A cationic conjugated polymer and a preparation method and application thereof

Abstract

The application discloses a cationic conjugated polymer and a preparation method and application thereof. The structure of the cationic conjugated polymer is shown as formula I, wherein Ar 1 and D represents a N-containing heteroaryl, a N-containing cycloalkenyl or other conjugated groups; Ar and Ar 2 represent an aryl, a heteroaryl or other conjugated groups; R 6 , R 7 and R 8 are the same or different, and are independently selected from hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol group, ether-containing substituent, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl or heteroaryl; Y ‑ represents an anion; and n represents a polymerization degree. The cationic conjugated polymer has high electron mobility, excellent solubility and film-forming property, and can be applied to organic electrochemical transistors and organic thermoelectric devices, so that high-efficiency energy conversion, excellent field-effect mobility, excellent conductivity, good on / off current ratio and high stability are realized.

Description

Technical Field

[0001] This invention relates to a class of organic conjugated polymers with cationic compounds as structural units and their preparation methods, as well as the application of such organic conjugated polymers as organic semiconductor materials in organic thermoelectric and organic electrochemical transistor devices, belonging to the field of organic polymer functional materials. Background Technology

[0002] The successful preparation of the conductive polymer polyacetylene in the 1970s brought organic conjugated polymers to the attention of researchers. In recent years, research on organic conjugated polymers in the field of optoelectronic materials has made rapid progress, especially in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells, where they have demonstrated excellent device performance. Compared with traditional inorganic semiconductor materials, organic conjugated polymer semiconductor materials have unparalleled advantages: the raw materials of organic conjugated polymers are inexpensive and readily available, lightweight, flexible, solution-processable, and their optical and electrical properties can be easily controlled through chemical modification (Bubnova, O.; Crispin, X. Energy Environ. Sci. 2012, 5, 9345-9362). These superior properties have driven the continuous deepening of research on organic conjugated polymers, which are also beginning to emerge in important optoelectronic fields such as thermoelectric devices, organic electrochemical cells (OLECs), and organic electrochemical transistors (OECTs).

[0003] Thermoelectric devices, as semiconductor devices that can directly convert heat energy into electrical energy, can convert a large amount of waste heat from industrial production and solar thermal energy into electrical energy, thus effectively solving the energy shortage problem. Compared with traditional inorganic thermoelectric materials, organic thermoelectric materials have advantages such as low toxicity, light weight, and large-area fabrication, which have led to widespread attention from researchers in recent years and have gradually achieved excellent device performance (Zhang, YH; Wang, YS; Gao, C.; Ni, ZJ; Zhang, XT; Hu, WP; Dong, HLChem. Soc. Rev., 2023, 52, 1331). Currently, the conductivity of organic thermoelectric materials is generally improved by doping (n-doping / p-doping). However, the final molecules obtained after doping are usually ionic compounds with positive and negative charges, which significantly reduces the stability of the material. Although the conductivity of organic thermoelectric materials after doping is significantly improved compared with that before doping, it still lags far behind that of traditional inorganic thermoelectric materials. Therefore, how to prepare high-conductivity organic conjugated materials that are stable in the final state after doping is a key problem that urgently needs to be solved in the field of organic thermoelectrics.

[0004] Organic electrochemical transistors (OECTs) have become a powerful platform for developing organic bioelectronic applications. They can operate in aqueous solutions, have low operating voltages (typically less than 1V), and exhibit transconductance (the sensitivity of source-drain current to gate voltage response) exceeding that of high-mobility materials such as graphene, demonstrating excellent bio-device interfaces and biocompatibility. Therefore, OECTs have wide applications in biochemical sensors, neural interface devices, and neuromorphic computing, attracting increasing attention. The performance of OECTs is often used to evaluate the mixed ion-electron transport properties of conjugated polymers. In recent years, various p-type polymers with μC* greater than 200 F cm⁻¹ have been developed. -1 V -1 s -1 (Kukhta, NA; Marks, A.; Luscombe, CKChem. Rev. 2022, 122, 4325-4355) These polymers have fast response times and are suitable for high-speed sensing applications. However, n-type OECT materials lag far behind, with most n-type OECT materials having μC* values ​​less than 10 F cm⁻¹. -1 V -1 s -1 Furthermore, the response time is relatively slow (Ding, L.; Yu, ZD; Wang, XY; Yao, ZF; Lu, Y.; Yang, CY; Wang, JY; Pei, J. Chem. Rev. 2023, 123, 7421-7497). In addition, the poor performance and stability of n-type OECT devices greatly limit their application.

[0005] The design of conjugated molecules, especially electron-donating or electron-accepting segments, is crucial for the preparation of high-performance conjugated polymers. While many types of high-performance p-type (electron-donating) polymers and bipolar polymers are available, n-type polymers with high electron affinity (approximately 4 eV) and stable processability are not abundant. Therefore, designing and synthesizing efficient organic optoelectronic materials and further fabricating high-performance electrochemical transistor devices has significant social value and practical application implications.

[0006] Cationic conjugated polymers are a class of polymers containing both positive and negative ions. The final polymers obtained after doping are electrically neutral and exhibit high stability. More importantly, cationic conjugated polymers have strong electron affinity, typically resulting in high electrical conductivity after doping. They generally exhibit good solubility in highly polar solvents such as water and trifluoroethanol, making them environmentally friendly and suitable for organic semiconductor device fabrication. Furthermore, they avoid sterically hindered substituents that impede charge transport between polymer chains, resulting in a close-packed structure in the solid state. This significantly reduces the intra- and inter-chain π-π packing distance, effectively enhancing charge transport between polymer chains.

[0007] US Patent 8318894B2 describes charged polymers and their applications in photovoltaic cells, field-effect transistors, and light-emitting diodes. Following their synthetic routes, a series of novel water-soluble, processable n-type conjugated polymers with bispyridine-phenyl conjugated donor-acceptor structural units are reported (Izuhara, D.; Swager, TM J Am. Chem. Soc. 2009, 131, 17724-17725. Izuhara, D.; Swager, TM J Mater. Chem. 2011, 21, 3579-3584.).

[0008]

[0009] Subsequently, homopolymers were used as n-type semiconductors in solution-processed organic thermoelectric generators (OTEGs) for testing (Hwang, S.; Jr, PWJ; Yang, YS; Park, IS; Matsushima, T.; Adachi, C. Phys. Chem. Chem. Phys. 2016, 18, 29199-29207). At a doping concentration of 2.5 mM, it exhibited high electron mobility (σ = 33.3 S cm⁻¹). -1 ) and a high power factor (0.81 μW / m²) -1 K -2 ).

[0010] This invention reveals that although such polymers exhibit good reversible electrochemical activity, electron affinity, and conductivity, the synthetic method has certain defects and limitations. The insolubility of the cationic polymer during ring-closure leads to incomplete ring-closure of the final product, weakening charge transport between polymer chains. Furthermore, the ring-closure reaction requires strongly acidic conditions, which significantly limits the repeating structural units of the copolymer and is highly destructive to unstable structural units. Specifically, the reaction conditions shown in the following formula cannot completely produce product a in the reaction equation.

[0011]

[0012] Furthermore, due to limitations and deficiencies in the synthesis methods, the variety of polymers is limited, and copolymers of this type of cationic conjugated donor-acceptor structural unit have not yet been applied to thermoelectric materials and organic electrochemical transistor devices. Therefore, designing and synthesizing efficient cationic conjugated polymers and exploring their applications in thermoelectric materials and organic electrochemical transistor devices has significant scientific value and importance. Summary of the Invention

[0013] To address a series of prominent problems faced by current organic thermoelectric and electrochemical transistor devices, such as low conductivity and poor stability, this invention uses two novel synthetic methods to design a series of cationic conjugated polymers with different conjugated structures, and systematically studies their molecular structures and corresponding device performance parameters.

