Side chain type polymer used as hole transport material, and synthesis method and application thereof

Abstract

The invention belongs to the technical field of organic hole transport materials, and discloses a side chain type polymer used as a hole transport material, and a synthesis method and application thereof. The side chain type polymer disclosed by the invention is a homopolymer or a copolymer; wherein the homopolymer only has a conjugated unit, the copolymer comprises the conjugated unit and a cross-linking unit, the conjugated unit mainly takes a triphenylamine unit with electricity supply as a core, so that the side chain type polymer has relatively high carrier mobility, and meanwhile, plane conjugated groups such as carbazole and fluorene are introduced, so that the thermal stability of the polymer is improved and the HOMO energy level is adjusted; in the copolymer, a flexible chain segment and a cross-linking group are introduced into a cross-linking unit, and good solvent resistance can be achieved through cross-linking.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronics, specifically relating to side-chain polymers used as hole transport materials, their synthesis methods and applications, particularly in OLEDs and QLEDs. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a novel display technology. Compared to traditional LCDs and LEDs, OLEDs possess a series of advantages, including low power consumption, self-illumination, fast response, high brightness, large-area fabrication capability, and flexibility. Therefore, they are highly favored in the display field and widely used in the displays of mobile phones, computers, and other devices. The first successful OLED device can be traced back to 1987. At that time, Chinese scientist Ching-Yun Tang used aromatic diamine as the hole transport layer and 8-hydroxyquinolinato aluminum [Tris(8-hydroxyquinolinato) aluminum] as the light-emitting layer to fabricate a bilayer organic thin-film device, successfully achieving an external quantum efficiency of 1%, marking a breakthrough in the field of organic display light emission. Currently, the external quantum efficiency of red and green OLEDs can reach 20-30%, maintaining both high efficiency and long lifetime, and has already achieved initial commercialization.

[0003] Currently, vacuum evaporation is the mainstream fabrication process for OLED devices. The main advantage of evaporation is its ability to produce high-purity and high-quality thin films; however, its complex process, high cost, and inability to support large-area device fabrication limit the large-scale commercialization of OLEDs. In contrast, solution spin coating, with its low cost and ability to support large-area device fabrication, has attracted significant attention from researchers. However, OLEDs fabricated using solution spin coating still suffer from several problems, such as interlayer miscibility. This means that during continuous coating, the next layer is easily washed away by the solvent of the previous layer, resulting in interlayer miscibility, particularly at the interface between the hole transport layer (HTL) and the emissive layer (EML). Therefore, it is necessary to develop hole transport materials with better solvent resistance to address these issues. Summary of the Invention

[0004] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a class of side-chain polymers that can be used as hole transport materials. These polymers possess a wide band gap, high carrier mobility, and good solvent resistance, and can be used to prepare solution-processable OLEDs and QLEDs.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This application provides a side-chain polymer for use as a hole transport material, having the following chemical structural formula:

[0007]

[0008] When the side-chain polymer is a homopolymer, x is the number of repeating units, and y = 0; when the side-chain polymer is a copolymer, x and y are the mole fractions of each unit, and 0 <x<1,0<y<1,x+y=1;

[0009] In the above chemical structural formula, Ar1 is an aromatic hydrocarbon group with 6 to 30 carbon atoms; Ar2 is an aromatic hydrocarbon group with 6 to 60 carbon atoms or an aromatic heterocyclic group with 3 to 60 carbon atoms containing at least one heteroatom; Ar3 is an aromatic hydrocarbon group with 6 to 60 carbon atoms or an aromatic heterocyclic group with 3 to 60 carbon atoms containing at least one heteroatom; and Ar4 is an alkoxy group with 0 to 30 carbon atoms containing at least one oxygen atom or a hydrocarbon group with 0 to 30 carbon atoms.

[0010] As a further preferred embodiment, the Ar1 described in this application is preferably one of the following structures or a halogenated, deuterated, or alkyl-substituted derivative thereof:

[0011]

[0012] Furthermore, the Ar2 or Ar3 described in the embodiments of this application are preferably one of the following structures or one of the following halogenated, deuterated, or alkyl-substituted derivatives:

[0013]

[0014] Furthermore, the Ar4 described in the embodiments of this application is preferably one of the following structures or a halogenated, deuterated, or alkyl-substituted derivative of the following structures:

[0015]

[0016] Furthermore, the side-chain polymer described in the embodiments of this application is preferably one of the following structures or one of the following halogenated, deuterated, or alkyl-substituted derivatives:

[0017]

[0018]

[0019]

[0020]

[0021] Furthermore, this application also provides a method for synthesizing a side-chain polymer, which yields a homopolymer with a core of an electron-donating triphenylamine conjugated unit and the introduction of planar conjugated groups such as carbazole and fluorene, comprising the following steps:

[0022] Synthesis of conjugated monomers: Under inert gas protection, the amine-containing Ar2 unit and the brominated Ar3 unit undergo a Buchwald-Hartwig aromatic amination reaction in a catalyst system, followed by a Buchwald-Hartwig aromatic amination reaction with the brominated vinyl Ar1 unit in a catalyst system to obtain a monomer with a conjugated structure. The general reaction formula is as follows:

[0023]

[0024] Polymerization reaction: Under inert gas protection, the above conjugated monomers are dissolved in an organic solvent, then a catalyst is added, and the mixture is heated to undergo free radical polymerization. After the reaction is completed, the target product is obtained.

