Receptor unit with skeleton containing thiophene modified benzoxadiazole derivative, side chain alkyl substitution and main chain vinyl bridging, and preparation and application thereof

Abstract

The invention relates to the technical field of organic chemical molecular design and organic photoelectric materials, in particular to an acceptor unit with a skeleton containing thiophene modified benzoxadiazole derivatives, side chain alkyl substitution and main chain vinyl bridging, and preparation and application of the acceptor unit. According to the present invention, the skeleton contains the thiophene-modified benzoxadiazole derivative, the side chain alkyl substituted and main chain vinyl bridged acceptor unit is the strong electron-deficient acceptor unit with high main chain planarity, and further, the n-type polymer is prepared through the improved co-catalysis direct arylation polymerization process based on the acceptor unit, and the commercialization process of organic electrons is greatly promoted. According to the invention, the n-type polymer with a unique electron-structure synergistic effect is used as an organic semiconductor layer, and the prepared organic field effect transistor shows a creative electron mobility.

Description

Technical Field

[0001] The present invention relates to the technical fields of organic chemical molecular design and organic optoelectronic materials, and in particular to an acceptor unit with a thiophene-modified benzoxadiazole derivative in the backbone, an alkyl substitution in the side chain, and a vinyl bridging in the main chain, and its preparation and application. Background Art

[0002] Due to the mechanical property limitations of rigid inorganic semiconductor electronic devices, it has been difficult to meet the diversified requirements of electronic technology for flexibility, light weight, and low power consumption. In the past few decades, semiconductor polymers have attracted extensive attention in the academic and industrial communities due to their broad application prospects in flexible and stretchable, solution-processable optoelectronic devices (such as organic photovoltaic cells, organic thin-film transistors, organic electrochemical transistors, and organic thermoelectric devices). Such materials not only provide key support for cutting-edge fields such as flexible wearable electronics, bio-integrated sensors, and intelligent medical detection, but also demonstrate unique application values in aerospace equipment, new energy conversion systems, and low-power Internet of Things (IoT) devices, and have been listed as a key research and development direction for strategic emerging materials by multiple major scientific and technological powers. Based on the difference in carrier transport types, organic semiconductor materials can be divided into p-type (hole-dominated), n-type (electron-dominated), and bipolar (with both transport characteristics). Compared with unipolar circuits, p-n complementary logic circuits can reduce the dynamic power consumption by two orders of magnitude, the physical layout compression rate exceeds 70%, and they have higher noise tolerance and anti-interference capabilities. However, p-type polymers have achieved a hole mobility (μ h ) breakthrough of 10 cm 2 V -1 s -1 , while the development of n-type polymers lags behind. Their electron mobility (μ e ) is generally lower than 1 cm 2 V -1 s -1 , and the serious imbalance of carrier mobility and the decline of electrical properties induced by water / oxygen in the air have greatly restricted the development of this field.

[0003] The acceptor units of ideal n-type polymers with high carrier mobility need to satisfy properties such as good solubility, relatively deep HOMO / LUMO energy levels, and a highly planar rigid main chain. The above performance indicators are highly correlated with the chemical structure of organic molecules. Designing and synthesizing new acceptor units using molecular engineering strategies is expected to break through the existing performance bottlenecks. In addition, most polymers face problems such as low yield, complex synthesis, and low output, which greatly limit the industrial development of polymer semiconductor materials. Due to the large differences in the chemical environment and electronic structure of different organic molecules, it is necessary to reasonably regulate the polymerization process according to the different molecular reaction activities during the synthesis process. Developing efficient, rapid, and simple polymerization methods can further increase the output of polymer materials and promote their commercial progress in organic electronics.

[0004] In summary, it is necessary to design and synthesize new acceptor units that combine excellent electronic properties and a highly planar structure, which is of crucial significance for preparing n-type polymer semiconductor materials with high electron mobility and excellent air stability. Summary of the Invention

[0005] To solve the above problems, the object of the present invention is to provide an acceptor unit with a backbone containing thiophene-modified benzoxadiazole derivatives, side-chain alkyl substitution, and a main-chain vinyl bridging, and its preparation and application. The acceptor unit with a backbone containing thiophene-modified benzoxadiazole derivatives, side-chain alkyl substitution, and a main-chain vinyl bridging provided by the present invention is a strongly electron-deficient acceptor unit with high main-chain planarity. Further, an n-type polymer (dimer n-type polymer) is prepared based on this acceptor unit by improving the co-catalyzed direct arylation polymerization process, which greatly promotes the commercial process of organic electronics. The n-type polymer with a unique electron-structure synergistic effect in the present invention is used as an organic semiconductor layer, and the prepared organic field-effect transistor exhibits a record electron mobility. The present invention realizes the creation and synthesis of new acceptor units and the large-scale preparation of polymers, promotes the development of n-type organic semiconductor molecules in the optoelectronic field and the flexible electronics field, and is of great significance for promoting the industrial development of organic electronic devices.

[0006] The object of the present invention can be achieved by the following technical solutions:

[0007] The first object of the present invention is to provide an acceptor unit with a backbone containing thiophene-modified benzoxadiazole derivatives, side-chain alkyl substitution, and a main-chain vinyl bridging, and the acceptor unit is selected from one of the following structural formulas:

[0008]

[0009] Among them, x and y independently select integers from 1 to 20.

[0010] The second object of the present invention is to provide a preparation method of a receptor unit with a backbone containing a thiophene-modified benzoxadiazole derivative, an alkyl-substituted side chain, and a vinyl-bridged main chain.