[0014] The first method of this invention is an optimization of the method mentioned in patent US8318894B2, which involves adding a dilute solution of a cyclizing reagent dropwise to a dilute solution of a halogenated compound under nitrogen-protected reflux to obtain a cationic conjugated polymer. Increasing the temperature and decreasing the concentration of the conjugated polymer increases its solubility, which is beneficial for complete ring closure. Based on the above research, it was found that the polymers synthesized by the above method are relatively limited. For example, polymers based on DPP (pyrrolopyrroledione) and IID (isoindigo) structural units cannot undergo ring closure via acid solutions (such as thionyl chloride) due to their structural instability. Therefore, the second method of this invention first performs ring closure on a small molecule compound using an acid solution (such as thionyl chloride) to achieve complete ring closure. Then, in a polar solvent (DMSO, NMP, etc.), it undergoes coupling reactions with different structural units (such as DPP, IID, etc.) via Stille, Suzuki, etc., to obtain a series of novel cationic conjugated polymers, which can be further used to prepare high-performance organic thermoelectric and electrochemical transistor devices.

[0015] In the field of thermoelectric devices, the conductivity of cationic polymers can reach up to 480 S cm⁻¹. -1The average maximum conductivity is 412 S cm⁻¹ -1 The power factor reaches its maximum value of 58 μW / m after 1 minute of doping. -1 K -2 This has significant practical implications for the research and application of thermoelectric devices. This series of cationic polymers exhibits high electron mobility; in organic electrochemical transistor devices, the electron mobility of cationic conjugated polymers can reach 0.25 cm⁻¹. 2 V -1 s -1 The volume capacitance can reach 485F cm⁻¹ -3 μC* can reach 120F cm -1 V -1 s -1 This provides a novel approach and direction for developing new, high-performance, and environmentally friendly electrochemical transistor devices. Furthermore, by culturing immortalized human epidermal cells in culture dishes containing modified polymer films, no cell death was observed, demonstrating the good biocompatibility of the cationic polymer films. This also enabled the amplification of human electrooculography and electrocardiography signals.

[0016] In a first aspect of the invention, a conjugated polymer of a nitrogen-containing heterocyclic cationic repeating unit with the structure shown in Formula I is provided:

[0017]

[0018] Among them, Ar 1 And D represents a heteroaryl, cycloalkenyl, or other conjugated group containing N; Ar and Ar 2 Represents aryl, heteroaryl, or other conjugated groups; R 6 R 7 and R 8 Whether identical or different, independently selected from hydrogen, halogen (F, Cl, Br, I), cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, ether-containing substituents, halogen-substituted alkyl, halogen-substituted alkoxy, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl, can form a ring independently, and / or can form a bond with another repeating unit or the end group of the polymer; Y - Represents anion; n is an integer representing the degree of polymerization of the polymer.

[0019] The alkyl group is preferably a straight-chain or branched alkyl group of C1-C46, more preferably a straight-chain or branched alkyl group of C1-C36, and most preferably a C1-C4 alkyl group.

[0020] The halogen-substituted alkyl group is preferably a straight-chain or branched halogen-substituted alkyl group of C1-C46, more preferably a straight-chain or branched halogen-substituted alkyl group of C1-C36, and most preferably a C1-C4 straight-chain alkyl group substituted with fluorine, chlorine and / or bromine.

[0021] The alkoxy group mentioned above is preferably a straight-chain or branched alkoxy group of C1-C46, and more preferably a straight-chain or branched alkoxy group of C1-C36.

[0022] The halogen-substituted alkoxy group is preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C46, more preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C36, and most preferably a halogen-substituted alkoxy group of C1-C4.

[0023] The alkyl-substituted aryl group is preferably a phenyl group having one to three C1-C4 alkyl substituents.

[0024] The aforementioned polyethylene glycol group is preferably a straight-chain or branched polyethylene glycol group of C2-C36, and more preferably a straight-chain or branched polyethylene glycol group of C2-C18.

[0025] The ether-containing substituents mentioned above are preferably C1-C3 ether-containing groups, such as -CH2-O-CH3 or -CH2-O-C2H5.

[0026] The alkenyl group mentioned above is preferably a C2-C18 alkenyl group, more preferably a C2-C10 alkenyl group, and most preferably a C2-C6 alkenyl group.

[0027] The aforementioned alkynyl group is preferably a C2-C18 alkynyl group, more preferably a C2-C10 alkynyl group, and most preferably a C2-C6 alkynyl group.

[0028] The aryl group mentioned above is preferably a C6-C30 aryl group, such as phenyl, biphenyl, naphthyl, anthracene, etc.

[0029] The aforementioned heteroaryl groups are preferably C2-C26 heteroaryl groups, such as pyridyl, thiophene, pyrazinyl, piperazinyl, etc.

[0030] The above-mentioned N-containing cycloalkenyl groups include, for example, 1,3-diazacyclopentadiene and 1,2-dihydropyridine.

[0031] Preferred, Ar, Ar 1 and Ar 2 It is an aryl group of C6-C30, or a heteroaryl group of C2-C26, or other conjugated groups of C2-C26, such as -C=C-, -C=CC=C-.

[0032] Y -The preferred anion is derived from halides (e.g., chlorides, bromides, iodides, fluorides), nitrates, sulfates, phosphates, carboxylates, and acetates, i.e., selected from I... - Cl - ,Br - F - NO3 - SO4 2- PO4 3- COO - CH3COO - wait.

[0033] Based on the above research, this invention proposes two new methods for synthesizing polymers of formula I. The first method is a method for synthesizing polymers of general formula d from raw materials (e.g., 2,5-dibromo-p-xylene derivatives). Subsequently, a halogenated organic solvent is used as the cyclization reaction solvent. Under nitrogen protection and reflux conditions, a dilute solution of the cyclization reagent is added dropwise to a dilute solution of polymer of formula d to obtain the quaternary nitrogen cationic polymer of general formula I.

[0034]

[0035] Among them, the derivatives (compound of formula c) of 2,5-dibromo-p-xylene are obtained through free radical reaction (bromination of bromosuccinimide (NBS)), Wittig reaction (reaction of benzyl bromide with triphenylphosphine to generate ylide, followed by reaction with aldehyde to generate styrene derivatives), oxidative addition reaction (alkenes are reacted with hydrogen peroxide to obtain phenylethanol derivatives), electrophilic substitution reaction (protection of hydroxyl groups by tert-butyldimethylchlorosilane (TBDMSCl)), and Suzuki coupling reaction (reaction with dipinane ester).

[0036] The reaction conditions (1) are the monomer shown in c and the aryl, heteroaryl or other conjugated monomer R*-Ar. 2 (R 8 The polymer shown in d is formed by the polymerization of )-R*, where R 11 Representing alkoxy or silanoxy, this functional group can be tert-butyldimethylsilanoxy, trimethylsilylalkoxy, dimethylisopropylsilylalkoxy, etc.; R 9 R* represents the functional group required for the polymerization reaction of the monomer. For example, for the Suzuki coupling reaction, this functional group can be a halogen, borate, or borate group. In this case, R* represents the functional group required for the polymerization reaction of the monomer. 9 It can be a borate group, a borate ester, or a halogen (note that when R* is a halogen, R...). 9 It is a borate ester or borate group; when R* is a borate ester or borate group, R 9(Halogen); for Stille coupling, the functional group can be halogen or alkyltin; for Sonogashira coupling, the functional group can be halogen or ethynyl; for Heck coupling, the functional group can be halogen or vinyl; for Kumada coupling, the functional group is halogen; for C-H bond activation coupling, the functional group can be halogen or hydrogen; for Hiyama coupling, the functional group can be halogen or silyl. 2 Represents a C6-C30 aryl group, a C2-C26 heteroaryl group, or another C2-C26 conjugated group that can be optionally substituted. Monomer R*-Ar 2 (R 8 )-R* can be selected from the compounds shown in formulas II-1 to II-20 below:

[0037]

[0038] R 12 It represents hydrogen atoms, halogen atoms (such as F, Cl, etc.), nitro, amino, cyano, alkyl, alkenyl, alkoxy, halogen-substituted alkyl, halogen-substituted alkoxy, etc.

