-type conjugated polymer in embodiment 1, embodiment 6 and embodiment 7, the absorption spectrum figure under solution and film state;
  • Fig. 2 is the J-V graph of the organic solar cell device based on ZnO and embodiment 1 respectively as electron transport layer in test example 2;
  • Fig. 4 is the conductivity-Seebeck coefficient-power factor performance figure of the n-type conjugated polymer of embodiment 1 and embodiment 2;
  • FIG. 5 is a diagram of the electromagnetic shielding ratio of the n-type conjugated polymer of Example 2 at different frequencies;
  • (b) in FIG. 5 is a diagram of the electromagnetic shielding effectiveness of the polymer of Example 2 at different frequencies.
  • the present invention uses the raw material aromatic diketones and the amount of oxidizing substances can be any ratio, such as: the molar ratio is 1:1, 0.01:1, 1:0.01, etc., aromatic diketones and oxidizing substances The amount of active substances is not 0.
  • reaction temperature is normal temperature to 150°C.
  • follow-up treatment is carried out; the follow-up treatment adopts conventional follow-up treatment methods, such as: filtration, dialysis; or filtration, washing, and drying; or precipitation in a precipitant.
  • FIG. 1 are the absorption spectrum diagrams of the n-type conjugated polymers in Example 1, Example 6 and Example 7 in solution and film state, respectively. It can be seen from the figure that the as-prepared n-type conjugated polymer has broad and strong absorption in the near-infrared region, which corresponds to its n-type polaron, reflecting the remarkable behavior of n-type conjugated polymers. This shows that the preparation method of the present invention can achieve in-situ doping of n-type polymers and obtain conductive n-type polymers without using common n-type dopants (such as N-DMBI).
  • N-DMBI common n-type dopants
  • Respectively the n-type conjugated polymer obtained in Examples 1 and 2 was settled to a solute concentration of 15 mg/ml with DMF (for the NCPO of Example 1) and DMSO (for the NCPO of Example 2), and then the above solution Films were formed by spin coating, and after the films were dry, the conductivity of the films was measured by the quadruped probe method.
  • the specific steps are:
  • the n-type conjugated polymer prepared in Example 1 was used as an electron transport layer in an organic solar cell, and related device data were tested.
  • ZnO was used as the electron transport layer at the same time, and tested under the same experimental conditions of the device structure.
  • the preparation of the organic solar cell device adopts a conventional process, and the preparation process is all carried out in a glove box with an oxygen and water content lower than 1ppm.
  • the effective area of a single device is 0.0516cm 2 .
  • ZnO was purchased from Sigma-Aldrich Company, model number 544906;
  • PM6 and Y6 are purchased from VAC company, and the structural formulas of PM6 and Y6 are as follows:
  • the power of the simulated sunlight was corrected to 100mW/cm 2 before testing using a silicon photodiode calibrated by the National Renewable Energy Laboratory (NREL) and a KG5 filter.
  • the energy conversion efficiency of the device was measured under the standard solar spectrum AM1.5 solar simulator (model 91192, Oriel, USA), and the current-voltage (JV) characteristics of the solar cell device were recorded with Keithley 2410 and Keithley 236 digital source meters, respectively.
  • Figure 2 is the J-V curves of organic solar cells based on ZnO and Example 1 respectively as the electron transport layer, it can be seen that the short-circuit current of the latter is obviously better than that of the former.
  • the photoelectric conversion efficiencies of the obtained devices are shown in Table 2.
  • the organic solar cell based on NCPO prepared in Example 1 as the electron transport layer has two parameters, the short-circuit current and the fill factor, which are more ideal than the data of the organic solar cell based on ZnO as the electron transport layer. This also leads to a higher final photoelectric conversion efficiency.
  • thermoelectric test was carried out on the NCPO obtained in Example 1-2.
  • thermoelectric figure of merit ZT
  • S represents the Seebeck coefficient
  • ⁇ represents the electrical conductivity
  • ⁇ represents the thermal conductivity
  • T represents the temperature when the device is working.
  • PF power factor
  • Example 1-2 we took the n-type conjugated polymer prepared in Example 1-2 as an example, prepared a thin film on a glass substrate by a drop coating method, tested its electrical conductivity and Seebeck coefficient, and characterized its thermoelectric performance.
  • the conductivity test adopts the four-probe test method.
  • the processing method of the Seebeck coefficient test device is similar to that of the conductivity test.
  • Glass is used as the substrate, and gold electrodes are obtained by photolithography as test electrodes. After cleaning the glass substrate with deionized water and isopropanol in sequence, the surface was blown dry with nitrogen. The glass was bombarded with plasma in a plasma etcher for 5 min. Then different n-type conjugated polymer solutions were drop-coated on the substrate and annealed at 80 °C for 15 min.
  • the two ends of the device are placed in a temperature gradient field, and (a) in Fig. 3 is the thermal voltage difference trend diagram of the n-type conjugated polymer in Example 2, and (b) in Fig. 3 is the n-type conjugated polymer in Example 2.
  • the corresponding thermoelectromotive force is measured by the change of the temperature difference between the two ends of the device, and then the Seebeck coefficient is measured. It can be seen from a-b in FIG. 3 that the polymer of the embodiment of the present invention exhibits the Seebeck effect of an n-type polymer under a weak temperature difference, and generates a thermoelectromotive force exceeding 30 ⁇ V/K.
  • the dielectric constant and electromagnetic shielding performance of the NCPO in Example 2 were tested in the 1-18 GHz band by coaxial method and waveguide method.
  • the NCPO experimental sample powder and paraffin wax in Example 2 were blended and ground according to a weight ratio of 50%, and the obtained powder material was pressed into a coaxial ring with an outer diameter of 7mm, an inner diameter of 3.04mm, and a thickness of 2mm by using a mold. Place the sample in the waveguide.
  • the main engine adopts DR-S01 vector network analyzer, the S parameter of the sample is tested by the network analyzer, and then the reflectance and absorption of the film sample are calculated according to the literature (Review of Scientific Instruments.2003, 74, 1098-1102) using the S parameter.
  • the rate parameter is used to obtain the electromagnetic shielding performance of the thin film sample.
  • FIG. 5 is a diagram of the electromagnetic shielding effectiveness of the polymer of Example 2 at different frequencies.
  • Figure 5(b) shows that the shielding effect of the powder material on electromagnetic waves exceeds 20dB, exhibiting excellent shielding performance on broadband electromagnetic waves. Among them, the absorption and shielding effectiveness corresponding to the absorption of electromagnetic waves by the material exceeds 15dB, and the average value of the reflection and shielding effectiveness corresponding to the reflection of the sample surface is 4.2dB. Therefore, NCPO can achieve excellent electromagnetic shielding in a wide frequency band, and has good application potential in the application of electromagnetic shielding.

