Conjugated polymers containing bithiazole units with ethylene glycol side chains, their preparation methods and applications

Abstract

This invention discloses a conjugated polymer containing bithiazole units with ethylene glycol side chains, its preparation method, and its applications, belonging to the fields of functional polymer materials and organic electronics. This invention overcomes the poor crystallinity of traditional organic mixed ionic conductor materials, improves the microstructure of the film and carrier transport, and features a simple synthesis method. The main chain of this conjugated polymer is a polythiazole or polythiazole / thiophene backbone, and the side chains are short polar ethylene glycol chains. This invention provides a method for preparing the above-mentioned conjugated polymer, which involves dissolving a dibromo monomer, a ditrialkyltin monomer, a palladium catalyst, and a ligand in an organic solvent under an inert atmosphere, and carrying out a Stille polymerization reaction under light-protected and reflux conditions to obtain a conjugated polymer containing bithiazole units with ethylene glycol side chains. This invention also provides the application of the above-mentioned conjugated polymer as an organic mixed ionic conductor in the channel material of organic electrochemical transistors.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer materials and organic electronics technology, specifically relating to a conjugated polymer containing a bithiazole unit with an ethylene glycol side chain, its preparation method, and its application. Background Technology

[0002] Organic hybrid ion-electron conductors (OMIEC) are a class of polymeric materials with a π-conjugated main chain structure that transport ions and electrons. They can be used as channel materials in organic electrochemical transistors (OECTs). OECTs are organic electronic devices that conduct or amplify ion-electron signals and detect molecules or electrons. Their working principle involves injecting ions into the channel material through a gate bias voltage, followed by electrochemical doping and charge compensation of the channel material by electrolyte ions. OMIECs not only possess semiconductor properties but also the plastic properties found in conventional polymeric materials, such as flexibility, light weight, low cost, solution processability, and biocompatibility. Based on these characteristics, OMIECs have broad application prospects in fields such as biosensors, energy storage, and neural computing.

[0003] To facilitate ion implantation and transport and improve the performance of OECT (Optical Electron Conduction), organic hybrid ion-electron conductors (OECs) need to possess good order. Currently, researched organic hybrid ion-electron conductor materials are mainly constructed using conjugated frameworks and ethylene glycol side chains, such as pyrrolopyrrole dione derivatives and naphthalimide derivatives containing ethylene glycol side chains. However, these conjugated frameworks are highly flexible and have poor crystallinity, which is detrimental to the formation of ordered microstructures in polymer films and, to some extent, limits carrier transport. Furthermore, the synthesis of these building blocks (conjugated frameworks) is difficult, hindering the large-scale preparation of organic hybrid ion-electron conductor materials and limiting the widespread application of OECT. Therefore, how to solve the aforementioned problems faced by organic hybrid ion-electron conductor materials through rational chemical structure design and develop high-performance organic hybrid ion-electron conductor materials has become one of the urgent problems to be solved by researchers. Summary of the Invention

[0004] This invention addresses the problems of existing organic mixed ionic-electron conductor materials, such as the strong flexibility and poor crystallinity of the conjugated backbone, which leads to poor microstructural order in polymer films and thus restricts carrier transport, as well as the difficulty in synthesizing the conjugated backbone, hindering the large-scale preparation of organic mixed ionic-electron conductor materials. It provides a conjugated polymer containing bithiazole units with ethylene glycol side chains, its preparation method, and its application. In this conjugated polymer, the polymer backbone is a polythiazole or polythiazole / thiophene backbone, consisting entirely of smaller π units linked by single bonds, with short polar ethylene glycol side chains. The preparation method of the conjugated polymer provided by this invention involves dissolving a bithiazole dibromo monomer with ethylene glycol side chains, a bis(trialkyltin) monomer, a palladium catalyst, and ligands in an organic solvent under an inert atmosphere. The reaction system is then subjected to Stille polymerization under light-protected and reflux conditions to obtain the conjugated polymer containing bithiazole units with ethylene glycol side chains. This conjugated polymer containing bithiazole units with ethylene glycol side chains can be used as an organic mixed ionic-electron conductor material in organic electrochemical transistors.

[0005] To achieve the above objectives, the following technical solution is adopted:

[0006] One objective of this invention is to provide a conjugated polymer containing a bithiazole unit with ethylene glycol side chains, wherein the conjugated polymer has a polythiazole or polythiazole / thiophene backbone as the molecular backbone and short polar ethylene glycol side chains.

[0007] Further specifying, the conjugated polymer structure is as follows:

[0008]

[0009] In the formula, n is an integer from 2 to 1000, and m is an integer from 1 to 10;

[0010] Ar can be one of the following structures:

[0011]

[0012] Furthermore, m is an integer from 2 to 6;

[0013] Ar for One of them. Further specifying, the conjugated polymer structural formula is as follows:

[0014]

[0015]

[0016] The second objective of this invention is to provide a method for preparing a conjugated polymer containing bithiazole units with ethylene glycol side chains. The steps are as follows: under an inert atmosphere, a dibromo monomer, a bis(trialkyltin) monomer, a palladium catalyst, and a ligand are dissolved in an organic solvent. The reaction system is subjected to Stille polymerization under light-protected and reflux conditions. After the reaction is completed, the obtained polymer is extracted and purified to obtain a conjugated polymer containing bithiazole units with ethylene glycol side chains.

[0017] Further specifying, the structural formula of the dibromo monomer is:

[0018]

[0019] Further specifying, the structural formula of the ditrialkyltin monomer is:

[0020]

[0021] Further specifying, the organic solvent is toluene; the palladium catalyst is tris(dibenzylacetone)dipalladium; and the ligand is tris(o-methylphenyl)phosphine.

[0022] Further specifying, the molar ratio of dibromo monomer, ditrialkyltin monomer, palladium catalyst, and ligand is 1:1:(0.01~0.05):(0.04~0.2).

[0023] Furthermore, the molar ratio of the dibromo monomer, the ditrialkyltin monomer, the palladium catalyst, and the ligand is 1:1:0.02:0.08.

[0024] Further specified, the concentrations of both dibromo monomers and bis(trialkyltin) monomers in the organic solvent are 0.005–0.1 mmol / L.

[0025] Furthermore, the concentrations of both dibromo monomers and ditrialkyltin monomers in the organic solvent are specified to be 0.02–0.06 mmol / L.

[0026] Furthermore, the reaction temperature for the Stille polymerization reaction is specified as 80–120 °C.

[0027] Furthermore, the reaction temperature for the Stille polymerization reaction is specified as 90–110 °C.

[0028] Further, the Stille polymerization reaction time is specified to be 1–96 h.

[0029] Furthermore, the Stille polymerization reaction time is specified to be 16–36 h.

[0030] A third objective of this invention is to provide the application of a conjugated polymer containing a bithiazole unit with an ethylene glycol side chain, which serves as an organic mixed ionic-electron conductor for use as a channel material in organic electrochemical transistors.

[0031] Further specified, the organic electrochemical transistor uses borosilicate glass as a substrate, the transmission channel width is 100-500 μm and the length is 10-200 μm, a metal electrode is deposited on the glass substrate, the electrolyte solution concentration is 0.1 mol / L, and the gate material is an Ag / AgCl electrode.