[0039] b and b' can be independently chosen from the following structures: —S—, —Se—, —O—, and —NR. 8 —;

[0040] c and c' can be independently chosen from the following structures: —N=, =N—, —SiR 8 =, =SiR 8 —,—CR 8 = and =CR 8 —;

[0041] d and d' can be independently chosen from the following structures: —N=, =N—, —SiR 8 =, =SiR 8 —,—CR 8 =, =CR 8 —, =CR 8 R 8 —CR 8 R 8 —,—CR 8 —CR 8 =;

[0042] e can be selected from the following structures: —S—, —S(O)—, —S(O)2—, —O—, —SiR 8 R 8 —,—CR 8 R 8 —CR 8 R8 —,—CR 8 =CR 8 —, —C(O)— and —C(C(CN)2)—;

[0043] g, h, g', h' can be independently selected from the following structures: —CR 8 =, =CR 8 —, and —N = and = N—;

[0044] R 14 and R 15 Same or different, selected from hydrogen, fluorine, cyano, alkyl, halogen-substituted alkyl, phenyl and alkyl-substituted phenyl;

[0045] The above R 8 It can be hydrogen, halogen (F, Cl, Br, I), cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, ether-containing substituents, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl or heteroaryl, etc.

[0046] The alkyl group is preferably a straight-chain or branched alkyl group of C1-C46, and more preferably a straight-chain or branched alkyl group of C1-C36.

[0047] The aforementioned polyethylene glycol group is preferably a straight-chain or branched polyethylene glycol group of C2-C36, and more preferably a straight-chain or branched polyethylene glycol group of C2-C18.

[0048] The halogen-substituted alkyl group is preferably a straight-chain or branched halogen-substituted alkyl group of C1-C46, and more preferably a straight-chain or branched halogen-substituted alkyl group of C1-C36.

[0049] The alkoxy group mentioned above is preferably a straight-chain or branched alkoxy group of C1-C46, and more preferably a straight-chain or branched alkoxy group of C1-C36.

[0050] The halogen-substituted alkoxy group is preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C46, and more preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C36.

[0051] The alkenyl group is preferably a C2-C18 alkenyl group, more preferably a C2-C10 alkenyl group, and most preferably a C2-C6 alkenyl group.

[0052] The alkynyl group is preferably a C2-C18 alkynyl group, more preferably a C2-C10 alkynyl group, and most preferably a C2-C6 alkynyl group.

[0053] Among them, the monomer R*-Ar 2 (R 8 )-R* is more preferably one of the following structures:

[0054]

[0055] Reaction condition (2) involves cyclizing the repeating unit containing the nitrogen heterocycle, such that R 11 The departure of the group yields a quaternary nitrogen cationic ring system, generating the cationic conjugated polymer shown in Formula I, wherein Y - The cyclization reaction is carried out using a halogenated organic solvent as the cyclization reaction solvent. Under anhydrous and oxygen-free conditions, the concentration of the reaction substrate (polymer of formula d) is controlled within the range of 3–5 mM, and the reaction temperature is 75–100 °C, preferably 80–85 °C. A cyclizing reagent with a concentration of 2–2.5 M (dissolved in the cyclization reaction solvent) is added dropwise to the polymer of formula d solution. The cyclizing reagent is preferably phosphoryl chloride, sulfonyl chloride, carboxyl chloride, and thioyl chloride, with sulfonyl chloride (dimethyl sulfoxide) being the most preferred. The cyclization reaction solvent is preferably dichloromethane, chlorobenzene, 1,1,2,2,-tetrachloroethane, or trichloromethane, with trichloromethane being more preferred. The reaction time is preferably 16–36 hours, more preferably 20–24 hours.

[0056] In the first synthetic method described above, the nitrogen-containing heterocyclic part in Formula I It can be one of the following structures:

[0057]

[0058] Below are some typical examples of polymer molecules of Formula I that can be prepared by the first synthetic method described above:

[0059]

[0060] This invention proposes a new method for synthesizing the polymer shown in Formula I. Compared to the first method, the second method has wider applicability. For example, polymers based on unstable structural units under acid conditions, such as DPP (pyrrolopyrrole dione) and IID (isoindigo), which cannot be obtained by the first method, can be successfully obtained by the second method. In the second synthesis method, the monomers represented by general formula g and monomer R*-Ar... 2 (R 8 The polymer shown in Formula I is synthesized by polymerization of )-R*, and due to the water solubility of the cationic monomer unit, a polar organic solvent (dimethyl sulfoxide, N-methylpyrrolidone, etc.) is used as the reaction solvent. In general formula g, R... 9 The functional group that is required for the polymerization reaction of the monomer is represented, such as halogen, borate or borate ester, alkyltin, ethynyl, vinyl, hydrogen and silane, etc.

[0061]

[0062] This invention provides a method for synthesizing a cationic repeating unit of general formula g from a raw material (e.g., a 2,5-dibromo-p-xylene derivative), and then polymerizing the repeating unit of general formula g and an aromatic or conjugated monomers in an anhydrous and oxygen-free polar organic solvent (e.g., dimethyl sulfoxide, N-methylpyrrolidone) to form a quaternary nitrogen cationic polymer of formula I.

[0063]

[0064] Reaction condition (3) is to cyclize the compound of general formula c, such that R 11 The departure of the group yields a quaternary nitrogen cationic ring system, producing the compound shown in formula g. Wherein, R... 11 The functional group represents an alkoxy or silanoxy group, which can be tert-butyldimethylsilanoxy, trimethylsilylalkoxy, dimethylisopropylsilylalkoxy, etc. The cyclizing agent is phosphoric acid chloride, sulfonyl chloride, carboxyl chloride, and thioyl chloride, etc., preferably sulfonyl chloride (dimethyl sulfoxide). The reaction temperature is 25–150°C, preferably 55–100°C, more preferably 80–85°C. The reaction solvent is preferably dichloromethane, tetrahydrofuran, acetonitrile, chlorobenzene, 1,1,2,2,-tetrachloroethane, or trichloromethane, more preferably trichloromethane. The reaction time is preferably 12–36 hours, more preferably 18–24 hours.

[0065] The reaction conditions (4) are the repeating unit monomer shown in formula g and the monomer R*-Ar. 2 (R 8 The polymer shown in I is formed by the polymerization of R-R*, wherein R 9 R* represents the functional group required for the polymerization of the monomer. For example, for the Suzuki coupling reaction, the functional group can be halogen, borate, or borate; for the Stille coupling reaction, the functional group can be halogen or alkyltin; for the Sonogashira coupling reaction, the functional group can be halogen or ethynyl; for the Heck coupling reaction, the functional group can be halogen or vinyl; for the Kumada coupling reaction, the functional group is halogen; for the C-H bond activated coupling reaction, the functional group can be halogen or hydrogen; for the Hiyama coupling reaction, the functional group can be halogen or silane. The reaction temperature is 25-200°C, preferably 80-150°C, more preferably 110°C. The reaction solvent is preferably o-xylene, o-dichlorobenzene, N,N-dimethylformamide, chlorobenzene, N-methylpyrrolidone, or dimethyl sulfoxide, more preferably dimethyl sulfoxide. The reaction time is preferably 12-72 hours, more preferably 36-48 hours. Ar 2 Represents a C6-C30 aryl group, a C2-C26 heteroaryl group, or another C2-C26 conjugated group that can be optionally substituted. The monomer R*-Ar 2 (R 8In addition to the compounds shown above, compounds represented by formulas IV-1 to IV-6 may also be selected:

[0066]

[0067] a and a' can be independently chosen from the following structures: —S—, —Se—, —O—, and —NR. 8 —;

[0068] m and m' can be independently chosen from the following structures: —S—, —S(O)—, —S(O)2—, —O—, —NR 8 —,—SiR 8 R 8 —,—CR 8 R 8 —CR 8 R 8 —,—CR 8 =CR 8 —, —C(O)— and —C(C(CN)2)—;

[0069] n and n' can be independently chosen from the following structures: —N=, =N—, —SiR 8 =, =SiR 8 —,—SiR 8 R 8 —,—CR 8 R 8 —CR 8 R 8 —and—CR 8 =CR 8 —;

[0070] The above R 8 It can be hydrogen, halogen (F, Cl, Br, I), cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, ether-containing substituents, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl or heteroaryl, etc.