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Abstract

本发明属于n型半导体材料的技术领域，公开了一种n型共轭聚合物及其制备方法与应用。方法：以溶剂为反应介质，反应单体在具有氧化性的物质的作用下发生反应，获得n型共轭聚合物。n型共轭聚合物包括一种或多种聚合单元，聚合单元为式(I)结构和/或式(II)结构，和/或其相应的烯醇式转变形式。本发明的原料为具有活泼亚甲基的芳香式二酮类物质，经具有氧化性的物质作用直接聚合反应。所述反应无需贵金属催化，且对反应气氛不敏感工艺简单，成本低廉，适用于商业化应用。本发明n型共轭聚合物具有优异的电子传输能力，较高的电导率以及较好的电磁波屏蔽效果。本发明的n型共轭聚合物应用于有机光电器件中，可以实现优异的光电效果。

Description

一种n型共轭聚合物及其制备方法与应用 技术领域
本发明属于n型有机半导体材料的技术领域，具体涉及一种n型共轭聚合物及其制备方法和应用。
背景技术
共轭聚合物的结构中包含了由离域的π电子组成的共轭体系，因而体现出特殊的光、电特性，引起了科学家的广泛关注。光电材料与器件所运用半导体材料，不仅具备金属或半导体的电子特性，更具备低成本、质量轻、可低温加工、易于实现大面积制备等特点，满足工业化大生产和大面积推广的要求，具有广大的商业前景。目前，共轭聚合物在有机太阳电池(OPV)、有机发光二极管(OLED)、有机场效应晶体管(OFET)以及有机热电(OTE)等领域已取得一系列令人瞩目的成果。
高性能的有机电子器件在工作时通常同时需要p型和n型两种半导体材料。PEDOT:PSS作为目前已经得到商业化应用的p型材料之一，由于具有高导电率以及可印刷加工的特点，在半导体器件中取得巨大的成功。
然而相比于发展成熟的p型材料，n型有机材料，尤其是具备高导电的有机n型共轭聚合物，则缺少相对应的合成策略。受限于n型有机半导体材料电子迁移率低、空气稳定性差，以及需要较长绝缘性烷基链以实现溶液加工等因素，发展具备高电导率以及合成简单、成本低廉、可溶液加工的n型有机半导体材料是目前研究的热点。
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮分子中含有两个强吸电子官能团，可以有效降低聚合物的最低未占据轨道(LUMO)，这有利于提高聚合物的电子迁移率以及确保聚合物n型掺杂的稳定性。基于3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮的聚合物已有诸多报道，如文献(Toward High Performance n-Type Thermoelectric Materials by Rational Modification of BDPPV Backbones.J.Am.Chem.Soc.2015,137,6979)报道了基于苯并二呋喃二酮的聚合物BDPPV，经过掺杂剂的优化，可以实现最高14S/cm的电导率；文献(High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air.Adv.Mater.2017,29,1606928)报道了利用四丁基氟化铵 掺杂基于苯并二呋喃二酮的聚合物，并获得空气稳定性较好的n型热电材料；另外，文献(Rigid Coplanar Polymers for Stable n-Type Polymer Thermoelectrics.Angew.Chem.Int.Ed.2019,58,11390)报道了利用酸催化羟醛缩合反应聚合，在避免使用贵金属催化剂的同时，获得了空气稳定同时具备高电导率的基于苯并二呋喃二酮的聚合物LPPV。
然而由于3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮优异的平面性，目前多数基于该单元的聚合物通常需要在共聚单元上引入较长的烷基链以保证其在有机溶剂中的溶解性；同时需要使用外加掺杂剂(如N-DMBI等)进行掺杂以获得高导电率，难以在空气中保持长期稳定。
而对于二酮类稠环化合物，文献(Synthese,Charakterisierung und Halbleitereigenschaften eines polymeren Indopheninhomologen.Macro.Chem.Phys.1975,176,333)公开了一种在硫酸催化的条件下可以进行脱水聚合，形成具备导电性的P型醌式聚合物；专利WO 2014/071524公布了含稠环结构的聚合物，并介绍其作为有机半导体在OFET中的应用；专利US 2019/0048015 A1公开了一类可不使用贵金属催化的近红外有机半导体聚合物。
另外，专利申请CN108699073公开了一种半导体聚合物及其合成方法，该半导体聚合物的结构为
Figure PCTCN2021124880-appb-000001
然而，该聚合物在制备的过程中所采用的原料之一为四酮A
Figure PCTCN2021124880-appb-000002
为一类经氧化反应后的中间体。合成该中间体需要耗费额外的工艺成本，导致合成路线不经济，难以商业化。同时部分四酮A结构，如
Figure PCTCN2021124880-appb-000003
在现有技术下实际上并未公开制备方法，难以通过已公开的文献获得适合于商业化的聚合物制备方法。
同时上述公开的聚合物中，并不涉及任何n型导电的性质，或者相关数据并不理想。且所公开的聚合物结构均含有烷基侧链，不含烷基链情况下仍可实现溶液加工的聚合物结构以及制备方法并未报道。
综上，如何开发一类结构简单、合成简易、成本低廉且可溶液加工的n型高导电共轭聚合物，并经过适用商业化的制备方法直接合成；同时应用于有机光电领域，并且实现理想的光电效果，是亟需解决的问题。
发明内容
为了克服现有技术的缺点和不足，本发明的目的在于提供一种n型共轭聚合物及其制备方法。本发明的方法中所采用的原料为具有活泼亚甲基的芳香式二酮类物质，在氧化剂存在的条件下，聚合反应直接得到n型共轭聚合物。所述反应无需贵金属催化，且对反应气氛不敏感，工艺简单，成本低廉，适用于商业化应用。通过本发明的方法所获得的n型共轭聚合物在一般的有机溶剂中具有良好的溶解性，可以实现溶液加工。同时，该n型共轭聚合物应用于有机光电器件中，可以实现优异的光电效果。
本发明的另一目的在于提供由上述方法制备得到的n型共轭聚合物的应用。所述n型共轭聚合物应用于有机光电器件中。具体的，本发明的n型共轭聚合物应用于有机太阳电池中，作为电子传输层；或者用作热电材料，或电磁屏蔽材料。
本发明的目的通过以下技术方案实现：
一种n型共轭聚合物为均聚物或共聚物，n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，和/或其相应的烯醇式转变形式：
Figure PCTCN2021124880-appb-000004
进一步地，n型共轭聚合物，其结构具体为式I、式II、式I与式II组成的结构、式I与式I组成的结构、或者式II与式II组成的结构、与式I相应的烯醇式转变形式、与式II相应的烯醇式转变形式、式I与之相应的烯醇式转变形式组成的结构、式II与之相应的烯醇式转变形式组成的结构、式I与式II以及相应的烯醇式转变形式组成的结构；其中式I与式I组成的结构中式I与式I不同，式II与式II组成的结构中式II与式II不同；式I与式II组成的结构中含有1个 或多个式I，含有1个或多个式II，式I相同或不同，式II相同或不同。
式I中，X独立地选自O、S、Se、Te或N-R 1；