[0025] Furthermore, this application also provides another method for synthesizing side-chain polymers, using conjugated units and crosslinking units as reactive monomers. The crosslinking units introduce flexible segments and crosslinking groups, comprising the following steps:

[0026] Synthesis of conjugated monomers: Under inert gas protection, the amine-containing Ar2 unit and the brominated Ar3 unit undergo a Buchwald-Hartwig aromatic amination reaction in a catalyst system, followed by a Buchwald-Hartwig aromatic amination reaction with the brominated vinyl Ar1 unit in a catalyst system to obtain a monomer with a conjugated structure. The general reaction formula is as follows:

[0027]

[0028] Synthesis of crosslinking monomers: Under inert gas protection, Ar4 or Ar4 iodide is reacted with 1-bromobenzocyclobutene in a catalyst system for substitution, followed by nucleophilic substitution with 4-chloromethylstyrene in a catalyst system to obtain crosslinking monomers with crosslinking groups. The general reaction formula is as follows:

[0029] or

[0030]

[0031] Polymerization reaction: Under inert gas protection, the above-mentioned conjugated monomers and crosslinking monomers are dissolved in an organic solvent, then a catalyst is added, and the mixture is heated to undergo a free radical polymerization reaction. After the reaction is completed, the target product is obtained.

[0032] As a further preferred embodiment, in the above synthesis method, the organic solvent is one of toluene, chlorobenzene, dichlorobenzene, etc.; the catalyst for free radical polymerization is one of AIBN, ABVN, etc., and the amount of catalyst used is 0.1% to 0.3% of the total molar amount of the reactants; the free radical polymerization reaction temperature is 80-85℃, and the reaction time is 20-25 hours.

[0033] The application of the aforementioned side-chain polymers in the preparation of organic / polymer electronic devices is characterized by dissolving the polymer in an organic solvent, or mixing it with at least one other substance and dissolving it in an organic solvent, and then forming a film by spin coating, inkjet printing, or printing to obtain the hole transport layer of the organic / polymer electronic device; the organic / polymer electronic device includes organic / polymer photodetectors, organic / polymer solar cells, organic / polymer thin-film transistors, organic / polymer light-emitting transistors, organic / polymer phototransistors, and organic / polymer organic light-emitting electrochemical cells; the organic solvent includes one or more of xylene, tetrahydrofuran, chlorobenzene, and dichlorobenzene.

[0034] Compared with the prior art, the significant advantages of the present invention are:

[0035] 1. The side-chain polymer described in this application is a homopolymer or copolymer; wherein the homopolymer contains only conjugated units, and the copolymer includes conjugated units and crosslinking units. The conjugated units are mainly based on the core of the charged triphenylamine unit, which gives the side-chain polymer a high carrier mobility. At the same time, the introduction of planar conjugated groups such as carbazole and fluorene is beneficial to improving the thermal stability of the polymer and adjusting the HOMO energy level. In the copolymer, the crosslinking units introduce flexible segments and crosslinking groups, which can have good solvent resistance through crosslinking.

[0036] 2. The side-chain polymer described in this application has a wide bandgap and high carrier mobility, which can accelerate hole transport between device layers, reduce transport loss, and promote efficient charge separation and transport. Combined with the wide bandgap characteristics, it can broaden the adaptability to photons of different energies, help to prepare high-efficiency optoelectronic devices such as OLEDs and QLEDs, improve photoelectric conversion efficiency, and reduce driving voltage.

[0037] 3. The side-chain polymer described in this application has high thermal stability, making it less prone to structural deformation and chemical decomposition due to heat during device fabrication (such as high-temperature annealing processes) and actual use (such as ambient temperature fluctuations and device self-heating). This maintains the regularity of the molecular structure and the stability of the charge carrier transport channels, improves the device's working life and resistance to thermal degradation, ensures stable operation under different environments and working conditions, and expands the application potential of optoelectronic devices in high-temperature scenarios (such as automotive lighting and industrial high-temperature environment displays).

[0038] 4. The side-chain polymer described in this application has good solvent resistance, which can prevent it from being eroded by the solvent of the subsequent coating layer when the solution is processed into film (such as spin coating and inkjet printing), stabilize its own film structure and electrical properties, solve the problems of interface defects and carrier transport obstruction caused by interlayer mutual solubility in the fabrication of OLED and QLED multilayer devices, ensure the quality of interlayer interface, and improve the stability and consistency of the device. Attached Figure Description

[0039] Figure 1 The absorption, emission, and low-temperature phosphorescence spectra of compound 4 in toluene solution and thin film form are shown.

[0040] Figure 2 The graph shows the solvent resistance of the Compound 4 film after annealing at 200°C.