[0032] Furthermore, the electrolyte solution is specified as NaCl solution or PBS phosphate buffer solution, etc.

[0033] Further specifying, the preparation method of the conjugated polymer as an organic electrochemical transistor channel material is as follows: dissolving the conjugated polymer in a solvent to prepare a solution, preparing a thin film on the transistor transmission channel, and then performing a thermal annealing treatment on the thin film.

[0034] Furthermore, the solvent is specified as chloroform, hexafluoroisopropanol, or chlorobenzene, and the solution concentration is 1–10 mg / mL. -1 .

[0035] Furthermore, the film thickness is specified to be 20–100 nm.

[0036] Furthermore, the thin film preparation method is spin coating, drop coating, or blade coating, etc.

[0037] Furthermore, the film heat annealing temperature is specified as 100–200°C, and the heat annealing time is specified as 5–60 min.

[0038] The beneficial effects achieved by this invention are as follows:

[0039] (1) This invention improves the flexibility and crystallinity of traditional organic mixed ion-electron conductor materials by designing the structure of organic mixed ion-electron conductor materials, making the microstructure of the material film more ordered and promoting the transport of charge carriers. At the same time, it simplifies the synthesis route of organic mixed ion-electron conductor materials, which facilitates the large-area fabrication of OECT devices.

[0040] (2) The conjugated polymer provided by the present invention is a P-type polymer, which is obtained by Stille polymerization reaction of dibromo monomer and bistrialkyltin monomer. The dibromo monomer is a bithiazole dibromo monomer containing ethylene glycol side chain, that is, 5,5'-bithiazole as the main body reacts with bistrialkyltin monomer. The presence of thiazole will reduce the HOMO energy level of the P-type polymer, which can avoid Faraday side reaction in organic electrochemical transistor applications and increase the stability of the device.

[0041] (3) In the synthetic route of the bithiazole monomer containing ethylene glycol side chain provided by the present invention, the bithiazole monomer is obtained by the Stille coupling reaction of thiazole followed by bromination. Compared with the traditional coupling reaction, it does not require the protection and deprotection of thiazole, making the overall synthesis steps of the conjugated polymer simpler. At the same time, since the chemical structure of the constituent units of the polymer chain in the conjugated polymer is simple, it is beneficial to the large-scale synthesis of organic mixed ionic electronic conductor materials.

[0042] (4) The conjugated polymer provided by this invention has an ethylene glycol side chain attached to the polymer backbone, specifically a polar ethylene glycol side chain attached to the fourth site of the thiazole. This structure makes S and O closer together, and the interaction between SO makes the backbone have good skeletal planarity, which is conducive to inter-chain stacking, promotes the crystallinity of the polymer chain, and makes it easy to form an ordered microstructure to obtain excellent electronic properties and promote electron transport. At the same time, the ethylene glycol side chain can achieve ion implantation, which is not possible with ordinary alkyl chains and alkoxy chains. The polymer backbone in the conjugated polymer is a polythiazole or polythiazole / thiophene backbone. This simple structural unit also makes the stacking of polymer chains easier, which is conducive to the formation of an ordered microstructure in organic mixed ionic electronic conductor materials, improves the transport performance of organic mixed ionic electronic conductor materials, and makes the polymer of this invention a promising material for channeling in organic electrochemical transistors.

[0043] (5) The conjugated polymer provided by the present invention has good solubility in organic solvents such as chloroform and hexafluoroisopropanol, and has good film-forming properties;

[0044] (6) Testing showed that the conjugated polymer provided by this invention, when applied in a p-type organic electrochemical transistor, exhibits low off-state current and excellent electrochemical stability, with a maximum transconductance of 20 Scm. -1 The maximum quality factor (μC*) is above 40 Fcm. -1 V -1 s -1 The above demonstrates the excellent performance of OECT devices; Attached Figure Description

[0045] Figure 1 The NMR spectrum of compound 2 in Example 1;

[0046] Figure 2 The NMR spectrum of compound 3 in Example 1;

[0047] Figure 3 The NMR spectrum of compound 4 in Example 1;

[0048] Figure 4 The NMR spectrum of 5, a dibromothiazole monomer, in Example 1;

[0049] Figure 5 The NMR spectrum of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0050] Figure 6 Cyclic voltammetry curves of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0051] Figure 7 Gel permeation chromatography of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0052] Figure 8 The output characteristic curve of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0053] Figure 9 The transfer characteristic curve of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0054] Figure 10 The transconductance-gate voltage curve of the conjugated polymer Pg2Tz-T(4O) prepared in Example 1;

[0055] Figure 11 The NMR spectrum of the conjugated polymer Pg2Tz-TT(4O) prepared in Example 10;

[0056] Figure 12 Cyclic voltammetry curves of the conjugated polymer Pg2Tz-TT(4O) prepared in Example 10;

[0057] Figure 13 Gel permeation chromatography of the conjugated polymer Pg2Tz-TT(4O) prepared in Example 10;

[0058] Figure 14 A schematic diagram of an organic electrochemical transistor device used for testing the performance of conjugated polymers. Detailed Implementation

[0059] To further illustrate the present invention, the following detailed description is provided in conjunction with specific embodiments. It should be noted that the following embodiments are only used to better understand the technical solutions of the present invention and should not be construed as limiting the scope of protection of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the field, which can be obtained by those skilled in the art through commercial channels.

[0060] The chemical substances involved in the following examples can be represented in the form of compound + number or chemical name + number. For example, 2,5-bis(trimethyltinyl)thiophene 6 and compound 6 represent the same substance.

[0061] Example 1

[0062] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole-co-thiophene](Pg2Tz-T(4O)) with the structural formula shown in Formula 1:

[0063]

[0064] (1) Preparation of the bithiazole dibromo monomer 5(2,2'-dibromo-4,4'-bis(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole containing an ethylene glycol side chain

[0065]

[0066] ① Under a nitrogen atmosphere, sodium hydride (4.0 g, 100 mmol, 60% dispersed in mineral oil) and 40 mL of ultra-dry tetrahydrofuran were added to a 250 mL dry round-bottom flask. Triethylene glycol monomethyl ether (16.4 g, 100 mmol) was slowly added dropwise. The reaction system was stirred at 300 rpm for 2 h at room temperature. Then, cuprous bromide (0.96 g, 6.7 mmol) and 4-bromothiazole (compound 1, 10.9 g, 66.5 mmol) were added. The reaction system was heated to 80 °C and stirred at 300 rpm for 2 h. After the reaction system cooled to room temperature, the reaction system was vacuum filtered and the solid was washed with dichloromethane. The filtrate was collected and concentrated under reduced pressure. The concentrated crude product was separated by silica gel column chromatography to obtain 4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)thiazole, i.e., compound 2 (C 10 H 17 NO4S, 8.5g, yield 52%.