其相应的烯醇式转变形式选自如下结构的一种或多种：
Figure PCTCN2021124880-appb-000005
所述R 1选自氢原子、烷基、亚烷基(R′-C n′H 2n′，R′为取代基，C n′H 2n′为亚烷基)、烷基衍生物、亚烷基衍生物的一种或多种；
所述烷基衍生物是指烷基上的一个或多个碳，被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代；
和/或
所述烷基衍生物上的一个或多个氢，被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代；
n为正整数；
所述M为n型共轭聚合物结构中的共轭部分，所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
所述芳环是指拥有共轭平面环体系，原子间成键是被离域π电子云覆盖的环状结构。如苯环及其衍生物。
所述芳杂环是指拥有共轭平面环体系，原子间成键是被离域π电子云覆盖的；且构成环的原子除碳原子外，还至少含有一个杂原子(如N、O、S等)的环状结构。如噻吩、呋喃、吡咯等。
所述稠合芳环是指拥有共轭平面环体系，原子间成键是被离域π电子云覆盖的两个或多个芳香环稠合(即共用环边)而成的结构。如萘、蒽及其衍生物。
所述稠合芳杂环是指拥有共轭平面环体系，原子间成键是被离域π电子云覆盖的两个或多个芳香环稠合而成的结构，并且至少一个环中的构成原子除碳原子外，还至少含有一个杂原子(如N、O、S等)。如喹啉、吲哚及其衍生物。
本发明中，所述n型高导电共轭聚合物具有多种共振形式。以M为苯环结构时为例，包括但不限于以下共振形式：
Figure PCTCN2021124880-appb-000006
同时，由于烯醇式转变的存在，以M为苯环结构时为例，所述n型高导电共轭聚合物，具有包括但不限于以下共振形式：
Figure PCTCN2021124880-appb-000007
进一步地，其不同共振形式间可通过分子间相互作用自组装形成如下超分子：
Figure PCTCN2021124880-appb-000008
需要特别指出的是，当X为氧原子，且M为苯环结构时，所得化合物还存 在如下所示互变异构：
Figure PCTCN2021124880-appb-000009
波浪线表示共轭聚合物的链段。
为方便起见，本发明的内容中均以第一种共振形式进行表达。
进一步地，所述M的结构选自以下结构：
Figure PCTCN2021124880-appb-000010
其中，所述X 2-X 4独立地选自O、S、Se、Te或N-R 1；
所述R 2-R 5独立地选自氢原子、羟基、硝基、卤素、氰基、硝基、烷基、烷 基衍生物的一种或多种；
所述烷基衍生物上的一个或多个碳，被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代；
和/或
所述烷基衍生物上的一个或多个氢，被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代。
需要说明的是，上述M的结构的可选对象中，芳环中的虚线
Figure PCTCN2021124880-appb-000011
表示此处与相邻的五元环或四元环的相互稠合，即共用环边。例如，当M的结构表示为
Figure PCTCN2021124880-appb-000012
时，其所代表的n型共轭聚合物的实际结构为：
Figure PCTCN2021124880-appb-000013
或其相应的烯醇式转变形式。
进一步地，所述n型共轭聚合物为均聚物或共聚物，
当所述n型共轭聚合物为均聚物时，所述n型共轭聚合物的结构选自如下结构的一种，或其相应的烯醇式转变形式：
Figure PCTCN2021124880-appb-000014
当所述n型共轭聚合物为共聚物时，所述n型共轭聚合物包括至少两种聚合单元；
所述每个聚合单元的结构独立地选自如下结构：
Figure PCTCN2021124880-appb-000015
或其相应的烯醇式转变形式；
其中
所述R 1选自氢原子、烷基、烷基衍生物的一种或多种；
所述烷基衍生物上的一个或多个碳，被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代；
和/或
所述烷基衍生物上的一个或多个氢，被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代；
所述n1-n6独立地为正整数；
所述M为n型共轭聚合物结构中的共轭部分，所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种。
上述结构中R 1、M如前面式I、式II所定义。
所述n型共轭聚合物的制备方法，包括如下步骤：
以溶剂为反应介质，反应单体在具有氧化性的物质的作用下发生反应，获得n型共轭聚合物。
所述反应单体为
Figure PCTCN2021124880-appb-000016
和/或
Figure PCTCN2021124880-appb-000017
和/或其相应的烯醇式转变形式；
其中，所述相应的烯醇式转变形式选自如下结构的一种或多种：
Figure PCTCN2021124880-appb-000018
结构中M，X如上述n型共轭聚合物所定义。
当n型共轭聚合物为均聚物时，反应单体为同一种结构的化合物；
当n型共轭聚合物为共聚物时，反应单体为不同结构的化合物；即反应单体为式I′化合物中两种以上或II′化合物中两种以上，或其相应的烯醇式转变形式；或者反应单体为式I′化合物与II′化合物，和/或其相应的烯醇式转变形式；
Figure PCTCN2021124880-appb-000019
当n型共轭聚合物为共聚物时，n型共轭聚合物的制备方法，还可以为：
1)将不同的反应单体分别在溶剂中以及具有氧化性的物质的作用下发生反应，分别获得不同聚合单元；
2)以溶剂为反应介质，步骤1)中不同聚合单元在具有氧化性的物质的作用下进一步发生共聚反应，获得n型共轭聚合物。
不同聚合单元优选为以下结构中两种以上，和/或其相应的烯醇式转变形式：
Figure PCTCN2021124880-appb-000020
当n型共轭聚合物为共聚物时，共聚物可以为二元共聚物或多元共聚物，不同的聚合单元之间可以相互聚合，从而形成新的长链共聚物。共聚物的结构，可以但不限于如下结构中的一种：
Figure PCTCN2021124880-appb-000021
所述具有氧化性的物质选自有机类具有氧化性的物质、无机类具有氧化性的物质的一种或多种的混合物。
进一步地，所述具有氧化性的物质为氧气、过氧化物、金属卤化物、过硫酸盐、过硼酸盐、次卤酸盐、亚卤酸盐、醌类化合物、过苯甲酸类化合物中的一种以上。
具体地，上述具有氧化性的物质可以但不限于：如氧气、过氧化氢、过氧化钠、过氧化钾、过氧化钙、过氧化锌、过氧化铜、硝酸铁、硝酸锌、硝酸镍、硝酸铝、硝酸镁、硝酸铵、氟化铁、氯化铁、溴化铁、碘化铁、高氯酸钠、高氯酸钾、高溴酸钠、高溴酸钾、高碘酸钠、高碘酸钾、过氯酸钾、过氯酸钠、过溴酸钾、过溴酸钠、过氯酸镁、过硫酸钠、过硫酸钾、过硫酸镁、过硫酸锌、过硫酸铁、过硫酸铜、过硫酸钙、过硼酸钾、过硼酸锌、过硼酸镁、过硼酸钙、次氟酸钠、次氟酸钾、次氯酸钠、次氯酸钾、次氯酸铁、次氯酸铜、次溴酸钠、 次溴酸钾、次碘酸钠、次碘酸钾、亚氯酸钠、亚氯酸钾、亚氯酸铁、亚溴酸钠、亚溴酸钾、亚碘酸钠、亚碘酸钾、苯醌及其衍生物、萘醌及其衍生物、蒽醌及其衍生物、菲醌及其衍生物、过苯甲酸及其衍生物中的一种以上。