[0011] When the chemical structural formula of the receptor unit is as shown in formula (I), the preparation method includes the following steps:

[0012] (A1) Under a nitrogen atmosphere, mix BN-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0), and toluene, and then carry out a Stille coupling reaction to prepare a first compound with the chemical structural formula as shown in formula (III): BN-T-H;

[0013] (A2) Mix the first compound prepared in step (A1), (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene, and then carry out a palladium-catalyzed coupling reaction to prepare the receptor unit: BBHE-H;

[0014] When the chemical structural formula of the receptor unit is as shown in formula (II), the preparation method includes the following steps:

[0015] (B1) Under a nitrogen atmosphere, mix BO-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0), and toluene, and then carry out a Stille coupling reaction to prepare a second compound with the chemical structural formula as shown in formula (IV): BO-T-H;

[0016] (B2) Under a nitrogen atmosphere, mix the second compound prepared in step (B1), (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene, and then carry out a palladium-catalyzed coupling reaction to prepare the receptor unit: BBOE-H;

[0017]

[0018] Wherein, x and y independently are integers selected from 1 to 20.

[0019] In an embodiment of the present invention, in step (A1), the dosage ratio of BN-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0), and toluene is 7.3 mmol: 4 - 10 mmol: 0.1 - 0.4 mmol: 10 - 50 mL;

[0020] During the Stille coupling reaction, the temperature is 60 - 120 °C and the time is 4 - 24 h.

[0021] In an embodiment of the present invention, in step (A1), after the Stille coupling reaction, extraction, purification, and drying are carried out in sequence to prepare BN-T-H.

[0022] In one embodiment of the present invention, in step (A2), the dosage ratio of BN-T-H, (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene is 1.7 mmol: 0.4 - 1 mmol: 0.1 - 0.2 mmol: 10 - 80 mL;

[0023] During the palladium-catalyzed coupling reaction, the temperature is 60 - 120 °C and the time is 4 - 24 h.

[0024] In one embodiment of the present invention, in step (A2), after the palladium-catalyzed coupling reaction, extraction, purification, and drying are carried out in sequence to prepare the acceptor unit.

[0025] In one embodiment of the present invention, in step (B1), the dosage ratio of BO-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0), and toluene is 4.5 mmol: 3 - 8 mmol: 0.1 - 0.3 mmol: 30 - 50 mL;

[0026] During the Stille coupling reaction, the temperature is 50 - 120 °C and the time is 10 - 24 h.

[0027] In one embodiment of the present invention, in step (B1), after the Stille coupling reaction, extraction, purification, and drying are carried out in sequence to prepare BO-T-H.

[0028] In one embodiment of the present invention, in step (B2), the dosage ratio of BO-T-H, (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene is 2.6 mmol: 1 - 3 mmol: 0.1 - 0.3 mmol: 30 - 50 mL;

[0029] During the palladium-catalyzed coupling reaction, the temperature is 50 - 120 °C and the time is 10 - 24 h.

[0030] In one embodiment of the present invention, in step (B2), after the palladium-catalyzed coupling reaction, extraction, purification, and drying are carried out in sequence to prepare the acceptor unit.

[0031] The third object of the present invention is to provide an application of an acceptor unit with a backbone containing a thiophene-modified benzoxadiazole derivative, side-chain alkyl substitution, and main-chain vinyl bridging in the preparation of an n-type polymer.

[0032] The fourth object of the present invention is to provide a method for preparing an n-type polymer (improved co-catalyzed direct arylation polymerization (DArP) process), which includes the following steps:

[0033] The first receptor unit, the second receptor unit, the palladium source, the ligand, the base and the co-catalyst are mixed and then subjected to polymerization reaction to prepare an n-type polymer;

[0034] Wherein, the first receptor unit is the receptor unit according to claim 1;

[0035] The molar ratio of the first receptor unit, the second receptor unit, the palladium source, the ligand, the base and the co-catalyst is 1:1:0.02-0.06:0.16:2-4:0.5-1.5;

[0036] During the polymerization reaction, the temperature is 80-150°C and the time is 12-24h;

[0037] The palladium source is selected from one or more of tri(tert-butyl)phosphine palladium, bis(dibenzylideneacetone)palladium(0), diphenylphosphinocenepalladium dichloride, tetrakistriphenylphosphine palladium, dichlorobistriphenylphosphine palladium, palladium chloride or palladium acetate;

[0038] The ligand is selected from one or more of tributylphosphine, triphenylphosphine, tri-tert-butylphosphine, dimethyldiphenylphosphine, tri(2-pyridyl)phosphine, dichlorodimethylphosphine, triphenylphosphine or tri(o-methoxyphenyl)phosphine;

[0039] The base is selected from one or more of cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide;

[0040] The promoter is selected from one or more of cuprous iodide, silver iodide, ferric iodide, ferrous iodide, nickel iodide or copper iodide.

[0041] The fifth object of the present invention is to provide an n-type polymer, which is prepared by the above method. The advantages of the above method are that the prepared n-type polymer has high electron mobility and high yield.

[0042] A sixth object of the present invention is to provide an application of an n-type polymer in preparing an organic electronic device.

[0043] In one embodiment of the present invention, in an organic electronic device, an n-type polymer serves as a semiconductor transport layer;

[0044] The organic optoelectronic device is selected from a field effect transistor, an electrochemical transistor, an electroluminescent transistor, a solar cell, an organic variable resistance memory, an organic thermal conduction generator, an organic light emitting diode, a photoconductive device, an optical switch, a sensor, an electronic skin, a modulator or a photodetector;

[0045] Wherein, the structure of the field effect transistor is selected from one of a bottom gate bottom contact type, a top gate top contact type, a top gate bottom contact type or a bottom gate top contact type.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] (1) The present invention proposes a new paradigm of "heterocyclic receptor dimerization". By synergistically integrating heteroatom substitution and receptor dimerization, while regulating the HOMO / LUMO energy levels, the molecular planarity is improved; specifically, by removing the alkyl chains in the side-chain thiophene units, the backbone planarity of the polymer is significantly improved. The dihedral angle measurement results confirm that it reaches the ideal planar configuration of 0°, and exhibits ultra-short π-π stacking distances, achieving a principled breakthrough in the design of n-type polymers.