[0041] Figure 3 The graph shows the solvent resistance of the Compound 7 film after annealing at 200°C. Detailed Implementation

[0042] The implementation of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the implementation and protection of the present invention are not limited thereto. It should be noted that any processes or parameters not specifically described below are those that can be understood or implemented by those skilled in the art by referring to the prior art.

[0043] Unless otherwise specified, all reagents used in the examples are commercially available.

[0044] Example 1

[0045] Preparation of compound 4

[0046] (1) Preparation of compound 1

[0047] In a 100 mL single-necked flask, phenyl-3-carbazole borate (2.0 g, 5.42 mmol), 1-bromo-4-iodobenzene (1.839 g, 6.50 mmol), and potassium carbonate (3.745 g, 27.1 mmol) were dissolved in a mixture of 20 mL toluene and 9 mL distilled water. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 8 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 2.315 g of a white solid product, with a yield of 88%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0048] (2) Preparation of compound 2

[0049] In a 100 mL single-necked flask, compound 1 (2.3 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 8 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 2.471 g of a yellow solid, with a yield of 85%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0050] (3) Preparation of compound 3

[0051] In a 100 mL single-necked flask, compound 2 (2.4 g, 4.93 mmol), 4-bromostyrene (0.992 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The solution was dried under vacuum at 50 °C for 24 h to obtain 2.540 g of a yellow-green solid, with a yield of 86%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0052] (4) Preparation of compound 4

[0053] Inside a glove box, compound 3 (9.0 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The reaction mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. The mixture was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. The product was filtered and dried under vacuum at 50 °C for 24 h to obtain 8.181 g of a white, lumpy solid with a yield of 90.9%, a weight-average molecular weight (Mw) of 146.9 kDa, and a polydispersity index (PDI) of 1.7.

[0054] The chemical reaction equations for the synthesis of compounds 1–4 are shown below:

[0055]

[0056] The UV-Vis absorption and fluorescence emission spectra of compound 4 were measured, and the electrochemical energy levels (HOMO and LUMO) of the compound were determined. The optical band gap (E0) of compound 4 was determined by absorption spectroscopy. g opt The triplet energy levels (E0) of compound 4 were measured using low-temperature phosphorescence spectroscopy. T ).

[0057] Table 1: Physicochemical properties of compound 4

[0058] Example 2

[0059] Preparation of compound 7

[0060] (1) Preparation of compound 5

[0061] In a 100 mL single-necked flask, 3-bromo-9-phenyl-9H-carbazole (2.0 g, 6.21 mmol), 4-aminobiphenyl (1.156 g, 6.83 mmol), and sodium tert-butyloxide (0.597 g, 6.21 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 8 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated by vacuum distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The solution was dried under vacuum at 50 °C for 24 h to obtain 2.255 g of a yellowish-brown solid, with a yield of 85%. 1 HNMR, 13CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0062] (2) Preparation of compound 6

[0063] In a 100 mL single-necked flask, compound 5 (2.2 g, 5.36 mmol), 4-bromostyrene (1.080 g, 5.90 mmol), and sodium tert-butyloxide (0.515 g, 5.36 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.684 g of a yellow powder solid, with a yield of 60%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0064] (3) Preparation of compound 7

[0065] Inside a glove box, compound 6 (6.0 g, 12.0 mmol, 1000 eq) and AIBN (2.0 mg, 0.012 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 4.8 mL of chlorobenzene, sealed, and removed from the glove box. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 5.520 g of a white, lumpy solid with a yield of 92.0%, a weight-average molecular weight (Mw) of 125.0 kDa, and a polydispersity index (PDI) of 2.1.

[0066] The chemical reaction equations for synthesizing compounds 5–7 are shown below:

[0067]

[0068] Example 3

[0069] Preparation of compound 10

[0070] (1) Preparation of compound 8

[0071] In a 100 mL single-necked flask, 2-bromodibenzothiophene (1.518 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 12 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated by vacuum distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The solution was dried under vacuum at 50 °C for 24 h to obtain 1.664 g of a yellow solid, with a yield of 78.1%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0072] (2) Preparation of compound 9

[0073] In a 100 mL single-necked flask, compound 8 (1.733 g, 4.93 mmol), 4-bromo-4'-vinyl-1,1'-biphenyl (1.404 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, the mixture was extracted with water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.901 g of a yellow-green solid, with a yield of 70.3%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0074] (3) Preparation of compound 10

[0075] Inside a glove box, compound 3 (8.104 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 7.221 g of a white, lumpy solid with a yield of 89.1%, a weight-average molecular weight (Mw) of 123.9 kDa, and a polydispersity index (PDI) of 1.6.