所述溶剂选自溶剂1，或溶剂2，或溶剂1和溶剂2的混合物；
所述溶剂1选自水、腈类溶剂、芳香族类溶剂、脂环烃类溶剂、脂环烃类溶剂、卤化烃类溶剂、醇类溶剂、醚类溶剂、酯类溶剂、砜类溶剂、酮类溶剂、酰胺类溶剂的一种或多种的混合物；
所述溶剂2为所述溶剂1的氘代溶剂。
具体地，上述溶剂1优选为极性溶剂，可以但不限于为：如四氢呋喃、甲基四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲苯、二甲苯、三甲苯、氯苯、二氯苯、三氯苯、甲醇、乙醇、丙醇、乙二醇、异丁醇、丙二醇、乙腈、甲酸、乙酸、丙酸、三氟乙酸、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、二甲基乙酰胺、丙酮、丁酮、环己酮、甲基丁酮、甲醚、乙醚、丙醚、吡啶、苯酚、N-甲基吡咯烷酮、乙二醇单甲醚、三甘醇单甲醚、三乙胺、四甲基乙二胺、三辛胺、苯胺、六甲基磷酸三胺的一种以上。
具体地，上述溶剂2为上述溶剂1所相对应的氘代溶剂，例如，溶剂2可以但不限于：氘代氯仿、氘代氯苯、氘代乙醇等。
优选地，所述溶剂选自溶剂1。
上述n型共轭聚合物在有机光电器件中的应用。所述n型共轭聚合物在电子传输层中应用。所述电子传输层包括上述n型共轭聚合物。
所述n型共轭聚合物在热电材料中的应用。所述热电材料包括上述n型共轭聚合物。
所述n型共轭聚合物在电磁屏蔽材料中的应用。所述电磁屏蔽材料包括上述n型共轭聚合物。
与现有技术相比，本发明具有如下优点及有益效果：
1.本发明所得的n型共轭聚合物原料为具有活泼亚甲基的芳香式二酮类物质，在具有氧化性的物质存在的条件下，聚合反应直接得到。所述反应无需贵金属催化，且对反应气氛不敏感，工艺简单，成本低廉，适合大规模商业化应用；所得产物溶解性优异，适用于溶液加工型的有机光电器件中。
2.本发明所得的n型共轭聚合物应用于有机太阳电池中，可作为电子传输层，相比于传统的电子传输层ZnO，具有更加优异的电子传输能力，从而获得更为优异的光电转换效率。
3.本发明所得的n型共轭聚合物，可作为热电材料，在不使用额外掺杂剂 的情况下，电导率最高可达到1060S/cm，应用于热电材料中可获得超过130μWm -1K -2的功率因子。
4.本发明所得的n型共轭聚合物，可作为电磁屏蔽材料，可以在2mm厚度下屏蔽超过96％的电磁波，且具有宽频相应功能。
附图说明
图1中(a)、(b)和(c)分别为实施例1、实施例6和实施例7中的n型共轭聚合物，在溶液和薄膜状态下的吸收光谱图；
图2为测试例2中分别基于ZnO和实施例1的作为电子传输层的有机太阳电池器件的J-V曲线图；
图3中(a)为实施例2中的n型共轭聚合物的热电压差变化趋势图，图3中(b)为实施例2中的n型聚合物的热电压差随温度的变化趋势拟合图；
图4为实施例1和实施例2的n型共轭聚合物的电导率-Seebeck系数-功率因子性能图；
图5中(a)为实施例2的n型共轭聚合物在不同频率的电磁屏蔽比例图；图5中(b)为实施例2的聚合物在不同频率的电磁屏蔽效能图。
具体实施方式
为了更清楚地说明本发明的技术方案，列举如下实施例。实施例中所出现的原料、反应和后处理手段，除非特别声明，均为市面上常见原料，以及本领域技术人员所熟知的技术手段。
本发明实施例中的原料之一，3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮，按照文献(A BDOPV-Based Donor–Acceptor Polymer for High-Performance n-Type and Oxygen-DopedAmbipolar Field-Effect Transistors.Adv.Mater.2013,25(45),6589)进行制备；实施例中的具有氧化性的物质采用杜醌或者辅酶Q10，采购自上海毕得医药科技股份有限公司。
本发明采用原料芳香式二酮类物质和具有氧化性的物质的用量可以为任意比例，如：摩尔比为1:1、0.01:1、1:0.01等，芳香式二酮类物质和具有氧化性的物质的用量不为0。
原料芳香式二酮类物质在具有氧化性的物质的作用下进行反应时，反应温度没有特别的要求，只要反应能进行即可，如：反应的温度为常温～150℃。
反应完后，进行后续处理；所述后续处理为采用常规后续处理方式，如：过滤，透析；或者过滤，洗涤，干燥；又或者在沉淀剂中沉淀。
实施例1：n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000022
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，和杜醌(1mmol)，溶于2ml的DMF中，经真空脱气后，充入氮气进行保护。在氮气氛围、100℃下搅拌反应4h。然后将所得粗产物用DMF稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝10kDa)在DMF溶液中透析3天，得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试，分子量Mn＝14kDa，PDI＝4.02。
实施例2：n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000023
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，和杜醌(1mmol)，溶于2ml的DMSO中，经真空脱气后，充入氮气进行保护。在氮气氛围、100℃下搅拌反应1h。然后将所得粗产物用DMSO稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝15kDa)在DMSO溶液中透析3天，得到产物NCPO。所得产物NCPO经以DMSO为流动相的凝胶渗透色谱测试，分子量Mn＝220kDa，PDI＝2.02。
实施例3：n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000024
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，和辅酶Q10(1mmol)，溶于2ml的DMF中，经真空脱气后，充入氮气进行保护。在氮气氛围、100℃下搅拌反应4h。然后将所得粗产物用DMF稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝10kDa)在DMF溶液中透析3天，得到产物NCPO。所得产物NCPO 经以DMF为流动相的凝胶渗透色谱测试，分子量Mn＝21kDa，PDI＝1.98。
实施例4：n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000025
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，和辅酶Q10(10mmol)，溶于4ml的DMF中，经真空脱气后，充入氮气进行保护。在氮气氛围、100℃下搅拌反应2h。然后将所得粗产物用DMF稀释至约15ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝10kDa)在DMF溶液中透析7天，得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试，分子量Mn＝76kDa，PDI＝1.72。