[0071] The alkyl group mentioned above is preferably a straight-chain or branched alkyl group of C1-C46, and more preferably a straight-chain or branched alkyl group of C1-C36.

[0072] The aforementioned polyethylene glycol group is preferably a straight-chain or branched polyethylene glycol group of C2-C36, and more preferably a straight-chain or branched polyethylene glycol group of C2-C18.

[0073] The halogen-substituted alkyl group is preferably a straight-chain or branched halogen-substituted alkyl group of C1-C46, and more preferably a straight-chain or branched halogen-substituted alkyl group of C1-C36.

[0074] The alkoxy group mentioned above is preferably a straight-chain or branched alkoxy group of C1-C46, and more preferably a straight-chain or branched alkoxy group of C1-C36.

[0075] The halogen-substituted alkoxy group is preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C46, and more preferably a straight-chain or branched halogen-substituted alkoxy group of C1-C36.

[0076] The alkenyl group is preferably a C2-C18 alkenyl group, more preferably a C2-C10 alkenyl group, and most preferably a C2-C6 alkenyl group.

[0077] The alkynyl group is preferably a C2-C18 alkynyl group, more preferably a C2-C10 alkynyl group, and most preferably a C2-C6 alkynyl group.

[0078] Among them, the aromatic or conjugated monomer R*-Ar 2 (R 8 )-R* is more preferably one of the following structures:

[0079]

[0080] Below are some typical examples of polymer molecules of Formula I prepared by the second synthetic method described above:

[0081]

[0082] In a second aspect of the invention, the cationic conjugated polymer shown in Formula I is used as an organic semiconductor material in organic thermoelectric devices. Thermoelectric conversion technology utilizes the Seebeck and Peltier effects of semiconductor materials to directly convert thermal energy into electrical energy. Thermoelectric conversion devices do not require moving parts or toxic working fluids, playing a crucial role in addressing increasingly severe global energy and environmental problems. It has been developed and utilized in fields such as the utilization of industrial waste heat and solar thermal power generation.

[0083] A thermoelectric conversion device generally consists of three parts: a heat source, a heat sink, and a thermopile. The thermopile is composed of a series of thermocouples connected in series, capable of converting heat energy into electrical energy. These thermocouples are typically composed of different types of N / P-type thermoelectric materials. When a temperature gradient exists between their two ends, i.e., the heat source end and the heat sink end, a potential difference is generated. Utilizing this principle of thermoelectric power generation, thermoelectric devices can generate electricity using the temperature difference between the human body and the external environment, providing power for wearable devices.

[0084] The manufacturing process of thermoelectric devices containing the polymer of the present invention can be referred to the processing techniques in CN108470818A, CN109524535A and CN108305935A.

[0085] This invention provides methods for synthesizing polymers of Formula I and their applications in organic electrochemical transistor devices and thermoelectric devices. Both synthesis methods can yield water-soluble cationic conjugated polymers that are unavailable through existing synthesis methods in high yield. The polymers of this invention exhibit excellent solubility and film-forming properties in polar solvents. When the polymers of this invention are used in organic electrochemical transistors and organic thermoelectric devices, efficient energy conversion, excellent field-effect mobility and / or excellent conductivity, good on / off current ratio, and / or excellent stability can be observed.

[0086] In a third aspect of the invention, the cationic conjugated polymer shown in Formula I above is used as an organic semiconductor material in optoelectronic devices such as organic electrochemical transistors (OECTs). Therefore, the present invention provides an OECT device comprising the polymer of the present invention. For the purposes of the present invention, the organic electrochemical transistor device utilizes the electrochemical redox reaction of an organic material. These devices contain an electrolyte and a conductive polymer capable of switching between oxidized and reduced states. One of these oxidized states corresponds to a low conductivity of the material, preferably zero, while another oxidized state corresponds to a higher conductivity than the first state. The manufacture of this OECT device can be referenced in CN1494743A.

[0087] The OECT device includes: a source contact; a drain contact; at least one gate; an electrochemically active element arranged between and in direct electrical contact with the source and drain contacts, the electrochemically active element comprising a transistor channel and composed of a material containing an organic material capable of electrochemically altering its conductivity by changing its redox state; and a solidified electrolyte in direct electrical contact with the electrochemically active element and the at least one gate, and placed therebetween in a manner that prevents electron flow between the electrochemically active element and the gate, thereby allowing control of electron flow between the source and drain contacts by a voltage applied to the gate.

[0088] The structure of the electrochemical transistor device according to the invention is advantageous because it enables layered transistor devices with only a few layers, for example, having a patterned material layer containing an organic material, which includes source, drain, and gate electrodes, as well as electrochemically active elements. Then, preferably, the source and drain contacts are formed by a conductive material forming direct electrical contacts using a continuous sheet of P2 material. The gate electrode can also be formed using another conductive material. To provide the necessary electrochemical reaction, thereby altering the conductivity of the active element, a cured electrolyte is mounted to form direct electrical contacts with both the active element and the gate.

[0089] The electrochemical transistor device can be fabricated by depositing different components of the polymer comprising the present invention onto a support using conventional printing methods such as screen printing, offset printing, inkjet printing, and lithography, as described in Modern Coating and Drying Technology (1992), eds. ED. Cohen and E.B. Gutoff, VCH Publisher Inc, New York, NY, USA, or coating methods such as blade coating, cast coating, extrusion coating, and dip coating. Attached Figure Description

[0090] Figure 1 The structural formula of the cationic conjugated polymer shown in Formula I of this invention is given.

[0091] Figure 2 The graph shows the change in conductivity of polymer P2 as the active layer material over doping time.

[0092] Figure 3 The graph shows the Seebeck coefficient of polymer P2 as the active layer material as a function of doping time.

[0093] Figure 4 The graph shows the power factor of polymer P2 as the active layer material as a function of doping time.

[0094] Figure 5 The graph shows the change in conductivity of polymer P4 as the active layer material over doping time.

[0095] Figure 6 The graph shows the Seebeck coefficient of polymer P4 as the active layer material as a function of doping time.

[0096] Figure 7 The graph shows the power factor of polymer P4 as the active layer material as a function of doping time.

[0097] Figure 8 This is a schematic diagram of the device structure of an organic electrochemical transistor made using the polymer of the present invention as the active layer material.

[0098] Figure 9 The active material is polymer P2. Figure 2 The transfer characteristic curve of the device shown (where V) DS For source-drain voltage, I DS For source and drain current, V GS (Gate voltage).

[0099] Figure 10 The active material is polymer P2. Figure 2 The output characteristic curve of the device shown is (where V) DS For source-drain voltage, I DSFor source and drain current, V GS (Gate voltage).

[0100] Figure 11 The active material is polymer P2. Figure 2 The switching test curve of the device shown (where V) DS For source-drain voltage, I DS For source and drain current, V GS (where τ is the gate voltage and τ is the response time).

[0101] Figure 12 The active material is polymer P2. Figure 2 The inverter voltage transfer characteristics and gain curve of the device shown are illustrated. Detailed Implementation

[0102] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the scope of the invention is not limited in any way.

[0103] Example 1

[0104]

[0105] Synthetic route of compound 1: 2,5-Dibromo-p-xylene (20 g, 76.4 mmol), bromosuccinimide (NBS) (30 g, 168.1 mmol), and azobisisobutyronitrile (AIBN) (2.6 g, 15.3 mmol) were added to a 1000 mL two-necked flask. The reaction system was anhydrous and oxygen-free. Carbon tetrachloride (500 mL) was added under nitrogen protection, and the reaction was carried out under reflux for 36 h. After cooling to room temperature, the mixture was evaporated to dryness, and the solvent in the reaction system was removed. The mixture was extracted three times with chloroform and water. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and recrystallized from ethanol to give 1 pale yellow-white crystals, approximately 26.7 g, with a yield of 83.6%. 1 HNMR (400MHz, Chloroform-d) δ7.66 (s, 1H), 4.51 (s, 2H).