[0067] NMR analysis of compound 2 yielded the following results: Figure 1 As shown, its structural characterization is as follows: 1 H NMR (500MHz, Chloroform-d) δ 8.53 (d, 1H), 6.21 (d, 1H), 4.33 (t, 2H), 3.87 (t, 2H), 3.73 (t, 2H), 3.66 (t, 4H), 3.55 (t, 2H), 3.38 (s, 3H).

[0068] Elemental analysis of compound 2: theoretical values: C, 48.57; H, 6.93; N, 5.66; O, 25.88; S, 12.96; measured values: C, 48.55; H, 6.95; N, 5.65; O, 25.87; S, 12.98.

[0069] ② Add compound 2 (2.47 g, 10 mmol) and 120 mL of chloroform to a 250 mL round-bottom flask. Protect the reaction system from light. Add N-bromosuccinimide (1.88 g, 10 mmol) in three batches. Stir the reaction system at 300 rpm for 2 h at room temperature. Quench the reaction with water. Extract the reaction solution three times with dichloromethane (50 mL each time). Wash the obtained organic phase with saturated brine. Dry the organic phase with 30 g of anhydrous sodium sulfate. Then concentrate the organic phase under reduced pressure. Separate the concentrated crude product by silica gel column chromatography to obtain 5-bromo-4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)thiazole, i.e., compound 3 (C 10 H 16 BrNO4S, 2.3g, yield 71%.

[0070] NMR analysis of compound 3 yielded the following results: Figure 2 As shown, its structural characterization is as follows: 1 H NMR (500MHz, Chloroform-d) δ 8.52 (s, 1H), 4.50 (t, 2H), 3.83 (t, 2H), 3.73 (t, 2H), 3.65 (t, 4H), 3.54 (t, 2H), 3.37 (s, 3H).

[0071] Elemental analysis of compound 3: theoretical values: C, 36.82; H, 4.94; Br, 24.50; N, 4.29; O, 19.62; S, 9.83; measured values: C, 36.80; H, 4.96; Br, 24.48; N, 4.28; O, 19.64; S, 9.84.

[0072] ③ Under a nitrogen atmosphere, compound 3 (1.4 g, 4.9 mmol), hexa-n-butylditin (1.6 g, 2.8 mmol), tris(dibenzylacetone)dipalladium (0.39 g, 0.49 mmol), tris(o-methylphenyl)phosphine (0.53 g, 1.96 mmol), and 30 mL of anhydrous toluene were added to a 100 mL dry round-bottom flask. The reaction system was stirred at 110 °C and 300 rpm for 48 h. After the reaction system was cooled to room temperature, water was added to quench the reaction. The reaction solution was extracted three times with dichloromethane (50 mL each time). The obtained organic phase was washed with saturated brine, and the organic phase was collected and dried with 30 g of anhydrous sodium sulfate. Then, the organic phase was concentrated under reduced pressure. The concentrated crude product was separated by silica gel column chromatography to obtain 4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole, i.e., compound 4 (C 20 H 32 N2O8S2, 0.43 g, yield 40%.

[0073] NMR analysis of compound 4 yielded the following results: Figure 3 As shown, its structural characterization is as follows: 1 H NMR (500MHz, Chloroform-d) δ 8.39 (s, 2H), 4.60 (t, 4H), 3.90 (t, 4H), 3.74 (t, 4H), 3.66 (t, 8H), 3.53 (t, 4H), 3.37 (s, 6H).

[0074] Elemental analysis of compound 4: theoretical values: C, 48.77; H, 6.55; N, 5.69; O, 25.98; S, 13.02; measured values: C, 48.78; H, 6.54; N, 5.68; O, 25.99; S, 13.02.

[0075] ④ Add compound 4 (320 mg, 0.65 mmol), N-bromosuccinimide (278 mg, 1.56 mmol), and 20 mL of chloroform to a 100 mL dry round-bottom flask. Stir the reaction mixture at 300 rpm for 1.5 h at 65 °C in the dark. After cooling to room temperature, quench the reaction with water. Extract the reaction mixture three times with dichloromethane (50 mL each time). Wash the resulting organic phase with saturated brine. Dry the organic phase with 30 g of anhydrous sodium sulfate. Then concentrate the organic phase under reduced pressure. Separate the concentrated crude product by silica gel column chromatography to obtain the bithiazole dibromo monomer 5 (C... 20 H 30 Br2N2O8S2, 220 mg, yield 52%).

[0076] NMR analysis of the dibromo 5 bis(thiazole) monomer showed the following results: Figure 4 As shown, its structural characterization is as follows:1 H NMR (500MHz, Chloroform-d) δ 8.39 (s, 2H), 4.60 (t, 4H), 3.90 (t, 4H), 3.74 (t, 4H), 3.66 (t, 8H), 3.53 (t, 4H), 3.37 (s, 6H).

[0077] Elemental analysis of the bithiazole dibromo monomer 5: theoretical values: C, 36.93; H, 4.65; Br, 24.57; N, 4.31; O, 19.68; S, 9.86; measured values: C, 36.94; H, 4.64; Br, 24.59; N, 4.29; O, 19.66; S, 9.88.

[0078] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis of the dibromo 5-bis(thiazolium) monomer: theoretical value 650.4; experimental value 650.4.

[0079] (2) Synthesis of Pg2Tz-T(4O)

[0080]

[0081] Weigh out 5 (130 mg, 0.2 mmol) of bithiazolyl dibromo monomer 5, 2,5-bis(trimethyltinyl)thiophene 6 (82 mg, 0.2 mmol), tris(dibenzylideneacetone)dipalladium (4 mg, 0.004 mmol) and tris(o-methylphenyl)phosphine (6 mg, 0.016 mmol) into a nitrogen-filled polymerization tube. Add 5 mL of dry toluene solvent and heat the reaction system to 100 °C under reflux in the dark for 24 h. After the reaction is complete, add 5 mL of chloroform to the system and transfer the reaction solution to 100 mL of methanol. Add 5 mL of hydrochloric acid and filter to collect the solid. Use a Soxhlet extractor to extract the solid sequentially with 120 mL of methanol, acetone, n-hexane, and chloroform. Finally, concentrate the chloroform extract, transfer it to methanol again to precipitate, collect it, and dry it in a vacuum (≈10 Torr) at room temperature for 24 h to obtain Pg2Tz-T(4O) (100 mg, yield 83%).

[0082] NMR analysis of Pg2Tz-T(4O) yielded the following results: Figure 5 As shown, its structural characterization is as follows: 1¹H NMR (500MHz, Chloroform-d) δ 7.05 (s, 1H), 4.79–3.21 (m, 30H); Elemental analysis of Pg₂Tz-T(₄O) showed: calculated C, 50.16; H, 5.96; N, 4.87; O, 22.27; S, 16.74; and measured C, 50.10; H, 6.02; N, 4.85; O, 22.21; S, 16.77. Cyclic voltammetry of Pg₂Tz-T(₄O) was performed, and the results are shown in Table 1. The cyclic voltammetry curves are shown in the figure. Figure 6 As shown; Pg2Tz-T(4O) was analyzed by gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃). The gel permeation chromatography results are as follows. Figure 7 As shown, Mn = 80872, PDI = 1.79.