[0076] The chemical reaction equations for the synthesis of compounds 8–10 are shown below:

[0077]

[0078] Example 4

[0079] Preparation of compound 14

[0080] (1) Preparation of compound 11

[0081] In a 100 mL single-necked flask, 4-iodostyrene (1.247 g, 5.42 mmol), 3-bromocarbazole (1.600 g, 6.50 mmol), and potassium carbonate (3.745 g, 27.1 mmol) were dissolved in a mixture of 20 mL toluene and 9 mL distilled water. Then, CuI₂ (3 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 8 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered, concentrated by vacuum distillation, and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.615 g of a white solid product, with a yield of 74.8%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0082] (2) Preparation of compound 12

[0083] In a 100 mL single-necked flask, 2-bromodibenzofuran (1.426 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixed solution, and the mixture was refluxed at 90 °C for 10 h under nitrogen. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.431 g of a yellow solid, with a yield of 70.2%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0084] (3) Preparation of compound 13

[0085] In a 100 mL single-necked flask, compound 12 (1.654 g, 4.93 mmol), compound 11 (1.887 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, the mixture was extracted with water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 2.483 g of a yellow-green solid, with a yield of 79.9%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0086] (4) Preparation of compound 14

[0087] Inside a glove box, compound 3 (9.222 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 7.940 g of a white lumpy solid, with a yield of 86.1%, a weight-average molecular weight (Mw) of 133.94 kDa, and a polydispersity index (PDI) of 1.9.

[0088] The chemical reaction equations for the synthesis of compounds 11–14 are shown below:

[0089] Example 5

[0090] Preparation of compound 18

[0091] (1) Preparation of compound 15

[0092] In a 100 mL single-necked flask, 3,6-dibromo-9-phenylcarbazole (2.607 g, 6.50 mmol), vinylboric acid (0.39 g, 5.42 mmol), and sodium hydroxide (0.217 g, 5.42 mmol) were dissolved in a mixture of 20 mL toluene and 9 mL distilled water. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 12 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.560 g of a white solid product, with a yield of 69.8%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0093] (2) Preparation of compound 16

[0094] In a 100 mL single-necked flask, 2-bromo-9,9'-dimethylfluorene (1.576 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 10 h under nitrogen. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.655 g of a yellow solid, with a yield of 75.6%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0095] (3) Preparation of compound 17

[0096] In a 100 mL single-necked flask, compound 16 (1.782 g, 4.93 mmol), compound 15 (1.887 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered, concentrated by vacuum distillation, and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The solution was dried under vacuum at 50 °C for 24 h to obtain 2.592 g of a yellow-green lumpy solid, with a yield of 80.1%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0097] (4) Preparation of compound 18

[0098] Inside a glove box, compound 3 (9.621 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The reaction mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 7.581 g of a white lumpy solid, with a yield of 78.8%, a weight-average molecular weight (Mw) of 107.54 kDa, and a polydispersity index (PDI) of 1.6.

[0099] The chemical reaction equations for synthesizing compounds 15–18 are shown below:

[0100] Example 6

[0101] Preparation of compound 22

[0102] (1) Preparation of compound 19

[0103] In a 100 mL single-necked flask, 3,6-dibromo-9-phenylcarbazole (2.607 g, 6.50 mmol), styrylboronic acid (0.802 g, 5.42 mmol), and sodium hydroxide (0.217 g, 5.42 mmol) were dissolved in a mixture of 20 mL toluene and 9 mL distilled water. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 12 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 2.006 g of a white solid product, with a yield of 75.8%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0104] (2) Preparation of compound 20

[0105] In a 100 mL single-necked flask, 9-(4-bromophenyl)-9H-carbazole (1.859 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 10 h under nitrogen. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The filtrate was dried under vacuum at 50 °C for 24 h to obtain 2.010 g of a yellow solid, with a yield of 81.3%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0106] (3) Preparation of compound 21

[0107] In a 100 mL single-necked flask, compound 20 (2.024 g, 4.93 mmol), compound 19 (2.300 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, the mixture was extracted with water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 3.031 g of a yellow-green solid, with a yield of 77.9%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0108] (4) Preparation of compound 22

[0109] Inside a glove box, compound 3 (11.535 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The reaction mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 8.766 g of a white, lumpy solid with a yield of 76.0%, a weight-average molecular weight (Mw) of 96.87 kDa, and a polydispersity index (PDI) of 1.7.

[0110] The chemical reaction equations for the synthesis of compounds 19–22 are shown below:

[0111] . Example 7

[0112] Preparation of compound 26

[0113] (1) Preparation of compound 23

[0114] In a 100 mL single-necked flask, (4-bromophenyl)boric acid (1.305 g, 6.50 mmol), compound 19 (2.300 g, 5.42 mmol), and sodium hydroxide (0.217 g, 5.42 mmol) were dissolved in a mixture of 20 mL toluene and 9 mL distilled water. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 12 h under nitrogen. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated by vacuum distillation, then purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 2.431 g of a white solid product, with a yield of 84.4%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0115] (2) Preparation of compound 24

[0116] In a 100 mL single-necked flask, 3-bromo-9-phenyl-9H-carbazole (1.859 g, 5.77 mmol), 4-aminobiphenyl (1.074 g, 6.35 mmol), and sodium tert-butyloxide (0.554 g, 5.77 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 90 °C for 10 h under nitrogen. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The chromatogram was dried under vacuum at 50 °C for 24 h to obtain 1.585 g of a yellow solid, with a yield of 64.1%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0117] (3) Preparation of compound 25