[0106] Example 2

[0107]

[0108] Synthetic route of compound 2: Compound 1 (2.5 g, 6.0 mmol) and triphenylphosphine (3.9 g, 15.0 mmol) were added to a 100 mL two-necked flask. The reaction system was anhydrous and oxygen-free. Under nitrogen protection, N,N-dimethylformamide (DMF) (30 mL) was added, and the reaction was carried out under reflux for 24 h. After cooling to room temperature, the reaction was stopped, and a large amount of white solid precipitated. The solid was filtered and dried. The white solid (4.0 g, 6.0 mmol) was transferred to a 100 mL two-necked flask, and paraformaldehyde (3.6 g, 120.0 mmol) was added. The reaction system was anhydrous and oxygen-free. Under nitrogen protection, THF (30 mL) was added, followed by the slow addition of a THF (10 mL) solution of potassium tert-butoxide (2.0 g, 18.0 mmol). The reaction was heated to about 65 °C and carried out for 12 h. The mixture was cooled to room temperature and extracted three times with dichloromethane and water. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography using petroleum ether as the eluent to obtain 2 white solid powders, approximately 1.56 g, with a yield of 92.6%. 1 H NMR (400MHz, Chloroform-d) δ7.72 (s, 1H), 6.95 (dd, J = 17.4, 11.0Hz, 1H), 5.71 (d, J = 17.4Hz, 1H), 5.40 (d, J = 11.1Hz, 1H).

[0109] Example 3

[0110]

[0111] Synthetic route of compound 3: Compound 2 (2.5 g, 8.7 mmol) was added to a 250 mL two-necked flask. The system was anhydrous and oxygen-free. THF (40 mL) was added under nitrogen protection, and the mixture was kept in an ice-water bath at approximately 0 °C. 9-BBN (0.5 M in THF, 45 mL, 22.5 mmol) was slowly added dropwise to the reaction system. After the addition was complete, the mixture was allowed to return to room temperature, and the reaction was continued for 12 h. The reaction system was then kept in an ice-water bath at approximately 0 °C, and methanol (15 mL) was slowly added dropwise to quench the reaction. Subsequently, an aqueous solution of sodium hydroxide (2 M, 75 mL) was injected into the reaction system, and hydrogen peroxide (15 mL) was added slowly in portions. The reaction was continued for 2 h under ice-water bath conditions. After returning to room temperature, the mixture was extracted three times with diethyl ether and water. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography using petroleum ether:ethyl acetate = 15:1 as the eluent to obtain a white solid 3, approximately 2.1 g, with a yield of 74.2%. 1H NMR (400MHz, Dimethyl sulfoxide-d6) δ7.55 (s, 1H), 4.76 (s, 1H), 3.59 (t, J = 6.8 Hz, 2H), 2.80 (t, J = 6.8 Hz, 2H).

[0112] Example 4

[0113]

[0114] Synthetic route of compound 4: Compound 3 (2.5 g, 7.8 mmol) and imidazole (2.1 g, 31.1 mmol) were added to a 100 mL two-necked flask. The system was subjected to anhydrous and oxygen-free conditions. DMF (10 mL) was added under nitrogen protection, and the mixture was heated to approximately 0 °C in an ice-water bath. A DMF (5 mL) solution of TBDMSCl (2.8 g, 18.7 mmol) was added to the reaction system, and the mixture was stirred for 30 min. Subsequently, the mixture was brought to room temperature and stirred for 24 h. After the reaction was complete, the mixture was extracted three times with saturated sodium chloride aqueous solution and ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography using petroleum ether:ethyl acetate = 20:1 as the eluent to obtain a white solid 4, approximately 3.57 g, with a yield of 83.5%. 1 H NMR (400MHz, Chloroform-d) δ7.44 (s, 1H), 3.79 (t, J = 6.7Hz, 2H), 2.90 (t, J = 6.7Hz, 2H), 0.87 (s, 9H), -0.02 (s, 6H).

[0115] Example 5

[0116]

[0117] Synthetic route of compound 5: Compound 4 (0.3 g, 0.5 mmol), Pd(dppf)Cl2 (23.7 mg, 0.03 mmol), pipinol borate ((BPin)2) (0.5 g, 2.0 mmol), and anhydrous potassium acetate (0.4 g, 4.0 mmol) were added to a 50 mL Schlenk tube. 1,4-dioxane (10 mL) was redistilled as a solvent. The mixture was subjected to three freeze-drying cycles to ensure anhydrous and oxygen-free conditions. The reaction was then heated to approximately 100 °C for 36 h. After cooling to room temperature, the solvent was evaporated, and the mixture was extracted three times with dichloromethane and water. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography using petroleum ether:ethyl acetate = 15:1 as the eluent. Approximately 0.25 g of a white solid 5 was obtained, with a yield of 72.3%. 1H NMR (400MHz, Chloroform-d) δ7.64 (s, 1H), 3.75 (t, J = 7.4Hz, 2H), 3.09 (t, J = 7.4Hz, 2H), 1.34 (s, 12H), 0.88 (s, 9H), -0.01 (s, 6H).

[0118] Example 6

[0119]

[0120] Synthetic route of compound 6: Compound 5 (0.3 g, 0.5 mmol), Pd(PPh3)4 (53.6 mg, 0.05 mmol), 5-bromo-2-iodopyridine (0.6 g, 2.0 mmol), and anhydrous cesium carbonate (1.0 g, 3.0 mmol), along with a mixed solution of ethylene glycol dimethyl ether (DME, 10 mL) and H2O (5 mL) as solvent, were added to a 50 mL Schlenk tube. The system was subjected to three freeze-drying cycles to eliminate oxygen. The reaction was heated to approximately 100 °C for 48 h. After cooling to room temperature, the reaction solution was concentrated and extracted three times with dichloromethane and water. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography using petroleum ether:ethyl acetate (25:1) as eluent to obtain a white solid powder 6, namely PyPh2Br, approximately 0.17 g, with a yield of 51.6%. 1 H NMR (400MHz, Chloroform-d) δ8.75 (d, J=2.2Hz, 1H), 7.88 (dd, J=8.3, 2.4Hz, 1H), 7.37 (d, J=8. 3Hz, 1H), 7.32 (s, 1H), 3.71 (t, J = 7.3Hz, 2H), 2.94 (t, J = 7.3Hz, 2H), 0.80 (s, 9H), -0.08 (s, 6H).

[0121] Example 7

[0122]

[0123] Synthetic route of polymer P1: Compound 6 (100 mg, 141.5 μmol), trans-1,2-bis(tributyltin)ethylene (85.77 mg, 141.5 μmol), Pd2(dba)3 (5.18 mg, 5.7 μmol), and P(o-tol)3 (6.89 mg, 22.6 μmol) were added to a 25 mL Schlenk tube. Toluene (6 mL) was redistilled as a solvent. The system was subjected to three freeze-drying cycles to ensure anhydrous and oxygen-free conditions. The reaction was heated to approximately 110 °C and reacted for 48 h. After cooling to room temperature, the reaction solution was poured into a methanol solution (200 mL), allowed to settle for 10 min, filtered, and the filter cake was washed several times with methanol. The obtained polymer was wrapped in filter paper and placed in a Soxhlet extraction apparatus. It was extracted with methanol, acetone, n-hexane, dichloromethane, and chloroform, respectively. The chloroform fraction was collected to obtain a grayish-white solid P1, about 29.1 mg, with a yield of 35.8%. 1 H NMR (400MHz, Chloroform-d) δ8.87(s,1H),7.99(s,1H),7.53(s,1H),7.42(s,1H),7.29(s,1H),3.78(s,2H),3.05(s,2H),0.83(s,9H),-0.05(s,6H).