[0083] The conjugated polymer Pg2Tz-T(4O) prepared in this embodiment was tested for OECT device performance, and its electrochemical performance was studied. The test results are listed in Table 1.

[0084] The output characteristic curve of Pg2Tz-T(4O) is shown in the figure. Figure 8 As can be seen from the figure, at a certain gate voltage, as the source-drain voltage increases, the source-drain current first passes through the linear region and then reaches the saturation region; the source-drain current in the saturation region increases with the increase of the gate voltage.

[0085] The transfer characteristic curve of Pg2Tz-T(4O) is shown in the figure. Figure 9 As can be seen from the figure, under a certain source-drain voltage, the source-drain current is regulated by the gate voltage and increases with the increase of the gate voltage.

[0086] The transconductance-gate voltage curve of Pg2Tz-T(4O) is shown below. Figure 10 As can be seen from the figure, under a certain source-drain voltage, the transconductance of the channel material (conjugated polymer) is regulated by the gate voltage, and increases first and then decreases as the gate voltage increases.

[0087] Example 2

[0088] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-thiophene](Pg2Tz-T(5O)) with the structural formula shown in Formula 2:

[0089]

[0090] (1) Preparation of the bithiazole dibromo monomer 7(4,4'-bis((2,5,8,11-tetraoxate-13-yl)oxy)-2,2'-dibromo-5,5'-bithiazole containing an ethylene glycol side chain

[0091] The synthesis of bithiazole dibromo monomer 7 differs from that in Example 1 (1) in that the side chain is... Replace with The triethylene glycol monomethyl ether was replaced with tetraethylene glycol monomethyl ether, and the remaining process steps and parameter settings were the same as in Example 1 (1), to obtain the bithiazole dibromo monomer 7 (C 24 H 38 Br2N2O 10 S2);

[0092] (2) Synthesis of Pg2Tz-T(5O)

[0093]

[0094] The difference between this step and (2) in Example 1 is that the dibromo monomer is bithiazole dibromo monomer 7, and its dosage is 147.7 mg (0.2 mmol). The remaining process steps and parameter settings are the same as in (2) of Example 1, and the conjugated polymer Pg2Tz-T(5O) (120 mg, yield 87%) is obtained.

[0095] Elemental analysis of the dibromodimethylamine monomer 7: Theoretical values: C, 39.03; H, 5.19; Br, 21.64; N, 3.79; O, 21.66; S, 8.68; Measured values: C, 39.03; H, 5.19; Br, 21.64; N, 3.79; O, 21.66; S, 8.68; MALDI-TOF analysis of the dibromodimethylamine monomer 7: Theoretical value: 738.50; Measured value: 738.50; Pg2Tz Elemental analysis of Pg2Tz-T(5O) was performed: calculated values ​​C, 50.74; H, 6.39; N, 4.23; O, 24.14; S, 14.51; and tested values ​​C, 50.70; H, 6.43; N, 4.21; O, 24.13; S, 14.54. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was used to analyze Pg2Tz-T(5O), and the results are as follows: Mn = 42854, PDI = 1.53.

[0096] Example 3

[0097] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-thiophene](Pg2Tz-T(6O)) with the structural formula shown in Formula 3:

[0098]

[0099] (1) Preparation of the bithiazole dibromo monomer 8(4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-2,2'-dibromo-5,5'-bithiazole containing an ethylene glycol side chain

[0100] The synthesis of bithiazole dibromo monomer 8 differs from that in Example 1 (1) in that the side chain is... Replace with The triethylene glycol monomethyl ether was replaced with pentaethylene glycol monomethyl ether, and the remaining process steps and parameter settings were the same as in Example 1 (1), to obtain the bithiazole dibromo monomer 8 (C 28 H 46 Br2N2O 12 S2);

[0101] (2) Synthesis of Pg2Tz-T(6O)

[0102]

[0103] The difference between this step and (2) in Example 1 is that the dibromo monomer is bithiazole dibromo monomer 8, and its dosage is 165.3 mg (0.2 mmol). The remaining process steps and parameter settings are the same as in (2) of Example 1, and the conjugated polymer Pg2Tz-T(6O) (105 mg, yield 85%) is obtained.

[0104] Elemental analysis of bis(thiazolium) dibromomon 8: Theoretical values: C, 40.69; H, 5.61; Br, 19.33; N, 3.39; O, 23.23; S, 7.76; Measured values: C, 40.66; H, 5.64; Br, 19.30; N, 3.37; O, 23.26; S, 7.78. MALDI-TOF analysis of bis(thiazolium) dibromomon 8: Theoretical value: 826.61; Measured value: 826.61. For Pg2Tz... Elemental analysis of Pg2Tz-T(6O) was performed: calculated values ​​C, 50.74; H, 6.39; N, 4.23; O, 24.14; S, 14.51; and tested values ​​C, 50.72; H, 6.37; N, 4.25; O, 24.16; S, 14.51. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was used to analyze Pg2Tz-T(6O), and the results are as follows: Mn = 46756, PDI = 1.69.

[0105] Example 4

[0106] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole-co-bithiophene](Pg2Tz-2T(4O)) with the structural formula shown in Formula 4:

[0107]

[0108] The difference between this embodiment and Embodiment 1 is as follows:

[0109] The conjugated polymer is Pg2Tz-2T(4O), and its synthesis reaction formula is as follows:

[0110]

[0111] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5'-bis(trimethyltinyl)-2,2'-bithiophene, i.e., compound 9. The amount of compound 9 was 98.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 1, and the conjugated polymer Pg2Tz-2T(4O) (116 mg, yield 87%) was obtained.

[0112] Elemental analysis of Pg2Tz-2T(4O) was performed: calculated values ​​C, 51.20; H, 5.52; N, 4.26; O, 19.49; S, 19.52; and measured values ​​C, 51.3; H, 5.42; N, 4.28; O, 19.51; S, 19.48. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-2T(4O), and the results are as follows: Mn = 56782, PDI = 1.75.

[0113] Example 5

[0114] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-bisthiaphene](Pg2Tz-2T(5O)) with the structural formula shown in Formula 5:

[0115]

[0116] The difference between this embodiment and Embodiment 2 is as follows:

[0117] The conjugated polymer is Pg2Tz-2T(5O), and its synthesis reaction formula is as follows:

[0118]

[0119] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5'-bis(trimethyltinyl)-2,2'-bithiophene, i.e., compound 9. The amount of compound 9 was 98.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 2, and the conjugated polymer Pg2Tz-2T(5O) (121 mg, yield 81%) was obtained.

[0120] Elemental analysis of Pg2Tz-2T(5O) was performed: calculated values ​​C, 51.59; H, 5.95; N, 3.76; O, 21.48; S, 17.21; and measured values ​​C, 51.69; H, 5.85; N, 3.73; O, 21.46; S, 17.27. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-2T(5O), and the results are as follows: Mn = 46732, PDI = 1.64.