[0118] In a 100 mL single-necked flask, compound 24 (2.024 g, 4.93 mmol), compound 23 (2.712 g, 5.42 mmol), and sodium tert-butyloxide (0.521 g, 5.42 mmol) were dissolved in 20 mL of toluene. Then, Pd(PPh3)4 (5 mol%) was added to the mixture, and the mixture was refluxed at 80 °C under nitrogen atmosphere overnight. After cooling to room temperature, extraction was performed by adding appropriate amounts of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The dried filtrate was concentrated by vacuum distillation and purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. The solution was dried under vacuum at 50 °C for 24 h to obtain 2.960 g of a yellow-green lumpy solid, with a yield of 68.8%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0119] (4) Preparation of compound 26

[0120] Inside a glove box, compound 3 (12.7 g, 15.3 mmol, 1000 eq) and AIBN (2.50 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. This solution was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. This product was filtered and dried under vacuum at 50 °C for 24 h to obtain 10.058 g of a white lumpy solid, with a yield of 79.2%, a weight-average molecular weight (Mw) of 111.32 kDa, and a polydispersity index (PDI) of 1.9.

[0121] The chemical reaction equations for the synthesis of compounds 23–26 are shown below:

[0122] . Example 8

[0123] Preparation of compound 30

[0124] (1) Preparation of compound 27

[0125] In a 250 mL double-necked flask, NBS (20.5 g, 115.2 mmol) was dissolved in 100 mL of chlorobenzene. The reaction was carried out under nitrogen atmosphere at room temperature in the dark for 30 min. Then, benzocyclobutene (10.0 g, 96 mmol) and benzoyl peroxide (BPO) (0.25 g, 1.06 mmol) were dissolved in 20 mL of chlorobenzene and slowly added dropwise to the reaction solution. The mixture was refluxed at 85 °C for 4 h under nitrogen atmosphere. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation. The filtrate was purified by column chromatography using a mixture of petroleum ether and dichloromethane as the chromatographic solvent. Vacuum distillation was then performed to obtain 12.442 g of a colorless and transparent liquid, with a yield of 71.1%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0126] (2) Preparation of compound 28

[0127] In a 50 mL two-necked flask, ethylene glycol (16.0 mL, 285.2 mmol) and potassium tert-butyloxide (8.19 g, 81.9 mmol) were added, followed by the slow addition of compound 27 (10.0 g, 54.6 mmol). The mixture was refluxed at 80 °C under nitrogen atmosphere and reacted overnight. After cooling to room temperature, the mixture was extracted with water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation. The solution was then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation yielded 4.931 g of a yellowish-brown transparent liquid, with a yield of 55.0%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0128] (3) Preparation of compound 29

[0129] In a 100 mL two-necked flask, compound 28 (4.0 g, 24.4 mmol) was dissolved in 20 mL of DMF. The flask was placed in an ice-water bath, and sodium hydride (0.878 g, 36.6 mmol) was injected in three portions under nitrogen atmosphere. The mixture was stirred for 20 min, then the ice-water bath was removed, and the mixture was allowed to react at room temperature for 2 h. Then, 4-chloromethylstyrene (5.586 g, 36.6 mmol) was slowly injected, and the mixture was refluxed at 60 °C under nitrogen atmosphere overnight. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation was then performed to obtain 3.421 g of a yellowish-brown transparent liquid, with a yield of 50.0%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0130] (4) Preparation of compound 30

[0131] Inside a glove box, weigh compound 7 (2.076 g, 4.05 mmol, 270 eq), compound 29 (0.126 g, 0.45 mmol, 30 eq), and AIBN (2.5 mg, 0.015 mmol, 1 eq) into a 48 ml pressure-resistant tube. Dissolve the contents in 9.2 ml of chlorobenzene, seal the tube, remove it from the glove box, and react it at 80 °C for 24 h. After cooling to room temperature, add 2 ml of chloroform to the reaction mixture to dissolve and dilute it. The product was added dropwise to 200 mL of methanol, and a yellow-green solid product precipitated. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone in a Soxhlet extractor. Finally, it was dissolved in chloroform and concentrated to 4-5 mL. The precipitate was added dropwise to 200 mL of methanol, and a solid product precipitated. The product was filtered and dried under vacuum at 50 °C for 24 h to obtain 1.962 g of white blocky solid with a yield of 89.1%, a weight-average molecular weight (Mw) of 149.2 kDa, and a polydispersity index (PDI) of 1.6.

[0132] The chemical reaction equations for synthesizing compounds 27–30 are shown below:

[0133] . Example 9

[0134] Preparation of compound 31

[0135] (1) Preparation of compound 31

[0136] Inside a glove box, compound 9 (1.907 g, 3.6 mmol, 240 eq), compound 29 (0.252 g, 0.9 mmol, 60 eq), and AIBN (2.5 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, and removed from the glove box. The mixture was reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. The mixture was then added dropwise to 200 mL of methanol, resulting in the precipitation of a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform and concentrated to 4-5 mL. The concentrate was then added dropwise to 200 mL of methanol, resulting in the precipitation of a solid product. The solid product was filtered and dried under vacuum at 50 °C for 24 h to obtain 1690 g of a white lumpy solid with a yield of 88.6%, a weight-average molecular weight (Mw) of 88.9 kDa, and a polydispersity index (PDI) of 1.6.