[0124] Example 8

[0125]

[0126] Synthetic route of polymer P2: Polymer P1 (50 mg, 87.0 μmol) obtained by trichloromethane fraction extraction was added to a 100 mL two-necked flask. The system was subjected to anhydrous and oxygen-free treatment. Under nitrogen protection, trichloromethane (HPLC, 50 mL) was added, and the temperature was raised to about 80 °C. The reaction was allowed to proceed for 10 min. A solution of 1 mL of thionyl chloride in 5 mL of trichloromethane was slowly added dropwise to the reaction system. After the addition was complete, the reaction was continued for 24 h. The mixture was cooled to room temperature, the solvent was evaporated to remove excess thionyl chloride, and trichloromethane was added to the reaction system. The mixture was filtered, and the filter cake was washed repeatedly with trichloromethane to obtain a brown solid P2, approximately 30.83 mg, with a yield of 92.5%. 1 ¹H NMR (400MHz, D₂O) δ 9.14 (s, 1H), 8.87 (s, 1H), 8.64 (s, 1H), 8.27 (s, 1H), 7.70 (s, 1H), 4.94 (s, 2H), 3.51 (s, 2H), number average molecular weight M n =23.4Kda.

[0127] Example 9

[0128]

[0129] Synthetic route of polymer P3: Compound 6 (100 mg, 141.5 μmol), (3,4-difluorothiophene-2,5-diyl)bis(trimethyltin) (63.07 mg, 141.5 μmol), Pd2(dba)3 (5.18 mg, 5.7 μmol), and P(o-tol)3 (6.89 mg, 22.6 μmol) were added to a 25 mL Schlenk tube. Toluene (6 mL) was redistilled as a solvent, and the system was subjected to three freeze-dip cycles to ensure anhydrous and oxygen-free conditions. The reaction was heated to approximately 110 °C and reacted for 48 h. After cooling to room temperature, the reaction solution was poured into a methanol solution (200 mL), allowed to settle for 10 min, filtered, and the filter cake was washed several times with methanol. The obtained polymer was wrapped in filter paper and placed in a Soxhlet extraction apparatus. It was extracted with methanol, acetone, n-hexane, dichloromethane, and chloroform, respectively. The chloroform fraction was collected to obtain a yellow solid P3, about 42.99 mg, with a yield of 45.6%. 1 H NMR(400MHz,Chloroform-d)δ9.03(s,1H),8.07(d,J=7.4Hz,1H),7.61(d,J=7 .3Hz,1H),7.44(s,1H),3.80(s,2H),3.06(s,2H),0.83(s,9H),-0.04(s,6H).

[0130] Example 10

[0131]

[0132] Synthetic route of polymer P4: Polymer P2 (50 mg, 75.0 μmol) obtained by trichloromethane fraction extraction was added to a 100 mL two-necked flask. The system was subjected to anhydrous and oxygen-free treatment. Under nitrogen protection, trichloromethane (HPLC, 50 mL) was added, and the temperature was raised to about 80 °C. The reaction was allowed to proceed for 10 min. A solution of 1 mL thionyl chloride in 5 mL of trichloromethane was slowly added dropwise to the reaction system. After the addition was complete, the reaction was continued for 24 h. The mixture was cooled to room temperature, the solvent was evaporated to remove excess thionyl chloride, and trichloromethane was added to the reaction system. The mixture was filtered, and the filter cake was washed repeatedly with trichloromethane to obtain a brownish-red solid P4, approximately 32.44 mg, with a yield of 91.2%. 1 H NMR (400MHz, D2O+MeOD) δ9.40(s,1H),8.98(s,1H),8.83(s,1H),8.42(s,1H),5.06(s,2H),3.60(s,2H).

[0133] Example 11

[0134]

[0135] Synthetic route of polymer P5: Compound 6 (100 mg, 141.5 μmol), 5,5'-bis(trimethyltinyl)-[2,2'-bithiophene]-3,3'-dicarboxynitrile (76.68 mg, 141.5 μmol), Pd2(dba)3 (5.18 mg, 5.7 μmol), and P(o-tol)3 (6.89 mg, 22.6 μmol) were added to a 25 mL Schlenk tube. Toluene (6 mL) was redistilled as a solvent, and the system was subjected to three freeze-dip evaporations to ensure anhydrous and oxygen-free conditions. The reaction was heated to approximately 110 °C and reacted for 48 h. After cooling to room temperature, the reaction solution was poured into a methanol solution (200 mL), allowed to settle for 10 min, filtered, and the filter cake was washed several times with methanol. The obtained polymer was wrapped in filter paper and placed in a Soxhlet extraction apparatus. It was extracted with methanol, acetone, n-hexane, dichloromethane, and chloroform, respectively. The chloroform fraction was collected to obtain a yellow solid P5, about 63.21 mg, with a yield of 58.6%. 1 H NMR (400MHz, Chloroform-d) δ9.01(s,1H),8.02(s,1H),8.00(s,1H),7.65(s,2H),7.45(s,1H),3.80(s,2H),3.05(s,2H),0.83(s,9H),-0.04(s,6H).

[0136] Example 12

[0137]

[0138] Synthetic route of polymer P6: Polymer P3 (50 mg, 65.6 μmol) obtained by trichloromethane fraction extraction was added to a 100 mL two-necked flask. The system was subjected to anhydrous and oxygen-free treatment. Trichloromethane (HPLC, 50 mL) was added under nitrogen protection, and the temperature was raised to about 80 °C. The reaction was allowed to proceed for 10 min. A solution of 1 mL thionyl chloride in 5 mL of trichloromethane was slowly added dropwise to the reaction system. After the addition was complete, the reaction was continued for 24 h. The mixture was cooled to room temperature, the solvent was evaporated to remove excess thionyl chloride, and trichloromethane was added to the reaction system. The mixture was filtered, and the filter cake was washed repeatedly with trichloromethane to obtain a brownish-red solid P6, approximately 33.69 mg, with a yield of 90.1%. 1 H NMR (400MHz, D2O+MeOD) δ9.49(s,1H),8.99(s,1H),8.81(s,1H),8.42(s,1H),8.32(s,1H),5.04(s,2H),3.62(s,2H).

[0139] Example 13

[0140]

[0141] Synthetic route of compound 7: Compound 6 (300 mg, 424.5 μmol) was added to a 100 mL Schlenk tube. The system was anhydrous and oxygen-free. Under nitrogen protection, chloroform (HPLC, 50 mL) was added, followed by the slow dropwise addition of thionyl chloride (8 mL) in chloroform (10 mL). After the addition was complete, the reaction was continued at room temperature for 24 h. The solvent was evaporated to remove excess thionyl chloride. Chloroform was added to the reaction system, and the mixture was filtered. The filter cake was repeatedly washed with chloroform to obtain a pale yellow solid 7, approximately 200.1 mg, with a yield of 91.5%. 1 H NMR (400MHz, D2O) δ9.09 (s, 1H), 8.70 (d, J = 8.6Hz, 1H), 8.41 (d, J = 8.8Hz, 1H), 8.13 (s, 1H), 4.77 (t, J = 6.3Hz, 2H), 3.45-3.28 (m, 2H).

[0142] Example 14

[0143]

[0144] Synthetic route of polymer P2-1: Compound 7 (30 mg, 58.2 μmol), trans-1,2-bis(tributyltin)ethylene (35.31 mg, 58.2 μmol), Pd2(dba)3 (2.13 mg, 2.3 μmol), P(o-tol)3 (2.84 mg, 9.3 μmol), and CuI (2.22 mg, 11.6 μmol) were added to a 10 mL Schlenk tube. Dry N-methylpyrrolidone (3 mL) was used as the solvent. The system was subjected to three freeze-drying cycles to ensure anhydrous and oxygen-free conditions. The reaction was heated to approximately 110 °C and reacted for 48 h. After cooling to room temperature, the reaction solution was poured into a methanol solution (200 mL), allowed to settle for 10 min, filtered, and the filter cake was washed several times with methanol. The obtained polymer was wrapped in filter paper and placed in a Soxhlet extraction apparatus. Extraction was performed using methanol, acetone, n-hexane, dichloromethane, chloroform, chlorobenzene, trifluoroethanol, and hexafluoroisopropanol, respectively. The trifluoroethanol fraction was collected to obtain a brownish-black solid, P2-1, approximately 14.6 mg, with a yield of 65.4% and a number-average molecular weight M. n =11.2 kDa.