[0048] (2) Aiming at the complex stannylation process problems involved in the synthesis of tin precursors in Stille coupling polymerization, the present invention prepares acceptor-acceptor (A-A) type copolymers through a C-H direct arylation polymerization (DArP) strategy; by improving the types and dosages of cocatalysts, the number-average molecular weight of the polymer is significantly increased to 32.9 kg / mol, and the yield is as high as 95%. Moreover, acceptor-acceptor type copolymers pN-BBNE-H and pN-BBOE-H can be successfully prepared on a 10-gram scale, providing an efficient reaction path for the synthesis of such polymers.

[0049] (3) The organic field-effect transistor (OTFT) prepared based on pN-BBOE-H exhibits an electron mobility of 11.2 cm 2 V -1 s -1 , setting a new high for the performance of single-polarity n-type polymers; in addition, device stability is a key indicator for the practical application of n-type OTFTs. After being stored in an environment with 40-50% humidity for two months, the electron mobility of pN-BBOE-H only decreases from 11.2 to 10.7 cm 2 V -1 s -1 (retention rate > 95%), showing excellent air stability.

[0050] (4) The present invention provides a new paradigm for the rational design of high-performance n-type polymers, marking a major breakthrough in the development of organic electronic materials. The technical solution of the present invention reasonably develops an efficient polymerization process, and improving the yield of the material also provides theoretical guidance for promoting the rational design and industrial development of high-performance n-type polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 1H NMR spectrum of BN-T-H prepared in Example 1 of the present invention;

[0052] Figure 2 1H NMR spectrum of BBNE-H prepared in Example 1 of the present invention;

[0053] Figure 3 1H NMR spectrum of BO-T-H prepared in Example 2 of the present invention;

[0054] Figure 4 1H NMR spectrum of BBOE-H prepared in Example 2 of the present invention;

[0055] Figure 5 1H NMR spectrum of BO-T-C6 prepared in Comparative Example 1 of the present invention;

[0056] Figure 6 1H NMR spectrum of BBOE-C6 prepared in Comparative Example 1 of the present invention;

[0057] Figure 7 Performance test chart of the organic field-effect transistor prepared in Example 5 of the present invention (prepared based on pN-BBOE-H of Example 4); wherein, (a) is the transfer curve; (b) is the output curve;

[0058] Figure 8 Performance change curve over time of the organic field-effect transistors prepared in Example 5, Example 6, and Comparative Example 1 of the present invention when stored under environmental laboratory conditions;

[0059] Figure 9 Performance test chart of the organic field-effect transistor prepared in Example 6 of the present invention (prepared based on pN-BBNE-H of Example 3) and the organic field-effect transistor prepared in Comparative Example 3 (prepared based on pN-BBOE-C6 of Comparative Example 2); wherein, (a) is the transfer curve of electrons of pN-BBNE-H; (b) is the transfer curve of electrons of pN-BBOE-C6. Detailed Description of the Invention

[0060] The present invention will be described in detail below with reference to the accompanying drawings and specific examples.

[0061] In the following examples, unless otherwise specified, the reagents used are commercially available reagents, and the detection means and methods used are conventional detection means and methods in the art.

[0062] Example 1

[0063] This example provides a preparation method for a receptor unit with a skeleton containing thiophene-modified benzotriazole, side-chain alkyl substitution, and main-chain vinyl bridging, specifically including the following steps (the synthesis route is shown in the following formula):

[0064]

[0065] (A1) Under a nitrogen atmosphere, a mixture of 4,7-dibromo-2-(2-ethylhexyl)-2H-benzo[d][1,2,3]triazole (2.84 g, 7.3 mmol), tributyl(thiophen-2-yl)stannane (3.00 g, 8.0 mmol), tetrakis(triphenylphosphine)palladium(0) (0.15 g, 0.13 mmol) and toluene (30 mL) was added to a 100 mL two-necked round-bottom flask to obtain a mixture; subsequently, the mixture was stirred at 120 °C for 24 hours to carry out the Stille coupling reaction; after the reaction was completed, the reaction solution was cooled to room temperature, toluene was removed, the residue was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 2:1) to obtain a light yellow oil, 4-bromo-7-(4-hexyl-2-thienyl)-2,1,3-benzotriazole: BN-T-H (2.18 g, yield 43%, the 1H NMR spectrum is as shown in Figure 1 shown).

[0066] 1 1H NMR (CDCl3, 400 MHz): δ = 8.06 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 12.0 Hz, 1H), 7.44 (d, J = 12.0 Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 7.16 (t, J = 8.0 Hz, 1H), 4.70 (d, J = 8.0 Hz, 2H), 2.28 (s, 2H), 1.33 - 1.24 (m, 8H), 0.96 - 0.85 (m, 6H) ppm.

[0067] 13 13C NMR (CDCl3, 100 MHz): δ = 144.69, 141.82, 139.60, 129.64, 128.63, 127.80, 126.34, 123.37, 109.09, 60.66, 40.71, 30.76, 28.76, 24.14, 23.23, 14.44, 10.96 ppm. MALDI-TOF MS (Mw = 389.1350): found m / z = 389.1550 [M+].

[0068] (A2) Under a nitrogen atmosphere, a mixture of 4-bromo-7-(4-hexyl-2-thienyl)-2,1,3-benzotriazole (0.66 g, 1.7 mmol) prepared in step (A1), (E)-1,2-bis(tributylstannyl)ethylene (0.49 g, 0.81 mmol), tetrakis(triphenylphosphine)palladium(0) (0.16 g, 0.14 mmol), and toluene (30 mL) was added to a 100 mL dry two-necked round-bottom flask to obtain a mixture; subsequently, the mixture was stirred at 120 °C for 24 hours to carry out the palladium-catalyzed coupling reaction; after the reaction was completed, the reaction solution was cooled to room temperature, and toluene was removed by evaporation. The residue was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 2:1) to obtain an orange solid: BBNE-H (0.22 g, yield 86%, and the nuclear magnetic resonance hydrogen spectrum is as Figure 2 shown).