[0121] Example 6

[0122] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-bisthiophene](Pg2Tz-2T(6O)) with the structural formula shown in Formula 6:

[0123]

[0124] The difference between this embodiment and Embodiment 3 is as follows:

[0125] The conjugated polymer is Pg2Tz-2T(6O), and its synthesis reaction formula is as follows:

[0126]

[0127] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5'-bis(trimethyltinyl)-2,2'-bithiophene, i.e., compound 9. The amount of compound 9 was 98.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 3, and the conjugated polymer Pg2Tz-2T(6O) (127 mg, yield 80%) was obtained.

[0128] Elemental analysis of Pg2Tz-2T(6O): calculated values: C, 51.90; H, 6.29; N, 3.36; O, 23.05; S, 15.39; tested values: C, 52.00; H, 6.19; N, 3.33; O, 23.02; S, 15.45.

[0129] Pg2Tz-2T(6O) was analyzed by gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃), and the results are as follows: Mn=56732, PDI=1.84.

[0130] Example 7

[0131] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole-co-2,2':5',2”-trithiophene](Pg2Tz-3T(4O)) with the structural formula shown in Formula 7:

[0132]

[0133] The difference between this embodiment and Embodiment 1 is as follows:

[0134] The conjugated polymer is Pg2Tz-3T(4O), and its synthesis reaction formula is as follows:

[0135]

[0136] In this process, the bis(trimethyltin)monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5”-bis(trimethyltinyl)-2,2':5',2”-trithiophene, i.e., compound 10. The amount of bithiazole dibromomonomer 5 was 130 mg (0.2 mmol), and the amount of compound 10 was 114.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 1, and the conjugated polymer Pg2Tz-3T(4O) (137 mg, yield 83%) was obtained.

[0137] Elemental analysis of Pg2Tz-3T(4O) was performed: calculated values ​​C, 52.01; H, 5.18; N, 3.79; O, 17.32; S, 21.69; and measured values ​​C, 52.11; H, 5.08; N, 3.76; O, 17.30; S, 21.74. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-3T(4O), and the results are as follows: Mn = 67894, PDI = 1.64.

[0138] Example 8

[0139] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-2,2':5',2”-trithiophene](Pg2Tz-3T(5O)) with the structural formula shown in Formula 8:

[0140]

[0141] The difference between this embodiment and Embodiment 2 is as follows:

[0142] The conjugated polymer is Pg2Tz-3T(5O), and its synthesis reaction formula is as follows:

[0143]

[0144] In this process, the bis(trimethyltin)monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5”-bis(trimethyltinyl)-2,2’:5’,2”-trithiophene, i.e., compound 10. The amount of bithiazole dibromomonomer 7 was 147.7 mg (0.2 mmol), and the amount of compound 10 was 114.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 2, and the conjugated polymer Pg2Tz-3T(5O) (143 mg, yield 80%) was obtained.

[0145] Elemental analysis of Pg2Tz-3T(5O): calculated values: C, 52.28; H, 5.61; N, 3.39; O, 19.34; S, 19.38; tested values: C, 52.39; H, 5.50; N, 3.36; O, 19.36; S, 19.39.

[0146] Pg2Tz-3T(5O) was analyzed by gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃), and the results are as follows: Mn=55763, PDI=1.89.

[0147] Example 9

[0148] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-2,2':5',2”-trithiophene](Pg2Tz-3T(6O)) with the structural formula shown in Formula 9:

[0149]

[0150] The difference between this embodiment and Embodiment 1 is as follows:

[0151] The conjugated polymer is Pg2Tz-3T(6O), and its synthesis reaction formula is as follows:

[0152]

[0153] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 5,5”-bis(trimethyltinyl)-2,2':5',2”-trithiophene, i.e., compound 10. The amount of compound 10 was 114.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 3, and the conjugated polymer Pg2Tz-3T(6O) (147 mg, yield 79%) was obtained.

[0154] Elemental analysis of Pg2Tz-3T(6O) was performed: calculated values ​​C, 52.50; H, 5.95; N, 3.06; O, 20.98; S, 17.52; tested values ​​C, 52.60; H, 5.85; N, 3.02; O, 20.99; S, 17.55. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-3T(6O), and the results are as follows: Mn = 71253, PDI = 1.77.

[0155] Example 10

[0156] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazol-co-thiopheno[3,2-b]thiophene](Pg2Tz-TT(4O)) with the structural formula shown in Formula 10:

[0157]

[0158] The difference between this embodiment and Embodiment 1 is as follows:

[0159] The conjugated polymer is Pg2Tz-TT(4O), and its synthesis reaction formula is as follows:

[0160]

[0161] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,5-bis(trimethyltinyl)thiophene[3,2-b]thiophene, namely compound 11. The amount of compound 11 was 93.2 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 1, and the conjugated polymer Pg2Tz-TT(4O) (111 mg, yield 82%) was obtained.

[0162] NMR analysis of Pg2Tz-TT(4O) yielded the following results: Figure 11 As shown, its structural characterization is as follows: 1 ¹H NMR (500MHz, Chloroform-d) δ 7.05 (s, 1H), 3.66 (m, 30H); Elemental analysis of Pg₂Tz-TT(₄O): Calculated C, 49.51; H, 5.43; N, 4.44; O, 20.29; S, 20.33; Measured C, 49.61; H, 5.33; N, 4.46; O, 20.27; S, 20.33.

[0163] Cyclic voltammetry tests were performed on Pg2Tz-TT(4O), and the results are shown in Table 1. The cyclic voltammetry curves are as follows: Figure 12 As shown.

[0164] Pg2Tz-TT(4O) was analyzed by gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃). The gel permeation chromatography results are as follows: Figure 13 As shown, Mn = 28581, PDI = 1.53.

[0165] Example 11

[0166] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-thieno[3,2-b]thiophene](Pg2Tz-TT(5O)) with the structural formula shown in Formula 11:

[0167]

[0168] The difference between this embodiment and Embodiment 2 is as follows:

[0169] The conjugated polymer is Pg2Tz-TT(5O), and its synthesis reaction formula is as follows:

[0170]

[0171] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,5-bis(trimethyltinyl)thiophene[3,2-b]thiophene, namely compound 11. The amount of compound 11 was 93.2 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 2, and the conjugated polymer Pg2Tz-TT(5O) (121 mg, yield 82%) was obtained.

[0172] Elemental analysis of Pg2Tz-TT(5O) was performed: calculated values: C, 50.12; H, 5.89; N, 3.90; O, 22.25; S, 17.84; tested values: C, 50.22; H, 5.79; N, 3.92; O, 22.25; S, 17.82. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-TT(5O), and the results are as follows: Mn = 28646, PDI = 1.86.

[0173] Example 12

[0174] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-thieno[3,2-b]thiophene](Pg2Tz-TT(6O)) with the structural formula shown in Formula 12:

[0175]

[0176] The difference between this embodiment and Embodiment 3 is as follows:

[0177] The conjugated polymer is Pg2Tz-TT(6O), and its synthesis reaction formula is as follows:

[0178]

[0179] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,5-bis(trimethyltinyl)thiophene[3,2-b]thiophene, namely compound 11. The amount of compound 11 was 93.2 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 3, and the conjugated polymer Pg2Tz-TT(6O) (128 mg, yield 77%) was obtained.

