Tri-acceptor polymer based on diisoindigo as well as preparation method and application of tri-acceptor polymer

Abstract

The invention discloses a tri-acceptor polymer based on diisoindigo and a preparation method and application thereof, and belongs to the technical field of organic semiconductor materials. The invention relates to a tri-acceptor polymer based on diisoindigo. In the structure of the tri-acceptor polymer, R1 and R2 are selected from at least one of C5-C80 straight-chain or branched-chain alkyl groups; x, Y and Z in the structure are selected from fluorine or hydrogen; and the polymerization degree n of the tri-acceptor polymer is 5-200. The tri-acceptor polymer is prepared through a Stille coupling reaction, an aldol condensation reaction and a Stille copolymerization reaction in sequence, the synthesis route is simple and easy to implement, the number of synthesis steps is small, and the method is suitable for large-scale synthesis. A field effect transistor taking the tri-acceptor polymer as an organic semiconductor layer has high bipolar transmission property, the highest electron mobility can reach 4.08 cm < 2 > V <-1 > s <-1 >, the highest hole mobility can reach 5.51 cm < 2 > V <-1 > s <-1 >, and the tri-acceptor polymer has a good application prospect in organic field effect devices.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic semiconductor materials, and particularly relates to a tri-acceptor polymer based on double isatin and a preparation method and application thereof. BACKGROUND

[0002] Field effect transistors are the core components of modern silicon-based microelectronics industry. In order to prepare highly integrated circuit elements, it is necessary to further reduce the device size of field effect transistors. However, the preparation of traditional silicon-based field effect transistors not only has high production raw materials and equipment, but also faces physical limits and many technical challenges. In addition, the rigidity of such materials is strong, which has not been able to meet the demand of humans for flexible electronic devices. Therefore, it has great research value and broad commercial prospects to develop new semiconductor materials to improve the device performance in field effect transistors and realize multifunctional applications. Polymer semiconductor materials have shown great potential in the preparation of field effect transistors due to low cost, molecular modifiability, good flexibility and solution processing. Since the first organic field effect transistor (OFETs) was invented in 1986, OFETs based on polymer semiconductors have made brilliant achievements in the past 40 years. Through the innovation of polymer molecular structure and device optimization, the carrier mobility of OFETs has been rapidly improved, and the functional applications in different fields such as chemical and biological sensors, electronic skin, photodetectors, artificial synapses based on OFETs have also been continuously developed.

[0003] The performance parameters of OFETs include field effect mobility (μ), on / off ratio (I on / I off ) and threshold voltage (V TH ). Among them, the larger the values of field effect mobility and on / off ratio are, the higher the performance of OFETs is; and the closer the threshold voltage (V TH ) is to 0, the smaller the voltage required for device opening is. Through the efforts of researchers, OFETs based on donor-acceptor (D-A) type conjugated polymer semiconductors have made great development, and their carrier mobility has also been continuously improved, because the frontier molecular orbital energy level and microstructure can be regulated by changing the structure of donor or acceptor units.

[0004] However, the performance of bipolar polymer semiconductors still cannot meet the application requirements, so it is of great significance to develop high-mobility bipolar polymer materials, especially to develop new tri-acceptor polymer materials, to further improve the polymer electron mobility for preparing high-mobility bipolar polymer semiconductors. SUMMARY

[0005] Therefore, the application discloses a kind of tri-acceptor polymers based on double isoindigo and preparation method and application thereof.

[0006] The application adopts the following technical solutions: A kind of tri-acceptor polymers, the structural formula of the tri-acceptor polymers is as shown in formula (I): , In formula (I), R 1 And R 2 It is one of linear or branched alkyl independently selected from C5-C 80 X, Y and Z are one of fluorine or hydrogen independently selected, and n is 5~200.

[0007] Further, in formula (I), R 1 And R 2 It is one of linear or branched alkyl independently selected from C 10 -C 30 , and n is 10~30.

[0008] Further, in formula (I), R 1 It is 4-decyl tetradecyl, R 2 It is 4-octadecyl docosyl, and n is 11, 13, 18 or 20.