[0069] 1 HNMR(CDCl 3 , 400 MHz): δ = 8.21 (s, 2H), 8.00 (d, J = 4.0 Hz, 2H), 7.47 (d, J = 12.0 Hz, 2H), 7.31 (d, J = 12.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.03 (t, J = 8.0 Hz, 2H), 4.60 (d, J = 8.0 Hz, 4H), 2.13 (s, 2H), 1.23 - 1.11 (m, 16H), 0.85 - 0.73 (m, 12H) ppm.

[0070] 13 C NMR(CDCl 3 , 100 MHz): δ = 142.94, 142.28, 140.49, 130.16, 128.26, 128.03, 127.27, 126.66, 125.67, 123.90, 122.75, 77.23, 59.46, 40.43, 30.63, 28.52, 24.00, 23.00, 14.04, 10.47 ppm. MALDI-TOF MS (Mw = 650.9480): found m / z = 650.9410 [M+].

[0071] Example 2

[0072] This example provides a preparation method for a receptor unit with a backbone containing thiophene-modified benzoxadiazole, side-chain alkyl substitution, and main-chain vinyl bridging, which specifically includes the following steps (the synthesis route is shown in the following formula):

[0073]

[0074] (B1) Under a nitrogen atmosphere, 4,7-dibromobenzo[c][1,2,5]oxadiazole (1.25 g, 4.50 mmol), tributyl(thiophen-2-yl)stannane (1.87 g, 5.00 mmol), tetrakis(triphenylphosphine)palladium(0) (0.15 g, 0.13 mmol), and toluene (30 mL) were added to a 100 mL two-necked round-bottom flask to obtain a mixture. Subsequently, the mixture was stirred at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then toluene was removed. The residue was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 8:1), to obtain the orange solid 4-bromo-7-(thiophen-2-yl)benzo[c][1,2,5]oxadiazole: BO-T-H (0.88 g, yield 75%, the nuclear magnetic resonance hydrogen spectrum is as Figure 3 shown).

[0075] 1 HNMR(CDCl 3 , 400 MHz): δ = 8.08 (s, 1H), 7.82 (d, J = 12.0 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.18 (d, J = 8.0 Hz, 1H) ppm.

[0076] 13 C NMR(CDCl 3 , 100 MHz): δ = 149.52, 147.55, 145.03, 136.55, 134.33, 130.80, 125.62, 123.64, 122.47, 106.08 ppm. MALDI-TOF MS (Mw = 281.1270): found m / z = 281.1260 [M+].

[0077] (B2) Under a nitrogen atmosphere, 4-bromo-7-(thiophen-2-yl)benzo[c][1,2,5]oxadiazole (0.73 g, 2.60 mmol) prepared in step (B1), (E)-1,2-bis(tributylstannyl)ethylene (0.72 g, 1.18 mmol), tetrakis(triphenylphosphine)palladium(0) (0.16 g, 0.14 mmol) and toluene (30 mL) were added to a 100 mL dry two-necked round-bottom flask to obtain a mixture; subsequently, the mixture was stirred at 120 °C for 24 hours; after the reaction was completed, the reaction solution was cooled to room temperature, and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 1:1) to obtain a red solid BBOE-H (0.58 g, yield 82%, and the proton nuclear magnetic resonance spectrum was as shown in Figure 4 shown).

[0078] 1 H NMR(CDCl 3 , 400 MHz): δ = 8.52 (d, J = 12.0 Hz, 2H), 8.19 (s, 2H), 7.92 (d, J = 8.0 Hz, 2H), 7.87 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 2H).

[0079] 13 C NMR(CDCl 3 , 100 MHz): δ = 151.57, 151.41, 148.49, 140.92, 134.81, 133.80, 133.72, 129.34, 128.97, 127.01, 125.82 ppm; MALDI-TOF MS (Mw = 428.4840): m / z = 428.4790 [M+].

[0080] Comparative Example 1

[0081] This comparative example provides a preparation method for a receptor unit with a backbone containing thiophene-modified benzoxadiazole, thiophene alkyl substitution, side-chain alkyl substitution, and main-chain vinyl bridging. The synthetic route is shown in the following formula, and specifically includes the following steps:

[0082]

[0083] (S1) Under a nitrogen atmosphere, 4,7-dibromobenzo[c][1,2,5]oxadiazole (1.26 g, 4.5 mmol), 3-hexyl-5-tributylstannylthiophene (2.3 g, 5.0 mmol), tetrakis(triphenylphosphine)palladium(0) (0.15 g, 0.13 mmol), and toluene (30 mL) were added to a 100 mL two-necked round-bottom flask to obtain a mixture. Subsequently, the mixture was stirred at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the toluene was removed, the residue was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 8:1), to obtain an orange solid BO-T-H-C6 (0.84 g, yield 72%, the 1H NMR spectrum was as shown in Figure 5 shown).

[0084] 1 1H NMR (CDCl3, 400 MHz): δ = 7.74 (s, 1H), 7.41 (d, J = 12.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, Ar), 6.92 (s, 1H, Ar), 2.57 (t, 2H, J = 12.0 Hz), 1.60 - 1.53 (m, 2H), 1.32 - 1.18 (m, 6H), 0.84 (t, J = 8.0 Hz, 3H) ppm.

[0085] 13 13C NMR (CDCl3, 100 MHz): δ = 150.11, 147.93, 145.66, 136.88, 134.66, 131.24, 125.95, 124.10, 122.85, 106.54, 32.19, 30.96, 30.76, 29.35, 23.09, 14.55 ppm. MALDI-TOF MS (Mw = 365.2890): found m / z = 365.2886 [M+].