[0180] Elemental analysis of Pg2Tz-TT(6O) was performed: calculated values: C, 50.60; H, 6.25; N, 3.47; O, 23.79; S, 15.89; tested values: C, 50.70; H, 6.15; N, 3.45; O, 23.80; S, 15.90. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-TT(6O), and the results are as follows: Mn = 31254, PDI = 1.79.

[0181] Example 13

[0182] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazolyl-co-dithiophene[3,2-b:2',3'-d]thiophene](Pg2Tz-TTT(4O)) with the structural formula shown in Formula 13:

[0183]

[0184] The difference between this embodiment and Embodiment 1 is as follows:

[0185] The conjugated polymer is Pg2Tz-TTT(4O), and its synthesis reaction formula is as follows:

[0186]

[0187] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,6-bis(trimethyltinyl)dithiophene[3,2-b:2',3'-d]thiophene, namely compound 12. The amount of compound 12 was 104.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 1, and the conjugated polymer Pg2Tz-TTT(4O) (113 mg, yield 79%) was obtained.

[0188] Elemental analysis of Pg2Tz-TTT(4O): Calculated values: C, 48.96; H, 4.99; N, 4.08; O, 18.63; S, 23.34; Analyzed values: C, 49.06; H, 4.89; N, 4.06; O, 18.62; S, 23.37. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-TTT(4O). The gel permeation chromatography results are as follows: Figure 10 As shown, Mn = 45289, PDI = 1.81.

[0189] Example 14

[0190] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-dithiopheno[3,2-b:2',3'-d]thiophene](Pg2Tz-TTT(5O)) with the structural formula shown in Formula 14:

[0191]

[0192] The difference between this embodiment and Embodiment 2 is as follows:

[0193] The conjugated polymer is Pg2Tz-TTT(5O), and its synthesis reaction formula is as follows:

[0194]

[0195] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,6-bis(trimethyltinyl)dithiophene[3,2-b:2',3'-d]thiophene, i.e., compound 12. The amount of compound 12 was 104.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 2, and the conjugated polymer Pg2Tz-TTT(5O) (116 mg, yield 73%) was obtained.

[0196] Elemental analysis of Pg2Tz-TTT(5O) was performed: calculated values ​​C, 49.59; H, 5.46; N, 3.61; O, 20.64; S, 20.68; and tested values ​​C, 49.70; H, 5.35; N, 3.63; O, 20.65; S, 20.65. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-TTT(5O), and the results are as follows: Mn = 64351, PDI = 1.96.

[0197] Example 15

[0198] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-dithiopheno[3,2-b:2',3'-d]thiophene](Pg2Tz-TTT(6O)) with the structural formula shown in Formula 15:

[0199]

[0200] The difference between this embodiment and Embodiment 3 is as follows:

[0201] The conjugated polymer is Pg2Tz-TTT(6O), and its synthesis reaction formula is as follows:

[0202]

[0203] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,6-bis(trimethyltinyl)dithiophene[3,2-b:2',3'-d]thiophene, i.e., compound 12. The amount of compound 12 was 104.4 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 3, and the conjugated polymer Pg2Tz-TTT(6O) (134 mg, yield 73%) was obtained.

[0204] Elemental analysis of Pg2Tz-TTT(6O) was performed: calculated values: C, 50.10; H, 5.84; N, 3.25; O, 22.24; S, 18.57; tested values: C, 50.22; H, 5.72; N, 3.23; O, 22.22; S, 18.61. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-TTT(6O), and the results are as follows: Mn = 72134, PDI = 1.93.

[0205] Example 16

[0206] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazolyl-co-(E)-1,2-di(thiophene-2-yl)ethylene](Pg2Tz-TvT(4O)) with the structural formula shown in Formula 16:

[0207]

[0208] (1) Preparation of bithiazole dibromo monomer 5 containing ethylene glycol side chain

[0209] The preparation method is the same as that of the bis(thiazolium) dibromo monomer 5 in Example 1;

[0210] (2) Synthesis of polymer Pg2Tz-TvT(4O)

[0211] Preparation of S1, vinyl-1,2-bis(5-(trimethyltinyl)thiophene-2-yl)ethylene monomer 15 ((E)-1,2-bis(5-(trimethyltinyl)thiophene-2-yl)ethylene)

[0212]

[0213] Under a nitrogen atmosphere, thiophene-2-carboxaldehyde, compound 13 (9.6 g, 50 mmol), and dry THF (100 mL) were added to a 250 mL two-necked flask. The reaction system was placed in an ice-salt bath and stirred at 300 rpm. TiCl4 (8.2 mL, 75 mmol) was slowly added dropwise. After the addition was complete, the reaction was maintained at a low temperature for 0.5 h. Then, zinc powder (10.2 g, 150 mmol) was added in three batches, and the reaction was continued at a low temperature for another 0.5 h. The reaction system was then heated to reflux and stirred at 300 rpm for 16 h. After the reaction system cooled to room temperature, the reaction was quenched with water. The reaction solution was extracted three times with dichloromethane (50 mL each time). The obtained organic phase was washed with saturated brine, and the organic phase was collected, dried over 30 g of anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrated crude product was separated by silica gel column chromatography to obtain (E)-1,2-di(thiophene-2-yl)ethylene, compound 14 (C 10 H8S2, 6.8g, yield 40%.

[0214] Elemental analysis of compound 14: theoretical values: C, 62.46; H, 4.19; S, 33.34; measured values: C, 62.45; H, 4.18; S, 33.36.

[0215] Under a nitrogen atmosphere, compound 14 (0.19 g, 1.0 mmol) and dry THF (35 mL) were added to a 100 mL two-necked flask. The reaction system was placed in a dry ice / acetone bath at -78 °C and stirred at 300 rpm. After complete cooling, lithium diisopropylaminolithium (LDA) solution (2.2 mL, 1 mmol / L) was slowly added dropwise to the reaction system. After the addition was complete, the reaction was maintained at low temperature for 1 h. Then, trimethyltin chloride (0.48 g, 2.4 mmol) was added to the reaction system, and the reaction system was brought back to room temperature for 2 h. The reaction was quenched with water, and the reaction solution was extracted three times with dichloromethane (50 mL each time). The obtained organic phase was washed with saturated brine, and the organic phase was collected, dried over 30 g of anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrated crude product was recrystallized from ethanol to obtain vinylbisthiophene bistrimethyltin monomer 15 (C 16 H 24 S2Sn2, 0.36g, yield 70%.

[0216] Elemental analysis of vinylbithiophene bistrimethyltin monomer 15: theoretical values: C, 37.11; H, 4.67; S, 12.38; Sn, 45.84; measured values: C, 37.10; H, 4.68; S, 12.36; Sn, 45.86.

[0217] Synthesis of S2, Pg2Tz-TvT(4O)

[0218]

[0219] Bis(thiazolium) dibromo monomer 5 (130 mg, 0.2 mmol), vinylbis(thiaphene) bis(trimethyltin) monomer 15 (103.6 mg, 0.2 mmol), tris(dibenzylacetone) dipalladium (4 mg, 0.004 mmol) and tris(o-methylphenyl)phosphine (6 mg, 0.016 mmol) were weighed into a nitrogen-filled polymerization tube. The following operations were the same as in Example 1 to obtain the conjugated polymer Pg2Tz-TvT(4O) (111 mg, yield 79%).