[0137] The chemical reaction equation for the synthesis of compound 31 is shown below:

[0138]

[0139] Example 10

[0140] Preparation of compound 34

[0141] (1) Preparation of compound 32

[0142] In a 50 mL two-necked flask, dihydroxyethyl ether (18.0 mL, 285.2 mmol) and potassium tert-butyloxide (8.19 g, 81.9 mmol) were added, followed by the slow addition of compound 27 (10.0 g, 54.6 mmol). The mixture was refluxed at 80 °C under nitrogen atmosphere and reacted overnight. After cooling to room temperature, the mixture was extracted with a suitable amount of water and dichloromethane. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation. The solution was then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation yielded 5.146 g of a yellowish-brown transparent liquid, with a yield of 52.3%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0143] (2) Preparation of compound 33

[0144] In a 100 mL two-necked flask, compound 32 (4.397 g, 24.4 mmol) was dissolved in 20 mL of DMF. The flask was placed in an ice-water bath, and sodium hydride (0.878 g, 36.6 mmol) was injected in three portions under nitrogen atmosphere. The mixture was stirred for 20 min, then the ice-water bath was removed, and the mixture was allowed to react at room temperature for 2 h. Then, 4-chloromethylstyrene (5.586 g, 36.6 mmol) was slowly injected, and the mixture was refluxed at 60 °C under nitrogen atmosphere overnight. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation was then performed to obtain 3.681 g of a yellowish-brown transparent liquid, with a yield of 50.9%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0145] (3) Preparation of compound 34

[0146] Inside a glove box, compound 7 (2.076 g, 4.05 mmol, 270 eq), compound 33 (0.133 g, 0.45 mmol, 30 eq), and AIBN (2.5 mg, 0.015 mmol, 1 eq) were weighed into a 48 mL pressure-resistant tube, dissolved in 9.2 mL of chlorobenzene, sealed, removed from the glove box, and reacted at 80 °C for 24 h. After cooling to room temperature, 2 mL of chloroform was added to the reaction mixture to dissolve and dilute it. The mixture was then added dropwise to 200 mL of methanol, precipitating a yellow-green solid product. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone using a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform, concentrated to 4-5 mL, and added dropwise to 200 mL of methanol, precipitating a solid product. The product was filtered, dried under vacuum at 50 °C for 24 h, yielding 1.853 g of a white lumpy solid with a yield of 83.9%, a weight-average molecular weight (Mw) of 97.9 kDa, and a polydispersity index (PDI) of 1.7.

[0147] The chemical reaction equations for synthesizing compounds 32-34 are shown below:

[0148] . Example 11

[0149] Preparation of compound 37

[0150] (1) Preparation of compound 35

[0151] In a 50 mL double-necked flask, compound 27 (10.0 g, 54.6 mmol) and magnesium powder (1.592 g, 65.5 mmol) were dissolved in 20 mL of THF. The mixture was refluxed at 60 °C under nitrogen for 2 h, followed by slow injection of 1,4-diiodobutane (8.7 mL, 65.5 mmol). After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation. The filtrate was then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation yielded 8.953 g of a yellowish-brown transparent liquid, with a yield of 57.3%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0152] (3) Preparation of compound 36

[0153] In a 50 mL double-necked flask, 4-chloromethylstyrene (8.333 g, 54.6 mmol) and magnesium powder (1.592 g, 65.5 mmol) were dissolved in 20 mL of THF. The mixture was refluxed at 60 °C under nitrogen for 2 h, and then compound 35 (13.02 g, 45.5 mmol) was slowly injected. After cooling to room temperature, water and dichloromethane were added for extraction. The lower organic phase was collected and dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure by distillation, then purified by column chromatography using a mixture of deionized water and EA as the chromatographic solvent. Vacuum distillation yielded 7.446 g of a yellowish-brown transparent liquid, with a yield of 59.2%. 1 HNMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0154] (4) Preparation of compound 37

[0155] Inside a glove box, weigh compound 7 (2.076 g, 4.05 mmol, 270 eq), compound 36 (0.124 g, 0.45 mmol, 30 eq), and AIBN (2.5 mg, 0.015 mmol, 1 eq) into a 48 ml pressure-resistant tube. Dissolve the contents in 9.2 ml of chlorobenzene, seal the tube, remove it from the glove box, and react it at 80 °C for 24 h. After cooling to room temperature, add 2 ml of chloroform to the reaction mixture to dissolve and dilute it. The product was added dropwise to 200 mL of methanol, and a yellow-green solid product precipitated. The coarse precipitate was collected by filtration and purified by extraction with methanol and acetone in a Soxhlet extractor. Finally, the precipitate was dissolved in chloroform and concentrated to 4-5 mL. The precipitate was added dropwise to 200 mL of methanol, and a solid product precipitated. The product was filtered and dried under vacuum at 50 °C for 24 h to obtain 1.758 g of white blocky solid with a yield of 79.9%, a weight-average molecular weight (Mw) of 102.3 kDa, and a polydispersity index (PDI) of 1.8.