[0086] (S2) Under a nitrogen atmosphere, 4-bromo-7-(4-hexylthiophen-2-yl)-2,1,3-benzoxadiazole (0.95 g, 2.6 mmol), (E)-1,2-bis(tributylstannyl)ethylene (0.72 g, 1.18 mmol), tetrakis(triphenylphosphine)palladium(0) (0.16 g, 0.14 mmol) and toluene (30 mL) were added to a 100 mL dry two-necked round-bottom flask to obtain a mixture; subsequently, the mixture was stirred at 120 °C for 24 hours; after the reaction was completed, the reaction solution was cooled to room temperature, and the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (the eluent was a mixture of n-hexane and dichloromethane, and the volume ratio of n-hexane to dichloromethane was 1:1) to obtain a red solid BBOE-C6 (0.60 g, yield 85%, and the 1H NMR spectrum was as shown in Figure 6 shown).

[0087] 1 1H NMR (CDCl3, 400 MHz): δ = 8.20 (s, 2H), 7.98 (s, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.12 (s, 2H), 2.78 (t, J = 8.0 Hz, 4H), 1.81 - 1.71 (m, 4H), 1.49 - 1.36 (m, 12H), 1.01 - 0.97 ppm (t, J = 8.0 Hz, 6H).

[0088] 13 13C NMR (CDCl3, 100 MHz): δ = 148.52, 148.31, 145.41, 137.81, 130.72, 130.59, 126.20, 125.82, 123.94, 122.64, 31.67, 30.60, 30.32, 28.99, 22.52, 13.81 ppm; MALDI-TOF MS (Mw = 596.8080): m / z = 596.8078 [M+].

[0089] Example 3

[0090] This example provides a method for preparing an n-type polymer pN-BBNE-H (improved co-catalyzed direct arylation polymerization (DArP) process), and the synthesis route is as shown in the following formula. Specifically, it includes the following steps:

[0091]

[0092] Under an argon atmosphere, 0.2 mmol of the acceptor monomer prepared in Example 1, 0.2 mmol of 5,11-dibromo-2,8-bis(2-decyltetradecyl)thieno[3',2':5,6]benzo[1,2,3,4-lmn]thieno[2,3-f][3,8]phenanthroline-1,3,7,9(2H,8H)-tetrone (NDTI-Br), the fourth-generation tris(tert-butyl)phosphine palladium complex (Pd-P(t-Bu) 3 -G 4 , with a dosage of 0.016 mol), tris(o-methoxyphenyl)phosphine (P(o-MeOPh) 3 , with a dosage of 0.064 mol), cesium carbonate (Cs 2 CO 3 , 0.6 mmol), pivalic acid (PivOH, 0.2 mmol) were dissolved in degassed toluene (1 mL) and added to a Schlenk tube. The reaction mixture was stirred at room temperature for 5 minutes, then heated to 120 °C and stirred at a speed of 500 revolutions per minute for 24 hours. After cooling to room temperature, the mixture was poured into cold methanol (100 mL) for precipitation. Subsequently, the crude polymer was collected by filtration and subjected to Soxhlet extraction with methanol, acetone, n-hexane, and chloroform in sequence for purification. The chloroform extract was concentrated, and after removing most of the solvent, it was poured into methanol for precipitation. The solid was collected by filtration and dried under vacuum to obtain the n-type polymer: pN-BBNE-H. In pN-BBNE-H, n is from 3 to 10,000.

[0093] Example 4

[0094] This example provides a method for preparing an n-type polymer pN-BBNE-H (improved co-catalyzed direct arylation polymerization (DArP) process). The synthesis route is shown in the following formula and specifically includes the following steps:

[0095]

[0096] Under an argon atmosphere, 0.2 mmol of the acceptor monomer prepared in Example 1, 0.2 mmol of 5,11-dibromo-2,8-bis(2-decyltetradecyl)thieno[3',2':5,6]benzo[1,2,3,4-lmn]thieno[2,3-f][3,8]phenanthroline-1,3,7,9(2H,8H)-tetrone (NDTI-Br), the fourth-generation tris(tert-butyl)phosphine palladium complex (Pd-P(t-Bu) 3 -G 4 , with a dosage of 0.016 mol), tris(o-methoxyphenyl)phosphine (P(o-MeOPh) 3 , with a dosage of 0.064 mol), cesium carbonate (Cs 2 CO3 , 0.6 mmol), pivalic acid (PivOH, 0.2 mmol) were dissolved in degassed toluene (1 mL) and added to a Schlenk tube. The reaction mixture was stirred at room temperature for 5 minutes and then heated to 120 °C and stirred at 500 revolutions per minute for 24 hours. After cooling to room temperature, the mixture was poured into cold methanol (100 mL) for precipitation. Subsequently, the crude polymer was collected by filtration and purified by Soxhlet extraction successively with methanol, acetone, n - hexane and chloroform. The chloroform extract was concentrated, and after removing most of the solvent, it was poured into methanol for precipitation again. The solid was collected by filtration and dried under vacuum to obtain an n - type polymer: pN - BBOE - H, where in pN - BBOE - H, n is from 3 to 10,000.