[0220] Elemental analysis of Pg2Tz-TvT(4O) was performed: calculated values ​​C, 52.77; H, 5.61; N, 4.10; O, 18.74; S, 18.78; and measured values ​​C, 52.87; H, 5.51; N, 4.12; O, 18.72; S, 18.78. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-TvT(4O), and the results are as follows: Mn = 58416, PDI = 1.84.

[0221] Example 17

[0222] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bisthiazolyl-co-(E)-1,2-di(thiophene-2-yl)ethylene](Pg2Tz-TvT(5O)) with the structural formula shown in Formula 17:

[0223]

[0224] (1) Preparation of bithiazole dibromo monomer 7 containing ethylene glycol side chain

[0225] The preparation method is the same as that of the bis(thiazole) dibromo monomer 7 in Example 2;

[0226] (2) Synthesis of polymer Pg2Tz-TvT(5O)

[0227] Preparation of S1, Vinylbisthiophene bistrimethyltin monomer 15

[0228] The preparation method of vinylbithiophene bistrimethyltin monomer 15 is the same as that in Example 16;

[0229] Synthesis of S2, Pg2Tz-TvT(5O)

[0230]

[0231] The difference between this step and S2 in Example 16 is that the dibromo monomer is bithiazole dibromo monomer 7, and the amount of bithiazole dibromo monomer 7 is 147.7 mg (0.2 mmol). The remaining process steps and parameter settings are the same as in S2 in Example 16, and the conjugated polymer Pg2Tz-TvT(5O) (122 mg, yield 80%) is obtained.

[0232] Elemental analysis of Pg2Tz-TvT(5O) was performed: calculated values ​​C, 52.97; H, 6.01; N, 3.63; O, 20.75; S, 16.63; and tested values ​​C, 53.10; H, 5.88; N, 3.65; O, 20.77; and S, 16.59. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-TvT(5O), and the results are as follows: Mn = 58469, PDI = 1.69.

[0233] Example 18

[0234] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bisthiazolyl-co-(E)-1,2-di(thiophene-2-yl)ethylene](Pg2Tz-TvT(6O)) with the structural formula shown in Formula 18:

[0235]

[0236] (1) Preparation of bithiazole dibromo monomer 8 containing ethylene glycol side chain

[0237] The preparation method is the same as that of the bis(thiazolium) dibromo monomer 8 in Example 3;

[0238] (2) Synthesis of polymer Pg2Tz-TvT(6O)

[0239] Preparation of S1, Vinylbisthiophene bistrimethyltin monomer 15

[0240] The preparation method of vinylbithiophene bistrimethyltin monomer 15 is the same as that in Example 16;

[0241] Synthesis of S2, Pg2Tz-TvT(6O)

[0242]

[0243] The difference between this step and S2 in Example 16 is that the dibromo monomer is bithiazole dibromo monomer 8, and the amount of bithiazole dibromo monomer 8 is 165.3 mg (0.2 mmol). The remaining process steps and parameter settings are the same as in S2 in Example 16, and the conjugated polymer Pg2Tz-TvT(6O) (130 mg, yield 78%) is obtained.

[0244] Elemental analysis of Pg2Tz-TvT(6O) was performed: calculated values ​​C, 53.13; H, 6.34; N, 3.26; O, 22.35; S, 14.93; and measured values ​​C, 53.23; H, 6.24; N, 3.28; O, 22.37; S, 14.89. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-TvT(6O), and the results are as follows: Mn = 62844, PDI = 1.72.

[0245] Example 19

[0246] This embodiment discloses a poly[4,4'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-5,5'-bithiazole-co-5,5'-bithiazole](Pg2Tz-2Tz(4O)) with the structural formula shown in Formula 19:

[0247]

[0248] The difference between this embodiment and Embodiment 1 is as follows:

[0249] The conjugated polymer is Pg2Tz-2Tz(4O), and its synthesis reaction formula is as follows:

[0250]

[0251] In this process, the bis(trimethyltin) monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,2'-bis(trimethyltinyl)-5,5'-bithiazole, i.e., compound 16. The amount of compound 16 was 98.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 1, and the conjugated polymer Pg2Tz-2Tz(4O) (113 mg, yield 79%) was obtained.

[0252] Elemental analysis of Pg2Tz-2Tz(4O) was performed: calculated values: C, 47.40; H, 5.20; N, 8.50; O, 19.43; S, 19.47; tested values: C, 47.50; H, 5.10; N, 8.52; O, 19.45; S, 19.43. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-2Tz(4O), and the results are as follows: Mn = 46381, PDI = 1.71.

[0253] Example 20

[0254] This embodiment discloses a poly[4,4'-bis((2,5,8,11-tetraoxatridecane-13-yl)oxy)-5,5'-bithiazole-co-5,5'-bithiazole](Pg2Tz-2Tz(5O)) with the structural formula shown in Formula 20:

[0255]

[0256] The difference between this embodiment and Embodiment 2 is as follows:

[0257] The conjugated polymer is Pg2Tz-2Tz(5O), and its synthesis reaction formula is as follows:

[0258]

[0259] In this process, the bis(trimethyltin)monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,2'-bis(trimethyltinyl)-5,5'-bithiazole, i.e., compound 16. The amount of compound 16 was 98.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 2, and the conjugated polymer Pg2Tz-2Tz(5O) (123 mg, yield 76%) was obtained.

[0260] Elemental analysis of Pg2Tz-2Tz(5O): calculated values ​​C, 48.24; H, 5.67; N, 7.50; O, 21.42; S, 17.17; tested values ​​C, 48.34; H, 5.57; N, 7.52; O, 21.41; S, 17.16. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was performed on Pg2Tz-2Tz(5O), and the results are as follows: M n =48816, PDI=1.69.

[0261] Example 21

[0262] This embodiment discloses a poly[4,4'-bis((2,5,8,11,14-pentahexadecane-16-yl)oxy)-5,5'-bithiazole-co-5,5'-bithiazole](Pg2Tz-2Tz(6O)) with the structural formula shown in Formula 21:

[0263]

[0264] The difference between this embodiment and Embodiment 3 is as follows:

[0265] The conjugated polymer is Pg2Tz-2Tz(6O), and its synthesis reaction formula is as follows:

[0266]

[0267] In this process, the bis(trimethyltin)monomer was changed from 2,5-bis(trimethyltinyl)thiophene 6 to 2,2'-bis(trimethyltinyl)-5,5'-bithiazole, i.e., compound 16. The amount of compound 16 was 98.8 mg (0.2 mmol). The remaining process steps and parameter settings were the same as in Example 3, and the conjugated polymer Pg2Tz-2Tz(6O) (133 mg, yield 71%) was obtained.