[0156] The chemical reaction equations for synthesizing compounds 35–37 are shown below:

[0157] . Application Example 1

[0158] Fabrication of quantum dot light-emitting diodes (QLEDs)

[0159] The ITO substrate was ultrasonically cleaned sequentially with tetrahydrofuran, deionized water, and isopropanol (10 minutes each), and then dried. After plasma treatment, PEDOT:PSS was spin-coated onto the ITO surface. The resulting PEDOT:PSS film was baked at 150°C for 10 min (~40 nm). The PEDOT:PSS coated substrate was transferred in a glove box with oxygen and humidity <10 ppm. Then, hole transport polymers (compounds 4, 7, 10, 14, 18, 22, and 26) were spin-coated onto the PEDOT:PSS layer. The resulting hole transport layer was baked at 100°C for 10 min (~30 nm). Then, a 15 nm green quantum dot layer (CdSeS / ZnSe / ZnS) and a 40 nm ZnO nanoparticle layer (ethanol solution) were sequentially prepared and baked at 90°C for 10 min. Finally, the device was transferred to a vacuum. Aluminum electrodes (120 nm) were deposited in a vacuum chamber and encapsulated using epoxy resin and a cover glass. QLED devices based on compounds 4, 7, 10, 14, 18, 22, and 26 as hole transport layers were designated D1–D7. Simultaneously, a QLED device based on poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)](TFB, CAS: 220797-16-0) as the hole transport layer was also fabricated as a control, designated D0. Device results are shown in Table 2.

[0160] Table 2: QLED Device Performance

[0161] Devices Hole transport layer Start-up voltage (V) External quantum efficiency (%) Emission peak (nm) D0 TFB 2.2 15.4 533 D1 Compound 4 2.2 19.2 533 D2 Compound 7 2.2 20.3 533 D3 Compound 10 2.2 21.5 533 D4 Compound 14 2.2 22.8 533 D5 Compound 18 2.2 22.4 533 D6 Compound 22 2.2 20.7 533 D7 Compound 26 2.2 20.5 533

[0162] As shown in Table 1, the devices based on P1 to P7 all exhibited lower turn-on voltages and higher device efficiencies under the same emission spectrum. The external quantum efficiencies of the fabricated QLED devices were all higher than those of the control hole-transporting polymer TFB. This indicates that these polymers can be used as hole-transporting materials to fabricate high-efficiency quantum dot light-emitting diodes.

[0163] Application Example 2

[0164] Fabrication of Organic Light Emitting Diode (OLED) Devices

[0165] Take a pre-made indium tin oxide (ITO) glass with a sheet resistance of 15Ω, and ultrasonically clean it sequentially with acetone, detergent, deionized water, and isopropanol, followed by plasma treatment for 10 minutes. First, spin-coat poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT: PSS, CAS: 155090-83-8) (HIL) to a thickness of 40nm, and anneal it at 165℃ in a nitrogen glove box for 20min. For HTL, spin-coat a chlorobenzene solution of compounds 30, 31, 34, and 37 (codes H30, H31, H34, and H37, respectively) onto HIL to a thickness of 35nm, and then anneal it at 160℃ for 30min. For the EML solution, 1 wt% mCP (CAS: 550378-78-4), 1 wt% DIC-TRZ (CAS: 1024598-01-3), and 1 wt% Ir(mppy)3 (CAS: 800394-58-5) were dissolved in chlorobenzene, mixed, and spin-coated onto HTL at 3000 rpm for 30 s to a thickness of 30 nm, followed by annealing at 100 °C for 30 min. Then, TPBi (CAS: 192198-85-9) was continuously deposited via thermal vacuum evaporation. 40nm), LiF ( 1nm) and Al( The 100nm green phosphorescent OLED device has the following structure: ITO / PEDOT:PSS / H30 (H31, H34, and H37) / mCP:DIC-TRZ:Ir(mppy)3 / TPBi / LiF / Al, with corresponding device designations D8 to D11. Additionally, a green phosphorescent OLED device without a hole transport layer was also fabricated, with the same structure: ITO / PEDOT:PSS / mCP:DIC-TRZ:Ir(mppy)3 / TPBi / LiF / Al. The device results are shown in Table 3.

[0166] Table 3: OLED Device Performance

[0167] Devices HTL <![CDATA[CE Max (cd / A)]]> EQE (%) Emission peak (nm) D8 Compound 30 78.2 23.2 515 D9 Compound 31 76.6 22.6 513 D10 Compound 34 72.8 20.8 516 D11 Compound 37 74.6 21.7 515 D12 none 50.7 15.4 520

[0168] The data for devices D8, D9, D10, D11, and D12 are shown in Table 1. Among them, device D8, based on H30, exhibits the highest efficiency, with a maximum current efficiency (CE) of 78.2 cd / A and a maximum external quantum efficiency (EQE) of 23.2%. It can be observed that devices D8, D9, D10, and D11 all have high device efficiencies, and their maximum current efficiency (CE) and maximum external quantum efficiency (EQE) are significantly higher than those of device D12 without HTL. This indicates that these polymers can be used as hole transport materials to fabricate high-efficiency solution-processed organic light-emitting diodes.