[0097] Comparative Example 2

[0098] This example provides a preparation method of an n - type polymer pN - BBNE - H (improved co - catalytic direct arylation polymerization (DArP) process), and the synthetic route is shown as follows. Specifically, it includes the following steps:

[0099]

[0100] Under an argon atmosphere, 0.2 mmol of the acceptor monomer prepared in Comparative Example 1, 0.2 mmol of 5,11 - dibromo - 2,8 - bis(2 - decyltetradecyl)thieno[3',2':5,6]benzothieno[1,2,3,4 - lmn]thieno[2,3 - f][3,8]phenanthroline - 1,3,7,9(2H,8H) - tetrone (NDTI - Br), the fourth - generation tris(tert - butyl)phosphine palladium complex (Pd - P(t - Bu) 3 -G 4 , with a dosage of 0.016 mol), tris(ortho - methoxyphenyl)phosphine (P(o - MeOPh) 3 , with a dosage of 0.064 mol), cesium carbonate (Cs 2 CO 3 , 0.6 mmol), pivalic acid (PivOH, 0.2 mmol) were dissolved in degassed toluene (1 mL) and added to a Schlenk tube. The reaction mixture was stirred at room temperature for 5 minutes and then heated to 120 °C and stirred at 500 revolutions per minute for 24 hours. After cooling to room temperature, the mixture was poured into cold methanol (100 mL) for precipitation. Subsequently, the crude polymer was collected by filtration and purified by Soxhlet extraction successively with methanol, acetone, n - hexane and chloroform. The chloroform extract was concentrated, and after removing most of the solvent, it was poured into methanol for precipitation again. The solid was collected by filtration and dried under vacuum to obtain an n - type polymer: pN - BBOE - C6, where in pN - BBOE - C6, n is from 3 to 10,000.

[0101] Example 5

[0102] This example provides a method for preparing an organic field-effect transistor, which is as follows:

[0103] The structure of the organic field-effect transistor is a top-gate / bottom-contact structure, and the pN-BBOE-H prepared in Example 4 is used as the semiconductor transport layer;

[0104] (S1) Source and drain electrodes (40-nm gold film) are prepared on a glass substrate (2×2 cm 2 ) by a standard thermal evaporation process, and then the patterned substrate is ultrasonically cleaned with acetone and isopropyl alcohol for 10 minutes each to obtain a pretreated glass substrate;

[0105] (S2) The pretreated glass substrate is transferred to a nitrogen glove box (O 2 and H 2 O concentration < 0.1 ppm) for functional layer deposition; the semiconductor transport layer is prepared by spin-coating with a chlorobenzene solution (5 mg mL -1 ), annealed at 240 °C for 10 minutes and then naturally cooled; the dielectric layer is spin-coated with a PMMA solution (weight-average molecular weight 996 KDa, 80 mg mL -1 PMMA dissolved in n-butyl acetate anhydride) to form a film (thickness 600 nm), and treated by annealing at 90 °C for 30 minutes; finally, an 80-nm silver film is thermally evaporated under high vacuum conditions (<10 -5 Torr) as the gate electrode to complete the preparation of the organic field-effect transistor (the performance test diagrams are as shown in Figure 7 and Figure 8 ).

[0106] Performance characterization is completed using a Keithley S4200SCS semiconductor parameter test system in a nitrogen glove box. According to the following formula, the saturation field-effect mobility (μ) is calculated by the average slope of the |I SD | 1 / 2 vs V g curve of the gate voltage V g :

[0107] I SD =(W / 2L)C i μ(V g -V th ) 2

[0108] where I SD is the drain current in the saturation region, W (4200 μm) and L (50 μm) are the width and length of the semiconductor channel respectively, and C iCi is the capacitance per unit area of the PMMA dielectric layer (Ci = 3.50 nF cm-2 when the thickness is 900 nm), V g and V th are the gate voltage and the threshold voltage, respectively.

[0109] Table 2 Summary of the performance of the organic field-effect transistors prepared in this example

[0110] Organic molecule type <![CDATA[Electron mobility (cm 2 V -1 s -1 )]]> Threshold voltage (V) On / off ratio pN-BBOE-H 11.2 9±5 <![CDATA[10 7 ~10 8 >

[0111] Example 6

[0112] This example provides a method for preparing an organic field-effect transistor, which is as follows:

[0113] The structure of the organic field-effect transistor is a top-gate / bottom-contact structure, and pN-BBNE-H prepared in Example 3 is used as the semiconductor transport layer;

[0114] (S1) Source and drain electrodes (40-nm gold film) are prepared on a glass substrate (2×2 cm 2 ) by a standard thermal evaporation process. Subsequently, the patterned substrate is ultrasonically cleaned with acetone and isopropyl alcohol for 10 minutes each to obtain a pretreated glass substrate;

[0115] (S2) The pretreated glass substrate is transferred to a nitrogen glove box (O 2 and H 2 O concentration < 0.1 ppm) for functional layer deposition; the semiconductor transport layer is prepared by spin-coating with a chlorobenzene solution (5 mg mL -1 ), annealed at 240 °C for 10 minutes and then naturally cooled; the dielectric layer is spin-coated with a PMMA solution (weight-average molecular weight 996 KDa, 80 mg mL -1 PMMA dissolved in n-butyl acetate anhydride) to form a film (thickness 600 nm), and treated by annealing at 90 °C for 30 minutes; finally, an 80-nm silver film is thermally evaporated under high vacuum conditions (<10 -5 Torr) as the gate electrode to complete the preparation of the organic field-effect transistor (the performance test diagrams are as shown in Figure 8 and Figure 9 ).

[0116] Performance characterization is completed using a Keithley S4200SCS semiconductor parameter test system in a nitrogen glove box. According to the following formula, the saturation field-effect mobility (μ) is calculated by the average slope of the |I SD | 1 / 2 vs V g curve for the gate voltage V g :

[0117] I SD = (W / 2L)Ci μ(V g -V th ) 2

[0118] where I SD is the drain current in the saturation region, W (4200 μm) and L (50 μm) are the width and length of the semiconductor channel respectively, C i is the capacitance per unit area of the PMMA dielectric layer (Ci = 3.50 nF cm-2 when the thickness is 900 nm), V g and V th are the gate voltage and threshold voltage respectively.