实施例5：n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000026
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，和氧化剂杜醌(0.1mmol)，溶于2ml的DMSO中。在100℃下搅拌反应24h。然后将所得粗产物用DMSO稀释至约10ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝15kDa)在DMSO溶液中透析3天，得到产物NCPO。所得产物NCPO经以DMSO为流动相的凝胶渗透色谱测试，分子量Mn＝23kDa，PDI＝1.20。
实施例6：n型共轭聚合物NCPS的制备
Figure PCTCN2021124880-appb-000027
(1)将苯并二噻吩(23mmol)溶解于无水四氢呋喃中(300ml)后，降温至-78℃,在90min内缓慢加入正丁基锂(2.5M的正己烷溶液，25.8ml,64.4mmol),于-78℃下搅拌3h后升温至0℃，加入硼酸三正丁酯(60mmol),搅拌1h后逐渐升到室温25℃，继续搅拌8h。利用旋转蒸发仪浓缩溶液至200ml，加入0.5M盐酸200ml，过滤得到粗产物。将粗产物利用四氢呋喃/正己烷沉淀出产物，并用冰甲苯洗涤，干燥固体(产率＝61％)，用于下一步反应。
(2)将上一步所的固体(7.5mmol)溶解于在四氢呋喃(100ml)中，于0℃下加入2.5ml过氧化氢水溶液(30wt％)，于室温下搅拌6h。利用旋转蒸发仪除去溶剂后，利用硅胶填充层析色谱柱(200-300目)，以乙酸乙酯：石油醚＝4：1为洗脱剂提纯产物，得到固体用正己烷和甲醇洗涤，得到3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(产率＝53％)。 1H NMR(CDCl 3,500MHz)δppm：7.31(s,2H),3.98(s,4H)。
(3)3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(1mmol)，和杜醌(1mmol)，溶于2ml的DMF中，经真空脱气后，充入氮气进行保护。在氮气氛围、120℃下搅拌48h，将溶液稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤。将溶液利用旋转蒸发仪浓缩，利用透析袋(截断分子量＝5kDa)在DMF溶液中透析三天，所得溶液利用DMF定容至15mg/ml后直接用于后续使用。经以DMF为流动相的凝胶渗透色谱测试分子量，Mn＝8.9kDa，PDI＝1.18。
实施例7：n型共轭聚合物NCP的制备
Figure PCTCN2021124880-appb-000028
(1)在500ml圆底反应烧瓶中加入150ml甲醇，在冰盐水浴的条件下缓慢同时加入醋酸乙烯酯(0.64mol)以及液溴(0.636mol)，滴加过程中体系温度控制在5℃以下。滴加完成后，逐渐升至室温反应12h。将混合溶液倒入冰水(200ml)中，分批次加入NaHCO 3(0.67mol)，并搅拌30min。待不再产生气泡后，加入二氯甲烷(3×200ml)萃取，合并有机相，用NaCl水溶液洗涤(3×100ml)。经无水硫酸镁干燥后，利用旋转蒸发仪除去低沸点溶剂，所得无色液体直接用于下一步反应。
(2)将所得无色液体加入250ml圆底反应瓶中，在冰浴条件下，分批次加入无水叔丁醇钾(0.64mol)，升至室温搅拌10h后，蒸馏收集，得到叔丁醇以及1,1-二甲氧基乙烯的混合溶液，直接用于下一步反应。
(3)在500ml圆底烧瓶中，加入氨基钠(0.73mol)，加入对二溴苯(0.12mol)以及150ml无水四氢呋喃。加入上一步所得全部溶液后，在80℃下搅拌8h。利用旋转蒸发仪除去易挥发性溶剂，所得粘稠棕色固体以乙酸乙酯：石油醚＝1：5为洗脱剂，利用硅胶填充层析色谱柱提纯。所得粗产物使用正己烷洗涤后，用乙醇/水重结晶得到白色固体三环[6.2.0.0 3,6]癸-1,3(6)，7-三烯-4,9-二酮(产率＝12％)。 1HNMR(CDCl 3,500MHz)δppm：7.84(s,2H),4.04(s,4H)。
(4)三环[6.2.0.0 3,6]癸-1,3(6)，7-三烯-4,9-二酮(1mmol)，和杜醌(1mmol)，溶于2ml的DMSO中，经真空脱气后，充入氮气进行保护。在氮气氛围下，120℃下搅拌48h，将溶液稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤。将溶液利用旋转蒸发仪除去溶剂，并依次用水(10ml)、四氢呋喃(20ml)和乙腈(20ml)洗涤所得固体，并经过真空干燥得到产物NCP。
实施例8：n型共轭聚合物NCPN的制备
Figure PCTCN2021124880-appb-000029
(1)将1,4-环己二酮(50.0mmol)溶解于500mL乙醇中，向其中加入正己胺(100mmol)。将所得混合物在空气下常温搅拌4h。通过减压蒸馏除去溶剂得到粗产物，并通过柱层析色谱纯化(石油醚：二氯甲烷：乙酸乙酯＝10：10：1)，得到灰黄色固体状的化合物(产率＝54.7％)。 1H NMR(CDCl 3，500MHz)δppm：6.54(s，4H)，3.15(br，2H)，3.03(tr，4H)，1.55-1.60(m，4H)，1.24-1.40(m，12H)，0.83-0.89(m，6H)。
(2)在0℃下向氯乙酰氯(3.56mmol)的THF(5mL)溶液中逐滴滴加上述灰黄色固体状的化合物(1.19mmol)和4-(二甲氨基)吡啶(DMAP)(1.11mmol)的THF(10ml)溶液。搅拌1小时后，加入50mL水淬灭反应，过滤收集不溶物。将收集的固体用水和甲醇洗涤后，真空干燥，得到白色固体状的产物(产率＝62.7％)。 1H NMR(CDCl 3，500MHz)δppm：7.32(s，4H)，3.82(s，4H)，3.27(t，4H)，1.53-1.55(m，4H)，1.26-1.32(m，12H)，0.87-0.88(m,6H)。
(3)在氩气保护下，将上述白色固体状的产物(11.6mmol)和无水氯化铝(81.5mmol)的混合物于190℃加热20分钟。冷却后，加入冰水淬灭反应，过滤收集沉淀。用水和甲醇洗涤后，干燥固体得到粗产物，通过柱层析色谱纯化(二氯甲烷∶乙酸乙酯＝10∶1)，得到白色固体状的1,5-二己基-5,7-二氢-1H，3H-吡咯并[2,3-f]吲哚-2,6-二酮(产率＝66.1％)。 1H NMR(CDCl 3，600MHz)δppm：6.78(m，2H)，3.68(m，4H)，3.55(m，4H)，1.61-1.69(m，4H)，0.98-1.48(m，12H)，0.88-0.89(m，6H)。
(4)将上述1,5-二己基-5,7-二氢-1H，3H-吡咯并[2,3-f]吲哚-2,6-二酮(1mmol)，和杜醌(1mmol)，溶于2ml的DMSO中。在氮气氛围下，120℃下搅拌48h，将溶液稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过 滤。将所得溶液利用旋转蒸发仪除去溶剂，并依次用水(10ml)、四氢呋喃(20ml)和乙腈(20ml)洗涤所得固体，并经过真空干燥得到产物NCPN(产率＝48％)。
实施例9 n型共轭聚合物NCPO的制备
Figure PCTCN2021124880-appb-000030