[0009] A kind of preparation method of the above-mentioned tri-acceptor polymers, the method comprises the following steps: S1, under the condition of palladium catalyst, compound shown in formula (II) and compound shown in formula (IV) are carried out Stille coupling reaction, and compound shown in formula (V) is obtained by reaction;Compound shown in formula (III) and compound shown in formula (IV) are carried out Stille coupling reaction, and compound shown in formula (VI) is obtained by reaction; In formula (II) and formula (V), X is hydrogen;In formula (III) and formula (VI), X is fluorine; S2, in the presence of organic acid, compound shown in formula (V) and compound shown in formula (VII) are carried out aldol condensation reaction, or compound shown in formula (VI) and compound shown in formula (VIII) are carried out aldol condensation reaction, and compound shown in formula (IX) is obtained by reaction; In formula (VII), Y is fluorine; In formula (VIII), Y is hydrogen; In formula (IX), X is one of hydrogen or fluorine; S3, reacting the compound of formula (IX) and the compound of formula (X) under catalysis of a palladium reagent and a ligand in an inert atmosphere to obtain the tri-acceptor polymer of formula (I); In formula (X), Z is selected from one of hydrogen or fluorine.

[0010] Further, the palladium catalyst in step S1 is tetrakis(triphenylphosphine)palladium; In the Stille coupling reaction in step S1, the molar ratio of the compound of formula (II) to the compound of formula (IV) is 1:2.2-2.5, the molar ratio of the compound of formula (III) to the compound of formula (IV) is 1:2.2-2.5, and the amount of the palladium catalyst is 1%-10% of the molar amount of the compound of formula (II) or (III).

[0011] Further, the Stille coupling reaction is carried out in an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the Stille coupling reaction is carried out in a solvent, and the solvent is at least one selected from tetrahydrofuran, toluene and chlorobenzene.

[0012] Further, the organic acid in step S2 is at least one selected from p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; In the aldol condensation reaction in step S2, the molar ratio of the compound of formula (V) to the compound of formula (VII) is 1:2.2-2.5, the molar ratio of the compound of formula (VI) to the compound of formula (VIII) is 1:2.2-2.5, and the molar ratio of the compound of formula (V) or (VI) to the organic acid is 1:0.10-0.40; the reaction temperature is 90-120°C, and the reaction time is 6-72 h. The aldol condensation reaction is carried out in an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere. The aldol condensation reaction is carried out in a solvent, and the solvent is at least one selected from tetrahydrofuran, toluene and chlorobenzene.

[0013] Further, in step S3, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the palladium reagent is tris(dibenzylideneacetone)dipalladium; the ligand is tri(o-tolyl)phosphine; the molar ratio of the compound of formula (IX), the compound of formula (X), the palladium reagent and the ligand in the reaction is 1:0.95-1.05:0.01-0.10:0.10-0.50; the reaction temperature is 90-120°C, and the reaction time is 0.01-48 h; and the reaction is carried out in a solvent, and the solvent is at least one selected from toluene and chlorobenzene.

[0014] An organic field effect transistor, an organic semiconductor layer of which is prepared from the above-mentioned tri-acceptor polymer.

[0015] Further, the thickness of the organic semiconductor layer is 10-50 nm.

[0016] The beneficial effects of the present application are as follows: 1. The synthesis raw materials of the tri-acceptor polymer based on bis-isatin blue in the present application can be simply synthesized or purchased in large quantities from commercial channels, which is suitable for large-scale synthesis. 2. The tri-acceptor polymer based on bis-isatin blue in the present application has excellent thermal stability, has a wide ultraviolet-visible light absorption property, and is easy to form a film, and is expected to prepare high-performance OFET devices by a solution method. 3. The OFETs prepared from the organic semiconductor layer of the tri-acceptor polymer based on bis-isatin blue in the present application have excellent electron / hole mobility (µ e / µ h ) (up to µ e / µ h 4.08 / 5.51 cm 2 V -1 s -1 ), and have a broad application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0018] Figure 1 It is a synthesis route schematic diagram of the tri-acceptor polymer based on bis-isatin blue shown in formula (I) of the present application. Figure 2 It is a synthesis route schematic diagram of the polymers P8F-1, P10F-1, P8F-2 and P10F-2 in embodiments 2, 3, 4 and 5 of the present application. Figure 3 It is a UV-visible absorption spectrum schematic diagram of the chlorobenzene solution of the polymers P8F-1, P10F-1, P8F-2 and P10F-2 in embodiments 2, 3, 4 and 5 of the present application, wherein Absorbance (a.u.) represents the normalized absorption intensity; wavelength (nm) represents the wavelength (nanometer); Figure 4UV-Vis absorption spectra of the polymer P8F-1, P10F-1, P8F-2 and P10F-2 films described in Examples 2, 3, 4 and 5 of the present application, wherein Absorbance (a.u.) represents normalized absorbance intensity; wavelength (nm) represents wavelength (nanometer); Figure 5 Thermogravimetric analysis curve of the polymer P8F-1, P10F-1, P8F-2 and P10F-2 described in Examples 2, 3, 4 and 5 of the present application, wherein Weight (wt%) represents mass percentage; Temperature (℃) represents temperature (degree Celsius); Figure 6 Output transfer characteristic curve and output characteristic curve of the OFETs based on P8F-1 of the representative polymer of the present application; Figure 7 Output transfer characteristic curve and output characteristic curve of the OFETs based on P10F-1 of the representative polymer of the present application; Figure 8 Output transfer characteristic curve and output characteristic curve of the OFETs based on P8F-2 of the representative polymer of the present application; Figure 9 Output transfer characteristic curve and output characteristic curve of the OFETs based on P10F-2 of the representative polymer of the present application; Figure 10 Structure of the bis-isatin-based tri-acceptor polymer represented by Formula (I) of the present application. DETAILED DESCRIPTION