[0169] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A side chain type polymer for use as a hole transporting material, characterized by, A homopolymer or copolymer having the following chemical structure: When the side chain polymer is a homopolymer, x is the number of repeating units, and y=0; when the side chain polymer is a copolymer, x and y are the mole fractions of each unit, 0 In the above chemical structure, Ar1 is an aromatic hydrocarbon group with 6-30 carbon atoms; Ar2 is an aromatic hydrocarbon group with 6-60 carbon atoms or an aromatic heterocyclic group with 3-60 carbon atoms containing at least one heteroatom; Ar3 is an aromatic hydrocarbon group with 6-60 carbon atoms or an aromatic heterocyclic group with 3-60 carbon atoms containing at least one heteroatom; and Ar4 is an alkoxy group with 0-30 carbon atoms containing at least one oxygen atom or a hydrocarbon group with 0-30 carbon atoms.

2. The side-chain type polymer according to claim 1, characterized by Ar1 is one of the following chemical structures or a derivative of the following structure:

3. The side-chain type polymer according to claim 1, characterized by Ar2 or Ar3 is one of the following chemical structures or a derivative of the following structure:

4. The side chain type polymer according to claim 1, characterized by Ar4 is one of the following chemical structures or a derivative of the following structure:

5. The side-chain type polymer according to claim 1, wherein The structure is one of the following structures:

6. A method for synthesizing the side chain type polymer according to any one of claims 1 to 5, characterized by, The method comprises the following steps: Synthesis of conjugated monomer: under inert gas protection, Buchwald-Hartwig aryl amination reaction of amine-containing Ar2 unit with brominated Ar3 unit in a catalyst system, then Buchwald-Hartwig aryl amination reaction with brominated vinyl Ar1 unit in a catalyst system to obtain a monomer with conjugated structure, the general reaction formula is as follows: Polymerization reaction: under inert gas protection, the conjugated monomer is dissolved in an organic solvent, then a catalyst is added, and a free radical polymerization reaction is carried out under heating, and the target product is obtained after the reaction is completed.

7. A method for synthesizing the side chain type polymer according to any one of claims 1 to 5, characterized by, The method comprises the following steps: Synthesis of conjugated monomer: under inert gas protection, Buchwald-Hartwig aryl amination reaction of amine-containing Ar2 unit with brominated Ar3 unit in a catalyst system, then Buchwald-Hartwig aryl amination reaction with brominated vinyl Ar1 unit in a catalyst system to obtain a monomer with conjugated structure, the general reaction formula is as follows: Synthesis of crosslinking monomer: under inert gas protection, substitution reaction of Ar4 or Ar4 iodide with 1-bromobenzocyclobutene in a catalyst system, then nucleophilic substitution reaction with 4-chloromethylstyrene in a catalyst system to obtain a crosslinking monomer with crosslinking groups; Polymerization reaction: under inert gas protection, the conjugated monomer and the crosslinking monomer are dissolved in an organic solvent, then a catalyst is added, and a free radical polymerization reaction is carried out under heating, and the target product is obtained after the reaction is completed.

8. The method of synthesis of claim 7, wherein, The synthesis of the crosslinking monomer is as follows: under inert gas protection, nucleophilic substitution reaction of Ar4 with 1-bromobenzocyclobutene in a catalyst, then nucleophilic substitution reaction with 4-chloromethylstyrene in a catalyst system, the general reaction formula is as follows or The synthesis of the cross-linking monomer is as follows: under the protection of inert gas, iodide of Ar4 is reacted with Grignard reagent synthesized from 1-bromobenzocyclobutene under the catalysis of a catalyst system, and then reacted with Grignard reagent synthesized from 4-chloromethylstyrene under the catalysis of a catalyst system to obtain a monomer with cross-linking groups, and the reaction formula is 9. The method of synthesis according to claim 6 or 7, wherein: The organic solvent is one of toluene, chlorobenzene, dichlorobenzene, etc.; the free radical polymerization catalyst is one of AIBN, ABVN, etc., and the amount of the catalyst is 0.1%-0.3% of the total amount of the monomers; the free radical polymerization temperature is 80-85℃, and the reaction time is 20-25 hours.

10. Use of the side-chain type polymer according to any one of claims 1 to 5 in the production of an organic / polymer electronic device, characterized in that, The side-chain polymer is used to make a hole transport layer of the organic / polymer electronic device; the organic / polymer electronic device includes an organic / polymer photodetector, an organic / polymer solar cell, an organic / polymer thin film transistor, an organic / polymer light-emitting transistor, an organic / polymer phototransistor, and an organic / polymer organic light-emitting electrochemical cell.

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