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol)，溶于2ml的DMF中，然后持续通入空气。在100℃下搅拌反应72h。然后将所得粗产物用DMF稀释至约10mg/ml后，利用0.45μm孔径的聚四氟乙烯滤头过滤，所得滤液采用旋转蒸发仪浓缩，利用透析袋(截断分子量＝5kDa)在DMF溶液中透析3天，得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试，分子量Mn＝8kDa，PDI＝1.98。
实施例10 一种n型共轭聚合物NCPO0.5-NCPS0.5的制备
Figure PCTCN2021124880-appb-000031
将3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(0.5mmol)以及3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(0.5mmol)，溶于2ml的六甲基磷酸三胺(HMPA)中，加入杜醌(1mmol)。在100℃下搅拌反应22h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中，过滤收集其中沉淀，得到产物NCPO0.5-NCPS0.5。所得产物经以DMSO为流动相的凝胶渗透色谱测试，分子量Mn＝12kDa，PDI＝2.01。
实施例11 一种n型共轭聚合物NCPO0.7-NCPN0.3的制备
Figure PCTCN2021124880-appb-000032
将3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(0.7mmol)以及1,5-二己基-5,7-二氢-1H，3H-吡咯并[2,3-f]吲哚-2,6-二酮(0.3mmol)，溶于2ml的六甲基磷酸三胺(HMPA)中，加入双氧水(1mmol,30wt％的水溶液)。在100℃下搅拌反应20h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中，过滤收集其中沉淀，得到产物NCPO0.7-NCPN0.3。所得产物经以DMSO为流动相的凝胶渗透色谱测试，分子量Mn＝2.8kDa，PDI＝1.08。
实施例12 一种n型共轭聚合物NCPS0.5-NCPN0.5的制备
Figure PCTCN2021124880-appb-000033
将3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(0.5mmol)以及1,5-二己基-5,7-二氢-1H，3H-吡咯并[2,3-f]吲哚-2,6-二酮(0.5mmol)，溶于2ml的六甲基磷酸三胺(HMPA)中，加入三氯化铁(1mmol)。在100℃下搅拌反应72h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中，过滤收集其中沉淀，得到产物NCPS0.5-NCPN0.5。所得产物经以DMSO为流动相的凝胶渗透色谱测试，分子量Mn＝3.0kDa，PDI＝1.11。
图1中(a)、(b)和(c)分别为实施例1、实施例6和实施例7中的n型共轭聚合物，在溶液和薄膜状态下的吸收光谱图。从图中可以看出，制备的n型共轭聚合物在近红外区具有宽而强的吸收，这与其n型极化子相对应，体现出了显著的n型共轭聚合物的行为。这说明了本发明的制备方法在不使用常用n型掺杂剂的情况下(如N-DMBI)，可以实现n型聚合物的原位掺杂，获得导电n型聚合物。
测试例1
分别将实施例1和2所得的n型共轭聚合物，用DMF(针对实施例1的NCPO)和DMSO(针对实施例2的NCPO)定容至溶质浓度为15mg/ml，然后将上述溶液分别旋涂成膜，待膜干燥后，利用四足探针法测量薄膜电导率。具体步骤为：
将石英玻璃片依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇作清洗溶剂在超声清洗仪洗涤，洗涤完后用氮气吹干表面，并用红外灯烘干，之 后置于恒温烘箱中备用。使用前，将玻璃片在等离子体刻蚀仪中以等离子体轰击10min。
完成玻璃片的准备后，将其放在加热台上，110℃加热后转移至旋转匀胶仪(KW-4A)上，用以上制备的n型共轭聚合物高速旋涂(共轭聚合物溶液的质量浓度为15mg/ml)，并同时用台阶仪实测监控膜的厚度。成膜完成后，利用四足探针电导率测试仪(RTS-8型四探针测试仪)测试其方阻，并计算电导率。所得结果如表1所示。
表1 实施例1-2的n型共轭聚合物的电导率测试
共轭聚合物 方阻(Ω/□) 厚度(nm) 导电率(S/cm)
实施例1 360 54 514
实施例2 180 68 817
从表1可知，本发明制备的共轭聚合物具有高的导电率。
测试例2
将实施例1中所制备的n型共轭聚合物，作为电子传输层，应用于有机太阳电池中，并测试相关的器件数据。作为对比，同时将ZnO作为电子传输层，在器件结构相同的实验条件下进行测试。有机太阳电池器件的制备采用常规工艺，其制备过程，均在氧气和水含量低于1ppm的手套箱中进行。
有机太阳电池结构为：ITO(100nm)/实施例1所制备的NCPO(或ZnO)(50nm)/活性层(PM6：Y6＝1:1.5，m/m共混，并加入1wt％的二碘辛烷)(120nm)/氧化钼(60nm)/银电极(60nm)。
其中，单个器件有效面积为0.0516cm 2。
ZnO采购自Sigma-Aldrich公司，型号为544906；
PM6和Y6采购自VAC公司，PM6和Y6的结构式如下：
Figure PCTCN2021124880-appb-000034
模拟太阳光的能量在测试前利用经过美国国家可再生能源实验室(NREL)校准的硅光电二极管和一个KG5滤波器校正为100mW/cm 2。器件的能量转换 效率在标准太阳光谱AM1.5太阳模拟器(型号91192，Oriel，USA)下测得，分别用Keithley 2410和Keithley 236数字源表记录太阳电池器件的电流-电压(J-V)特性。
图2为分别基于ZnO和实施例1的作为电子传输层的有机太阳电池的J-V曲线图，可以看出，后者的短路电流明显优于前者。所得器件的光电转换效率如表2所示。
表2 基于不同界面层的有机太阳电池性能
Figure PCTCN2021124880-appb-000035
从表2可以看出，基于实施例1所制备的NCPO作为电子传输层的有机太阳电池，其短路电流和填充因子两个参数，比基于ZnO作为电子传输层的有机太阳电池数据更为理想，这也导致了最终的光电转换效率更高。
测试例3
对实施例1-2中所得的NCPO进行热电测试。
材料的热电性能常用热电优值(ZT)来描述，具体公式如下：
ZT＝S 2σT/κ；
其中S代表Seebeck系数，σ代表电导率，κ代表热导率，T代表器件工作时的温度。对于有机材料而言，其热导率远低于无机材料，因此常用功率因子(PF)来描述有机材料的热电性能，其中PF＝S 2σ。
在该测试例中我们以实施例1-2所制备的n型共轭聚合物为例，利用滴涂法在玻璃基底上制备薄膜，测试其电导率和Seebeck系数，表征其热电性能。电导率测试采用四探针测试法。
将玻璃基底依次用去离子水、异丙醇清洗后，用氮气吹干表面。将玻璃在等离子体刻蚀仪中以等离子体轰击5min。然后将不同n型共轭聚合物溶液滴涂于基底上，并于80℃退火15min后测量电导率。电导率测试结果如表3所示。
表3 利用滴涂法制备薄膜的电导率
共轭聚合物 实施例1 实施例2
电导率(S/cm) 720 1060