[0145] Example 15

[0146]

[0147] Synthetic route of polymer P7: Compound 7 (20 mg, 38.8 μmol), 2,5-bis(2-(2-methoxyethoxy)ethyl)-3,6-bis(5-(tributyltinyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (62.13 mg, 38.8 μmol), Pd(PPh3)4 (1.80 mg, 1.6 μmol), and CuI (0.59 mg, 3.1 μmol) were added to a 10 mL Schlenk tube. Dry N-methylpyrrolidone (4 mL) was used as the solvent. The system was subjected to three freeze-drying cycles to ensure anhydrous and oxygen-free conditions. The reaction was heated to approximately 135 °C and reacted for 48 h. After cooling to room temperature, the reaction solution was poured into a methanol solution (200 mL), allowed to settle for 10 min, filtered, and the filter cake was washed several times with methanol. The obtained polymer was wrapped in filter paper and placed in a Soxhlet extraction apparatus. It was extracted with methanol, acetone, n-hexane, dichloromethane, chloroform, chlorobenzene, trifluoroethanol, and hexafluoroisopropanol, respectively. The trifluoroethanol fraction was collected to obtain a blackish-brown solid P7, about 38.58 mg, with a yield of 76.4%.

[0148] Example 16

[0149] The thermoelectric properties of materials are usually described by the thermoelectric figure of merit (ZT), and the specific formula is as follows:

[0150]

[0151] Where S represents the Seebeck coefficient, σ represents electrical conductivity, κ represents thermal conductivity, and T represents the operating temperature of the device. For organic materials, their thermal conductivity is much lower than that of inorganic materials; therefore, the power factor (PF) is commonly used to describe the thermoelectric properties of organic materials. We take polymer P2 as an example to test its electrical conductivity and Seebeck coefficient under doping conditions to characterize its thermoelectric properties. Glass was used as the substrate, and gold electrodes were obtained using photolithography as the test electrodes. The substrate was sequentially cleaned with acetone, detergent, water, and isopropanol, and then dried with nitrogen. A 3 mg / mL polymer P2 solution (using trifluoroethanol and water in a 1:1 volume ratio) was then spin-coated onto the substrate in air. In a glove box (nitrogen atmosphere), the polymer film was sequentially doped with a 1-butyl-3-methylimidazolium dicyandiamide salt ([BMIm][N(CN)2]) ionic liquid containing TDAE (TDAE:[BMIm][N(CN)2] volume ratio 1:3000). The surface residue of the ionic liquid was then washed away with a mixed solvent of acetonitrile / n-butyl acetate (volume ratio 1:4). The doping level of the polymer could be controlled by adjusting the residence time of the dopant / ionic liquid solution on the film surface. The device was placed at both ends in a temperature gradient field, and the corresponding thermoelectric potential was measured by measuring the change in temperature difference between the two ends, thus determining the Seebeck coefficient. Simultaneously, the conductivity was measured using a four-probe method. The test results are as follows: Figures 2-4 As shown, with increasing doping time, the conductivity first increases and then decreases, while the Seebeck coefficient first decreases and then remains almost constant. After 5 minutes of doping, the conductivity reaches a maximum of 480 S / cm, with an average maximum conductivity of 412 S / cm. After 1 minute of doping, the power factor reaches its maximum value of 58 μW / m. -1 K -2 Compared to previous polymers, the conductivity is improved by approximately four times. The polymer's conductivity and Seebeck coefficient were measured using a Lakeshore 1500 semiconductor tester.

[0152] Using glass as a substrate, gold electrodes were prepared using photolithography to serve as test electrodes. The substrate was sequentially cleaned with acetone, detergent, water, and isopropanol, and then dried with nitrogen. A 3 mg / mL polymer P4 solution (trifluoroethanol as solvent) was then spin-coated onto the substrate in air. Vapor doping of the polymer film was performed using TDAE in a glove box (nitrogen atmosphere), and the test results are as follows. Figures 5-7 As shown, the conductivity initially increases and then decreases with increasing doping time, reaching a maximum of 20.0 S / cm at approximately 30 minutes. The Seebeck coefficient of the polymer is negative and decreases with increasing doping degree, achieving a conductivity of 17.2 μW / cm. -1 K -2The maximum power factor was measured. The polymer's conductivity and Seebeck coefficient were measured using a Lakeshore 1500 semiconductor tester.

[0153] Using glass as a substrate, gold electrodes were obtained using photolithography to serve as test electrodes. The substrate was sequentially cleaned with acetone, detergent, water, and isopropanol, and then dried with nitrogen. A 3 mg / mL polymer P6 solution (trifluoroethanol as solvent) was then spin-coated onto the substrate in air. No conductivity was measured for the undoped polymer P6 film, indicating intrinsic non-conductivity. Vapor doping of the polymer film was performed using TDAE in a glove box (nitrogen atmosphere) for 0.5 minutes, yielding a polymer film with a conductivity of 2.81 × 10⁻⁶. -2 The conductivity was initially measured in S / cm. Further increasing the doping time resulted in a conductivity of 0.51 S / cm at approximately 15 minutes. Subsequent increases in doping time led to a slight decrease in conductivity. The polymer's conductivity and Seebeck coefficient were measured using a Lakeshore 1500 semiconductor tester.

[0154] Example 17

[0155] Organic electrochemical transistor (OECT) devices Figure 8 The processing method and related performance parameters, including the determination methods for transconductance, electron mobility, and volumetric capacitance, are as follows: Using silicon dioxide or glass as a substrate, gold electrodes are obtained as source and drain electrodes using photolithography. The substrate is sequentially cleaned with acetone, detergent, water, and isopropanol, and then dried with nitrogen. The channel is patterned by depositing and etching two layers of parylene. Then, an aqueous solution of the polymer (or small molecules) is spin-coated onto the substrate and annealed at different temperatures. Subsequently, the sacrificial layer of parylene is peeled off, leaving the polymer film within the channel. The polymer transfer curve, output curve, and response time are tested on a Keithley 4200 semiconductor tester, and the volumetric capacitance is tested on a BioLogic Science Instruments SP-300 electrochemical workstation. The material mobility is then calculated.

[0156] The table below shows the parameter specifications of organic electrochemical transistor devices based on polymer P2. The performance parameters of devices fabricated using water / P2 are shown in the attached figures in the instruction manual.

[0157] Table 1

[0158]

[0159] From the corresponding polymer P2 transfer curve and output curve Figure 9 and Figure 10It is evident that the organic electrochemical transistor device based on the water-processed polymer P2 exhibits ideal current amplification characteristics and electron-ion transport performance. Furthermore, Figure 11 The pulse switching test showed that the device has good switching performance and a relatively fast response speed among n-type materials. Figure 12 The transfer and output of inverters prepared for this material and another p-type material.

[0160] As shown in the table, devices processed using water as a solvent in the polymerization of polymer P2 exhibit excellent performance, currently ranking highest in the field of n-type organic electrochemical transistor materials. We believe this is due to two main reasons. First, the final polymer obtained after doping is electrically neutral, exhibiting high stability in its charged state. More importantly, cationic conjugated polymers have strong electron affinity, typically achieving high conductivity after doping. Second, cationic conjugated polymers generally have good solubility in highly polar solvents such as water and methanol, making them environmentally friendly and green in the processing of organic semiconductor devices. Furthermore, they avoid sterically hindered substituents from impeding charge transport between polymer chains, resulting in a close-packed structure in the solid state. This significantly reduces the π-π packing distance within and between chains, effectively enhancing charge transport capabilities between polymer chains. Therefore, the synthesis method and application of cationic conjugated polymers proposed in this invention have significant effects and importance in the field of organic semiconductors.