[0119] Table 1 Summary of the performance of the organic field-effect transistors prepared in this example

[0120] Organic molecule type <![CDATA[Electron mobility (cm 2 V -1 s -1 )]]> Threshold voltage (V) On / off ratio pN-BBOE-H 2.86 19±6 <![CDATA[10 5 ~10 6 >

[0121] Comparative Example 3

[0122] This comparative example provides a method for preparing an organic field-effect transistor, which is as follows:

[0123] The structure of the organic field-effect transistor is a top-gate / bottom-contact structure, and pN-BBOE-C6 prepared in Comparative Example 2 is used as the semiconductor transport layer;

[0124] (S1) Source and drain electrodes (40-nm gold film) are prepared on a glass substrate (2 × 2 cm 2 ) by a standard thermal evaporation process, and then the patterned substrate is ultrasonically cleaned with acetone and isopropyl alcohol for 10 minutes each to obtain a pretreated glass substrate;

[0125] (S2) The pretreated glass substrate is transferred to a nitrogen glove box (O 2 and H 2 O concentration < 0.1 ppm) for functional layer deposition; the semiconductor transport layer is prepared by spin-coating with a chlorobenzene solution (5 mg mL -1 ), annealed at 240 °C for 10 minutes and then naturally cooled; the dielectric layer is spin-coated with a PMMA solution (weight-average molecular weight 996 KDa, 80 mg mL -1 PMMA dissolved in n-butyl acetate anhydride) to form a film (thickness 600 nm), and treated by annealing at 90 °C for 30 minutes; finally, an 80-nm silver film is thermally evaporated under high vacuum conditions (< 10 -5 Torr) as the gate electrode to complete the preparation of the organic field-effect transistor (the performance test diagrams are as shown in Figure 8 and Figure 9 ).

[0126] Performance characterization was completed using a Keithley S4200SCS semiconductor parameter test system in a nitrogen glove box. According to the following formula, the saturation field-effect mobility (μ) was calculated by the average slope of the |I SD | 1 / 2 vs V g curve for the gate voltage V g :

[0127] I SD =(W / 2L)C i μ(V g -V th ) 2

[0128] where I SD is the drain current in the saturation region, W (4200 μm) and L (50 μm) are the width and length of the semiconductor channel respectively, C i is the capacitance per unit area of the PMMA dielectric layer (Ci = 3.50 nF cm-2 when the thickness is 900 nm), V g and V th are the gate voltage and threshold voltage respectively.

[0129] Table 3 Performance summary table of the organic field-effect transistors prepared in this comparative example

[0130] Organic molecule type <![CDATA[Electron mobility (cm 2 V -1 s -1 )]]> Threshold voltage (V) On / off ratio pN-BBOE-C6 0.73 5±3 <![CDATA[10 3 ~10 4 >

[0131] pN-BBOE-H exhibits a unique electron-structure synergistic effect: the oxadiazole-containing acceptor unit exhibits a deeper LUMO energy level, which stems from the stronger electronegativity of the oxadiazole group compared to triazole and thiadiazole. The dihedral angle of the vinyl-bridged BBOE is sharply reduced to 0°, and the introduction of vinyl effectively alleviates the steric hindrance between the benzene ring-expanded acceptor units, significantly enhancing the planarity of the main chain. By removing the alkyl chains of the flanking thiophene units, the π-π stacking distance is shortened to which can effectively promote the interchain charge hopping transport of pN-BBOE-H. The polymer based on pN-BBOE-H sets a current record for the performance of single-polar n-type polymers.

[0132] The above embodiments are only specific cases, but within the following condition ranges, the acceptor unit with the chemical structure shown in formula (I) can be prepared by the method of the present invention, and only the product yield has a slight difference;

[0133] The specific condition ranges are as follows:

[0134] 1) In step (A1), the dosage ratio of BN-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0) and toluene is 7.3 mmol: 4 - 10 mmol: 0.1 - 0.4 mmol: 10 - 50 mL;

[0135] During the Stille coupling reaction, the temperature is 60 - 120 °C and the time is 4 - 24 h.

[0136] 2) In step (A2), the dosage ratio of the first compound, (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene is 1.7 mmol : 0.4 - 1 mmol : 0.1 - 0.2 mmol : 10 - 80 mL;

[0137] During the palladium-catalyzed coupling reaction, the temperature is 60 - 120 °C and the time is 4 - 24 h.

[0138] Within the following condition ranges, the acceptor unit with the chemical structure shown in formula (II) can be prepared by the method of the present invention, and only the product yields are slightly different;

[0139] 1) In step (B1), the dosage ratio of BO-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0), and toluene is 4.5 mmol : 3 - 8 mmol : 0.1 - 0.3 mmol : 30 - 50 mL;

[0140] During the Stille coupling reaction, the temperature is 50 - 120 °C and the time is 10 - 24 h.

[0141] 2) In step (B2), the dosage ratio of the second compound, (E)-1,2-bis(tributylstannyl)ethylene, tetrakis(triphenylphosphine)palladium(0), and toluene is 2.6 mmol : 1 - 3 mmol : 0.1 - 0.3 mmol : 30 - 50 mL;

[0142] During the palladium-catalyzed coupling reaction, the temperature is 50 - 120 °C and the time is 10 - 24 h.

[0143] Within the following condition ranges, the n-type polymer of the present invention can be prepared by the method of the present invention, and only the product yields are slightly different;

[0144] The molar ratio of the first acceptor unit, the second acceptor unit, the palladium source, the ligand, the base, and the cocatalyst is 1 : 1 : 0.02 - 0.06 : 0.16 : 2 - 4 : 0.5 - 1.5;

[0145] During the polymerization reaction, the temperature is 80 - 150 °C and the time is 12 - 24 h;

[0146] The palladium source is selected from one or more of palladium(III) tert-butylphosphine, bis(dibenzylideneacetone)palladium(0), dichlorobis(η5-cyclopentadienyl)palladium(II) diphenylphosphine, tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, palladium(II) chloride, or palladium(II) acetate;

[0147] The ligand is selected from one or more of tributylphosphine, triphenylphosphine, tri-tert-butylphosphine, dimethyldiphenylphosphine, tri(2-pyridyl)phosphine, dichlorodimethylphosphine, triphenylphosphine or tri(o-methoxyphenyl)phosphine;

[0148] The base is selected from one or more of cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide;

[0149] The promoter is selected from one or more of cuprous iodide, silver iodide, ferric iodide, ferrous iodide, nickel iodide or copper iodide.