Seebeck系数测试器件加工方法与电导率测试的加工方法相似，使用玻璃作为基底，利用光刻方法得到金电极作为测试电极。将玻璃基底依次用去离子水、异丙醇清洗后，用氮气吹干表面。将玻璃在等离子体刻蚀仪中以等离子体轰击5 min。然后将不同n型共轭聚合物溶液滴涂于基底上，并于80℃退火15min。
将器件两端放置于温度梯度场中，图3中(a)为实施例2中的n型共轭聚合物的热电压差变化趋势图，图3中(b)为实施例2中的n型聚合物的热电压差随温度的变化趋势拟合图。通过器件两端温差的变化测试对应的温差电动势，进而测得Seebeck系数。从图3中a-b上可以看出，本发明实施例的聚合物在微弱的温差下，展示出n型聚合物的Seebeck效应，并产生超过30μV/K的温差电动势。
图4为实施例1和实施例2的电导率-Seebeck系数-功率因子性能图，其中功率因子由PF＝S 2σ所得。由上述测试可以得到室温下功率因子最大为139.5μWm -1K -2，在现有n型共轭聚合物中处于较高水平。相关数据如表4所示。
表4 利用滴涂法制备薄膜的Seebeck系数
共轭聚合物 实施例1 实施例2
Seebeck系数(μV/K) -31.48±0.16 -36.28±1.88
功率因子(μWm -1K -2) 77.5 139.5
测试例4
为了本发明中的聚合物在电磁屏蔽上的应用，采用同轴法和波导法在1-18GHz波段，对实施例2中的NCPO进行介电常数以及电磁屏蔽性能测试。将实施例2中的NCPO的实验样品粉末与石蜡按照50％的重量比共混研磨后所得粉末材料，利用模具压制成外径7mm、内径3.04mm、厚2mm的同轴环。将样品放置于波导管中。主机采用DR-S01矢量网络分析仪，通过网络分析仪测试出样品的S参数，然后使用S参数根据文献(Review of Scientific Instruments.2003,74,1098-1102)计算得到薄膜样品的反射率、吸收率参数，进而得到薄膜样品的电磁屏蔽性能。
实施例2中的NCPO的粉末材料的电磁屏蔽效率与吸收占比如图5(a)所示，其在1-18GHz的宽屏范围内均可实现超过96％的电磁波屏蔽，其中约40％的电磁波被粉末材料所吸收。图5中(b)为实施例2的聚合物在不同频率的电磁屏蔽效能图。图5中(b)显示了该粉末材料对电磁波的屏蔽效能超过20dB，展现出对宽频电磁波优异的屏蔽性能。其中材料对电磁波的吸收作用对应的吸收屏蔽效能超过15dB，样品表面的反射作用对应的反射屏蔽效能平均值为4.2dB。因此，NCPO可以实现宽频段优异的电磁屏蔽，在电磁屏蔽上的应用上具有良好的应用潜力。
以上测试例说明本发明中的n型共轭聚合物在各种有机光电器件中均有广泛的应用。

Claims (12)

  1. 一种n型共轭聚合物的制备方法，其特征在于：包括如下步骤：
    以溶剂为反应介质，反应单体在具有氧化性的物质的作用下发生反应，获得n型共轭聚合物；
    所述反应单体为
    Figure PCTCN2021124880-appb-100001
    和/或
    Figure PCTCN2021124880-appb-100002
    和/或其相应的烯醇式转变形式；
    所述相应的烯醇式转变形式选自如下结构的一种或多种：
    Figure PCTCN2021124880-appb-100003
    所述n型共轭聚合物为均聚物或共聚物，n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100004
    聚合单元中，所述相应的烯醇式转变形式选自
    Figure PCTCN2021124880-appb-100005
    反应单体、聚合单元中，各自X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    反应单体、聚合单元中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
    式I、式II、相应的烯醇式转变形式中n为正整数。
  2. 根据权利要求1所述n型共轭聚合物的制备方法，其特征在于：
    R 1中，所述烷基衍生物是指烷基上的一个或多个碳，被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代；
    和/或
    所述烷基衍生物上的一个或多个氢，被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代；
    所述M独自选自以下结构：
    Figure PCTCN2021124880-appb-100006
    其中，所述X 2-X 4独立地选自O、S、Se、Te或N-R 1；N-R 1中R 1选自氢原 子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    所述R 2-R 5独立地选自氢原子、羟基、硝基、卤素、氰基、硝基、烷基、烷基衍生物的一种或多种；
    上述M的结构中，芳环中的虚线---表示此处与相邻的五元环或四元环的相互稠合即共用环边；
    所述具有氧化性的物质选自有机类具有氧化性的物质、无机类具有氧化性的物质的一种或多种；
    所述溶剂选自溶剂1，或溶剂2，或溶剂1和溶剂2的混合物；
    所述溶剂1选自水、腈类溶剂、芳香族类溶剂、脂环烃类溶剂、脂环烃类溶剂、卤化烃类溶剂、醇类溶剂、醚类溶剂、酯类溶剂、砜类溶剂、酮类溶剂、酰胺类溶剂的一种或多种；
    所述溶剂2为溶剂1的氘代溶剂。
  3. 根据权利要求2所述n型共轭聚合物的制备方法，其特征在于：
    所述具有氧化性的物质为氧气、过氧化物、金属卤化物、过硫酸盐、过硼酸盐、次卤酸盐、亚卤酸盐、醌类化合物、过苯甲酸类化合物中的一种以上；
    所述溶剂1为四氢呋喃、甲基四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲苯、二甲苯、三甲苯、氯苯、二氯苯、三氯苯、甲醇、乙醇、丙醇、乙二醇、异丁醇、丙二醇、乙腈、甲酸、乙酸、丙酸、三氟乙酸、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、二甲基乙酰胺、丙酮、丁酮、环己酮、甲基丁酮、甲醚、乙醚、丙醚、吡啶、苯酚、N-甲基吡咯烷酮、乙二醇单甲醚、三甘醇单甲醚、三乙胺、四甲基乙二胺、三辛胺、苯胺、六甲基磷酸三胺中的一种以上；
    所述溶剂2为溶剂1所相对应的氘代溶剂。
  4. 根据权利要求1所述n型共轭聚合物的制备方法，其特征在于：
    n型共轭聚合物的结构为式I、式II、式I与式II组成的结构、式I与式I组成的结构、式II与式II组成的结构、与式I相应的烯醇式转变形式、与式II相应的烯醇式转变形式、式I与之相应的烯醇式转变形式组成的结构、式II与之相应的烯醇式转变形式组成的结构、式I与式II以及相应的烯醇式转变形式组成的结构；其中式I与式I组成的结构中式I与式I不同，式II与式II组成的结构中式II与式II不同；式I与式II组成的结构中含有1个或多个式I，含有1个或多个式II，式I相同或不同，式II相同或不同；
    当n型共轭聚合物为均聚物时，反应单体为同一种结构和/或其相应的烯醇式转变形式的化合物；
    当n型共轭聚合物为共聚物时，反应单体为不同结构的化合物或不同结构的化合物及其相应的烯醇式转变形式。
  5. 根据权利要求4所述n型共轭聚合物的制备方法，其特征在于：