[0268] Elemental analysis of Pg2Tz-2Tz(6O) was performed: calculated values ​​C, 48.91; H, 6.04; N, 6.71; O, 22.99; S, 15.36; tested values ​​C, 49.02; H, 5.93; N, 6.75; O, 22.97; S, 15.34. Gel permeation chromatography (GPC, hexafluoroisopropanol, polystyrene as standard, 35℃) was also performed on Pg2Tz-2Tz(6O), and the results are as follows: M n =52813, PDI=1.74.

[0269] The end capping groups, molecular weight, and distribution of the conjugated polymers provided by this invention are not particularly limited and can be selected according to the conventional methods used by those skilled in the art. As long as the conjugated polymer has the structure described in the following formula, the technical problem of this invention can be solved and the corresponding effect can be achieved.

[0270]

[0271] Performance testing

[0272] The conjugated polymers synthesized in Examples 1-21 were used as organic hybrid ionic-electron conductors, and subsequently as channel materials for p-type organic electrochemical transistor devices, to test their electrochemical performance. The structures were as follows... Figure 14An organic electrochemical transistor device was developed using borosilicate glass as a substrate. A standard positive photoresist process (AZ5214, purchased from Suzhou Ruicai) was used to deposit 40 nm thick interdigitated gold electrodes on the substrate, resulting in a transport channel 400 μm wide and 30 μm long. Residual photoresist was washed away with acetone, leaving only the gold electrode pattern on the borosilicate glass surface. Two adjacent gold electrodes constitute the carrier transport channel. A standard negative photoresist process (SU-8, purchased from Suzhou Ruicai) was used to protect the area outside the electrode channel, acting as a protective layer. AZ5214 (also purchased from Suzhou Ruicai) was used to protect the area outside the electrode channel using a standard positive photoresist process, acting as a sacrificial layer. A conjugated polymer was prepared in a solvent to a concentration of 1–10 mg / mL. -1 The solution, with chloroform as the solvent, was used to prepare a 20-100 nm thick film on the channel by spin coating. After solvent washing, the sacrificial positive adhesive was peeled off, leaving only the channel region containing the polymer film. The remaining negative adhesive served as the electrode protective layer. The polymer film was then subjected to thermal annealing at 100-200°C for 5-60 min to obtain the channel material prepared by the conjugated polymer provided by this invention. During the fabrication of the organic electrochemical transistor, it was observed that the prepared conjugated polymer film was in good condition, indicating that the conjugated polymer prepared by this invention has good film-forming properties. The holes of the hollow polydimethylsiloxane groove were aligned and attached to the electrode, and an appropriate amount of 0.1 mol / L NaCl solution or PBS phosphate buffer solution was added. The gate material was Ag / AgCl. The organic electrochemical transistor was tested, and the results are shown in Table 1.

[0273] This performance test does not impose any particular restrictions on the choice of film preparation method and solvent; conventional choices made by those skilled in the art are acceptable. Preferred film preparation methods include spin coating, drop coating, or blade coating. Preferred solvents include chloroform, hexafluoroisopropanol, or chlorobenzene. Preferred electrolyte solutions include NaCl solution or PBS phosphate buffer solution. This invention does not impose any particular restrictions on the structure and parameters of the organic electrochemical transistor used to test polymer performance, such as polymer film thickness, electrode thickness and type on the substrate, channel fabrication process, and electrolyte solution; conventional devices familiar to those skilled in the art can be used. There are also no particular restrictions on the characterization of the organic electrochemical transistor; conventional methods familiar to those skilled in the art can be used.

[0274] Table 1. HOMO energy levels and electrochemical performance parameters of OECT using the conjugated polymers prepared in this invention as channeling materials.

[0275]

[0276]

[0277] The data in the table shows that the highest transconductance of organic electrochemical transistor devices is 20 S cm⁻¹. -1 The maximum quality factor (μC*) is above at 40 F cm⁻¹. -1 V -1 s -1 The above; among them, Pg2Tz-T exhibits superior organic electrochemical transistor performance compared to other polymers.

[0278] The above embodiments are merely examples to clearly illustrate the technical solutions of the present invention, and are not intended to limit the implementation methods. Those skilled in the art can make other variations or modifications based on the above description, and it is neither necessary nor possible to exhaustively list all possible implementation methods here. However, obvious variations or modifications derived therefrom are still within the protection scope of this invention.

Claims

1. A conjugated polymer containing a bithiazole unit with an ethylene glycol side chain, characterized in that, The conjugated polymer has a polythiazole or polythiazole / thiophene backbone as the molecular backbone and polar ethylene glycol short chains as side chains. The structural formula of the conjugated polymer is shown below: In the formula, n is an integer from 2 to 1000, and m is an integer from 1 to 10; Ar can be one of the following structures: 。 2. The conjugated polymer containing a bithiazole unit with an ethylene glycol side chain according to claim 1, characterized in that, m is an integer from 2 to 6; Ar can be one of the following structures: 。 3. The conjugated polymer containing a bithiazole unit with an ethylene glycol side chain according to claim 1, characterized in that, The structural formula of the conjugated polymer is shown below: 。 4. A method for preparing the conjugated polymer according to any one of claims 1 to 3, characterized in that, The steps are as follows: Under an inert atmosphere, the dibromo monomer, the ditrialkyltin monomer, the palladium catalyst and the ligand are dissolved in an organic solvent. The reaction system is subjected to Stille polymerization under light-protected and reflux conditions. After the reaction is completed, the obtained polymer is extracted and purified to obtain a conjugated polymer containing bithiazole units with ethylene glycol side chains. The structural formula of the dibromo monomer is: In the formula, m is an integer from 1 to 10; The structural formula of the bis(trialkyltin) monomer is one of the following structural formulas: 。 5. The method for preparing the conjugated polymer according to claim 4, characterized in that, m is an integer from 2 to 6.

6. The method for preparing the conjugated polymer according to claim 4, characterized in that, The organic solvent is toluene; The palladium catalyst is tris(dibenzylacetone)dipalladium; The ligand is tris(o-methylphenyl)phosphine; The molar ratio of the dibromo monomer, the ditrialkyltin monomer, the palladium catalyst, and the ligand is 1:1:(0.01~0.05):(0.04~0.2). The concentrations of both the dibromo monomer and the bis(trialkyltin) monomer in the organic solvent are 0.005–0.1 mmol / L.

7. The method for preparing the conjugated polymer according to claim 6, characterized in that, The molar ratio of the dibromo monomer, the ditrialkyltin monomer, the palladium catalyst, and the phosphine ligand is 1:1:0.02:0.

08. The concentrations of both the dibromo monomer and the ditrialkyltin monomer in the organic solvent are 0.02~0.06 mmol / L.

8. The method for preparing the conjugated polymer according to claim 4, characterized in that, The Stille polymerization reaction is carried out at a temperature of 80~120℃ and for a reaction time of 1~96h.

9. The method for preparing the conjugated polymer according to claim 8, characterized in that, The Stille polymerization reaction is carried out at a temperature of 90-110°C for 16-36 hours.

10. The application of a conjugated polymer containing a bithiazole unit with an ethylene glycol side chain as described in any one of claims 1 to 3, characterized in that, This conjugated polymer is used as an organic mixed ionic electronic conductor material in organic electrochemical transistors.

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