[0150] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. The framework contains a thiophene-modified benzoxadiazole derivative, a side chain alkyl substitution, and a main chain vinyl bridged receptor unit, characterized in that: The receptor unit is selected from one of the following structural formulas: wherein x and y are independently selected from integers ranging from 1 to 20.

2. A method for preparing an acceptor unit having a thiophene-modified benzoxadiazole derivative as claimed in claim 1, wherein the acceptor unit has a side chain alkyl substitution and a main chain vinyl bridge. When the chemical structural formula of the receptor unit is as shown in formula (I), the preparation method comprises the following steps: (A1) under a nitrogen atmosphere, mixing BN-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0) and toluene and performing a Stille coupling reaction to prepare a first compound having a chemical structure as shown in formula (III); (A2) mixing the first compound prepared in step (A1), (E)-1,2-bis(tributyltinyl)ethylene, tetrakis(triphenylphosphine)palladium(0) and toluene, and performing a palladium-catalyzed coupling reaction to prepare a receptor unit; When the chemical structural formula of the receptor unit is as shown in formula (II), the preparation method comprises the following steps: (B1) under a nitrogen atmosphere, BO-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0) and toluene are mixed and then subjected to a Stille coupling reaction to prepare a second compound having a chemical structure as shown in formula (IV); (B2) under a nitrogen atmosphere, mixing the second compound prepared in step (B1), (E)-1,2-bis(tributyltinyl)ethylene, tetrakis(triphenylphosphine)palladium(0) and toluene, and performing a palladium-catalyzed coupling reaction to prepare a receptor unit; wherein x and y are independently selected from integers ranging from 1 to 20.

3. The method for preparing the receptor unit having a thiophene-modified benzooxadiazole derivative as the skeleton, alkyl substitution on the side chain and vinyl bridging on the main chain according to claim 2, characterized in that: In step (A1), the amount ratio of BN-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0) and toluene is 7.3 mmol:4-10 mmol:0.1-0.4 mmol:10-50 mL; During the Stille coupling reaction, the temperature is 60 to 120°C and the time is 4 to 24 hours.

4. The method for preparing the receptor unit having a skeleton containing a thiophene-modified benzooxadiazole derivative, a side chain alkyl substitution, and a main chain vinyl bridge according to claim 2, characterized in that: In step (A2), the first compound, (E)-1,2-bis(tributyltinyl)ethylene, tetrakis(triphenylphosphine)palladium(0) and toluene are used in a ratio of 1.7 mmol: 0.4-1 mmol: 0.1-0.2 mmol: 10-80 mL; During the palladium-catalyzed coupling reaction, the temperature is 60 to 120° C. and the time is 4 to 24 hours.

5. The method for preparing the receptor unit having a skeleton containing a thiophene-modified benzooxadiazole derivative, a side chain alkyl substitution, and a main chain vinyl bridge according to claim 2, characterized in that: In step (B1), the ratio of BO-Br, tributyl(thiophen-2-yl)stannane, tetrakis(triphenylphosphine)palladium(0) and toluene is 4.5mmol:3-8mmol:0.1-0.3mmol:30-50mL; During the Stille coupling reaction, the temperature is 50-120°C and the time is 10-24 hours.

6. The method for preparing the receptor unit having a thiophene-modified benzooxadiazole derivative as the skeleton, alkyl substitution on the side chain and vinyl bridging on the main chain according to claim 2, characterized in that: In step (B2), the second compound, (E)-1,2-bis(tributyltinyl)ethylene, tetrakis(triphenylphosphine)palladium(0) and toluene are used in a ratio of 2.6 mmol: 1-3 mmol: 0.1-0.3 mmol: 30-50 mL; During the palladium-catalyzed coupling reaction, the temperature is 50 to 120° C. and the time is 10 to 24 hours.

7. Use of the receptor unit with a skeleton containing a thiophene-modified benzoxadiazole derivative, a side chain alkyl substitution, and a main chain vinyl bridge as claimed in claim 1 in the preparation of an n-type polymer.

8. A method for preparing an n-type polymer, characterized in that: The following steps are involved: The first receptor unit, the second receptor unit, the palladium source, the ligand, the base and the co-catalyst are mixed and then subjected to polymerization reaction to prepare an n-type polymer; Wherein, the first receptor unit is the receptor unit according to claim 1; The molar ratio of the first receptor unit, the second receptor unit, the palladium source, the ligand, the base and the co-catalyst is 1:1:0.02-0.06:0.16:2-4:0.5-1.5; During the polymerization reaction, the temperature is 80-150°C and the time is 12-24h; The palladium source is selected from one or more of tri(tert-butyl)phosphine palladium, bis(dibenzylideneacetone)palladium(0), diphenylphosphinocenepalladium dichloride, tetrakistriphenylphosphine palladium, dichlorobistriphenylphosphine palladium, palladium chloride or palladium acetate; The ligand is selected from one or more of tributylphosphine, triphenylphosphine, tri-tert-butylphosphine, dimethyldiphenylphosphine, tri(2-pyridyl)phosphine, dichlorodimethylphosphine, triphenylphosphine or tri(o-methoxyphenyl)phosphine; The base is selected from one or more of cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide or potassium hydroxide; The promoter is selected from one or more of cuprous iodide, silver iodide, ferric iodide, ferrous iodide, nickel iodide or copper iodide.

9. An n-type polymer, characterized in that The n-type polymer is prepared by the method according to claim 8.

10. Use of the n-type polymer according to claim 9 in preparing an organic electronic device.

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