    当n型共轭聚合物为均聚物时，所述n型共轭聚合物的结构选自如下结构的一种，或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100007
    相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100008
    X对应选自O、S、Se、Te或N-R 1；相应的烯醇式转变形式中n为正整数；
    当n型共轭聚合物为共聚物时，所述n型共轭聚合物包括至少两种聚合单元；
    所述每个聚合单元的结构独立地选自以下结构或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100009
    相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100010
    X对应选自O、S、Se、Te或N-R 1；相应的烯醇式转变形式中n为正整数；
    其中
    n型共轭聚合物中，所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    所述烷基衍生物或亚烷基衍生物上的一个或多个碳，被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代；
    和/或
    所述烷基衍生物或亚烷基衍生物上的一个或多个氢，被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代；
    所述n1-n6独立地为正整数；
    所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种。
  6. 根据权利要求1～5任一项所述制备方法得到的n型共轭聚合物，其特征在于：为均聚物或共聚物；
    n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，和/或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100011
    式I中，各自X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    式I、式II中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
    式I、式II中n为正整数；
    其相应的烯醇式转变形式是指与式I结构相应的烯醇式转变形式或式II结构相应的烯醇式转变形式；
    其相应的烯醇式转变形式选自以下结构中一种以上；
    Figure PCTCN2021124880-appb-100012
    n为正整数。
  7. 根据权利要求6所述n型共轭聚合物在有机光电器件中的应用，其特征在于：所述n型共轭聚合物用于电子传输层、热电材料和/或电磁屏蔽材料。
  8. 一种电子传输层，其特征在于：包括n型共轭聚合物；
    所述n型共轭聚合物为均聚物或共聚物，n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，和/或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100013
    式I中，X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    式I、式II中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
    式I、式II中n为正整数；
    其相应的烯醇式转变形式是指与式I结构相应的烯醇式转变形式或式II结构相应的烯醇式转变形式；
    其相应的烯醇式转变形式选自以下结构中一种以上；
    Figure PCTCN2021124880-appb-100014
    n为正整数。
  9. 一种热电材料，其特征在于：包括n型共轭聚合物；
    所述n型共轭聚合物为均聚物或共聚物，n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，和/或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100015
    式I中，X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    式I、式II中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
    式I、式II中n为正整数；
    其相应的烯醇式转变形式是指与式I结构相应的烯醇式转变形式或式II结构相应的烯醇式转变形式；
    其相应的烯醇式转变形式选自以下结构中一种以上；
    Figure PCTCN2021124880-appb-100016
    n为正整数。
  10. 一种电磁屏蔽材料，其特征在于：包括n型共轭聚合物；
    所述n型共轭聚合物为均聚物或共聚物，n型共轭聚合物包括一种或多种聚合单元，聚合单元为式I结构和/或式II结构，和/或其相应的烯醇式转变形式：
    Figure PCTCN2021124880-appb-100017
    式I中，X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    式I、式II中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、 稠合芳杂环的一种；
    式I、式II中n为正整数；
    其相应的烯醇式转变形式是指与式I结构相应的烯醇式转变形式或式II结构相应的烯醇式转变形式；
    其相应的烯醇式转变形式选自以下结构中一种以上；
    Figure PCTCN2021124880-appb-100018
    n为正整数。
  11. 一种超分子n型共轭聚合物，其特征在于：由式I结构或式II结构以及相应的烯醇式转变形式所形成的不同共振形式间通过分子间相互作用自组装形成；
    Figure PCTCN2021124880-appb-100019
    式I中，X独立地选自O、S、Se、Te或N-R 1；所述R 1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种；
    式I、式II中，各自M独立为共轭部分，选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种；
    式I、式II中n为正整数；
    其相应的烯醇式转变形式是指与式I结构相应的烯醇式转变形式或式II结构相应的烯醇式转变形式；
    其相应的烯醇式转变形式选自以下结构中一种以上；
    Figure PCTCN2021124880-appb-100020
    n为正整数；
    当M为苯环时，超分子n型共轭聚合物具有以下结构：
    Figure PCTCN2021124880-appb-100021
  12. 根据权利要求11所述超分子n型共轭聚合物，其特征在于：当X为氧原子，且M为苯环结构时，所述超分子n型共轭聚合物具有以下互变异构：
    Figure PCTCN2021124880-appb-100022
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