Claims

1. A method for preparing a cationic conjugated polymer, wherein the structure of the cationic conjugated polymer is shown in Formula I below: in, Ar 1 And D represents N-containing heteroaryl, N-containing cycloalkenyl, or other conjugated groups; Ar and Ar 2 Represents aryl, heteroaryl, or other conjugated groups; R 6 R 7 and R 8 Whether identical or different, independently selected from hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl, forming a ring independently, and / or forming a bond with another repeating unit or the end group of the polymer; Y - Represents anion; n is an integer representing the degree of polymerization of the polymer; The method is characterized by the following reaction formula: Step 1.1, mix the monomer shown in formula c with monomer R*-Ar 2 (R) 8 The polymer shown in formula d is formed by the polymerization of R-R*, wherein R 11 Represents alkoxy or silanoxy, R 9 R* represents the functional group required for the polymerization reaction of monomers; Step 1.2: Under anhydrous and oxygen-free conditions, using a halogenated organic solvent as the cyclization reaction solvent, controlling the substrate concentration at 3–5 mM and the reaction temperature at 75–100 °C, the repeating unit containing the nitrogen heterocycle in the polymer shown in formula d is cyclized, resulting in R… 11 The group leaves, yielding a quaternary nitrogen cationic ring system, generating the cationic conjugated polymer shown in Formula I.

2. The preparation method according to claim 1, characterized in that, The alkyl group is a C1-C46 alkyl group; the alkenyl group is a C2-C18 alkenyl group; the alkynyl group is a C2-C18 alkynyl group; the alkoxy group is a C1-C46 alkoxy group; the polyethylene glycol group is a C2-C36 polyethylene glycol group; the aryl group is a C6-C30 aryl group; the heteroaryl group is a C2-C26 heteroaryl group; and the nitrogen-containing cycloalkenyl group is 1,3-diazacyclopentadiene or 1,2-dihydropyridine.

3. The preparation method according to claim 1, characterized in that, The cationic conjugated polymer is selected from one of the following polymers: 。 4. The preparation method according to claim 1, characterized in that, The monomer R*-Ar 2 (R) 8 -R* is selected from one of the compounds shown in formulas II-1 to II-20 below: Among them, R 12 Represents hydrogen atom, halogen atom, nitro group, amino group, cyano group, alkyl group, alkenyl group, alkoxy group, halogen-substituted alkyl group, or halogen-substituted alkoxy group; b and b' are independently selected from: —S—, —Se—, —O— and —NR— 8 —; c and c' are independently selected from: —N=, =N—, —SiR 8 =,=SiR 8 —,—CR 8 = and =CR 8 —; d and d' are independently selected from: —N=, =N—, —SiR 8 =,=SiR 8 —,—CR 8 = and =CR 8 —; e is selected from: —S—, —S(O)—, —S(O)2—, —O—, —SiR 8 R 8 —, —CR 8 R 8 —CR 8 R 8 —, —CR 8 =CR 8 —, and —C(O)—; g, h, g', h' are independently selected from: —CR 8 =,=CR 8 —, and —N= and =N—; Among them, R 8 It can be hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl.

5. The preparation method according to claim 1, characterized in that, The monomer R*-Ar 2 (R) 8 -R* is selected from one of the compounds with the following structures: Among them, R 12 Represents hydrogen atom, halogen atom, nitro group, amino group, cyano group, alkyl group, alkenyl group, alkoxy group, halogen-substituted alkyl group, or halogen-substituted alkoxy group; R 8 It can be hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl.

6. The preparation method according to claim 1, characterized in that, Step 1.1 employs the Suzuki coupling reaction, Stille coupling reaction, Sonogashira coupling reaction, Heck coupling reaction, Kumada coupling reaction, C-H bond activation coupling reaction, or Hiyama coupling reaction; Step 1.2 uses phosphoric acid chloride, carbonyl chloride, or thiocyanate chloride as the cyclizing reagent for the ring-closing reaction, and the reaction solvent is selected from one or more of dichloromethane, chlorobenzene, 1,1,2,2,-tetrachloroethane, and trichloromethane, with a reaction time of 12-36 hours.

7. A method for preparing a cationic conjugated polymer, wherein the structure of the cationic conjugated polymer is shown in Formula I below: in, Ar 1 And D represents N-containing heteroaryl, N-containing cycloalkenyl, or other conjugated groups; Ar and Ar 2 Represents aryl, heteroaryl, or other conjugated groups; R 6 R 7 and R 8 Whether identical or different, independently selected from hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl, forming a ring independently, and / or forming a bond with another repeating unit or the end group of the polymer; Y - Represents anion; n is an integer representing the degree of polymerization of the polymer; The method is characterized by the following reaction formula: Step 2.1, cyclize compound c to make R 11 The group leaves to obtain a quaternary nitrogen cationic ring system, generating the compound shown in formula g; wherein the cyclizing reagent used in the ring-closing reaction is phosphoric acid chloride, carbonyl chloride or thioyl chloride, the reaction temperature is 25-150 ℃, the reaction solvent is selected from one or more of dichloromethane, tetrahydrofuran, acetonitrile, chlorobenzene, 1,1,2,2,-tetrachloroethane and trichloromethane, and the reaction time is 12-36 hours; Step 2.2: Using the Suzuki coupling reaction, Stille coupling reaction, Sonogashira coupling reaction, Heck coupling reaction, Kumada coupling reaction, C-H bond activation coupling reaction, or Hiyama coupling reaction, the monomer shown in formula g is coupled with the monomer R*-Ar. 2 (R) 8 The cationic conjugated polymer of Formula I is polymerized in a polar organic solvent, wherein the reaction solvent is selected from one or more of o-xylene, o-dichlorobenzene, N,N-dimethylformamide, chlorobenzene, N-methylpyrrolidone and dimethyl sulfoxide; Among them, R 11 Represents alkoxy or silanoxy, R 9 R* represents the functional group required for the polymerization reaction of monomers.

8. The preparation method according to claim 7, characterized in that, The monomer R*-Ar 2 (R) 8 -R* is selected from one of the compounds with the following structures: Among them, R 12 Represents hydrogen atom, halogen atom, nitro group, amino group, cyano group, alkyl group, alkenyl group, alkoxy group, halogen-substituted alkyl group, or halogen-substituted alkoxy group; b and b' are independently selected from: —S—, —Se—, —O— and —NR— 8 —; c and c' are independently selected from: —N=, =N—, —SiR 8 =,=SiR 8 —,—CR 8 = and =CR 8 —; d and d' are independently selected from: —N=, =N—, —SiR 8 =,=SiR 8 —,—CR 8 = and =CR 8 —; e is selected from: —S—, —S(O)—, —S(O)2—, —O—, —SiR 8 R 8 —, —CR 8 R 8 —CR 8 R 8 —, —CR 8 =CR 8 —, and —C(O)—; g, h, g', h' are independently selected from: —CR 8 =,=CR 8 —, and —N= and =N—; a and a' are independently selected from: —S—, —Se—, —O— and —NR— 8 —; m and m' are independently selected from: —S—, —S(O)—, —S(O)2—, —O—, —NR 8 —,—SiR 8 R 8 —,—CR 8 R 8 —CR 8 R 8 —,—CR 8 =CR 8 —, —C(O)— and —C(C(CN)2)—; n and n' are independently selected from: —N=, =N—, —SiR 8 =,=SiR 8 —,—SiR 8 R 8 —,—CR 8 R 8 —CR 8 R 8 —and—CR 8 =CR 8 —; Among them, R 8 It can be hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl.

9. The preparation method according to claim 7, characterized in that, The monomer R*-Ar 2 (R) 8 -R* is selected from one of the compounds with the following structures: Among them, R 8 It can be hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, polyethylene glycol, halogen-substituted alkyl, aryl, heteroaryl, alkyl-substituted aryl, or heteroaryl.

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