[0019] In order to better understand the technical solutions of the present application, the embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0020] In order to make the purpose, technical solutions and advantages of the present application more clear, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application. The reagents not described in detail in the present application are conventional reagents, and can be obtained from commercial channels; the methods not described in detail are conventional experimental methods, and can be known from the prior art.

[0021] It should be clear that the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative efforts are within the scope of protection of the present application.

[0022] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0023] Unless otherwise specified, all materials and reagents used in the following examples can be purchased commercially.

[0024] In the examples below, reaction substrates 1 and 4 were synthesized according to references Adv. Mater. 2019, 31, 1805761 and Adv. Mater. 2016, 28, 7213–7219, respectively, and 6-bromo-7-fluoro-1-(4-octadecyltecosane)indoline-2,3-dione was synthesized according to reference J. Am. Chem. Soc. 2014, 136, 2135–2141. All other reaction substrates, solvents, and catalysts used were commercially available.

[0025] Example 1 A tri-receptor polymer, the structural formula of which is shown in formula (I): , In equation (I), R 1 and R 2 Each is selected independently from C5-C 80 It is one of straight-chain or branched alkyl groups, where X, Y and Z are each independently selected from fluorine or hydrogen, and n is 5 to 200.

[0026] Furthermore, in equation (I), R 1 and R 2 Each is selected independently from C 10 -C 30 One of straight-chain or branched alkyl groups, where n is 10 to 30.

[0027] Furthermore, in equation (I), R 1 It is 4-decyltetradecyl, R 2 It is 4-octadecyl dodecyl, where n is 11, 13, 18 or 20.

[0028] A method for preparing the above-mentioned three-receptor polymer, such as Figure 1 As shown, the method includes the following steps: S1. Under palladium catalyst conditions, the compound shown in formula (II) and the compound shown in formula (IV) are subjected to a Stille coupling reaction to obtain the compound shown in formula (V); the compound shown in formula (III) and the compound shown in formula (IV) are subjected to a Stille coupling reaction to obtain the compound shown in formula (VI) after the reaction is completed. X is hydrogen in formula (II) and formula (V); X is fluorine in formula (III) and formula (VI); S2, in the presence of an organic acid, a compound represented by formula (V) is subjected to an aldol condensation reaction with a compound represented by formula (VII), or a compound represented by formula (VI) is subjected to an aldol condensation reaction with a compound represented by formula (VIII), to obtain a compound represented by formula (IX); Y is fluorine in formula (VII); Y is hydrogen in formula (VIII); X is selected from one of hydrogen or fluorine in formula (IX); S3, under a inert atmosphere, a compound represented by formula (IX) is subjected to a reaction with a compound represented by formula (X) under catalysis of a palladium reagent and a ligand, to obtain a tri-acceptor polymer represented by formula (I); the structure of the tri-acceptor polymer is shown as Figure 10

[0029] Z is selected from one of hydrogen or fluorine in formula (X).

[0030] Further, the palladium catalyst in step S1 is tetrakis(triphenylphosphine)palladium; In the Stille coupling reaction in step S1, the feeding molar ratio of the compound represented by formula (II) to the compound represented by formula (IV) is 1:2.2-2.5; the feeding molar ratio of the compound represented by formula (III) to the compound represented by formula (IV) is 1:2.2-2.5; the amount of the palladium catalyst used is 1%-10% of the feeding molar amount of the compound represented by formula (II) or (III); the reaction temperature is 90-120 ℃, and the reaction time is 6-24 h.

[0031] Further, the Stille coupling reaction is carried out in an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the Stille coupling reaction is carried out in a solvent; and the solvent is selected from at least one of tetrahydrofuran, toluene and chlorobenzene.

[0032] Further, the organic acid in step S2 is selected from at least one of p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; In the aldol condensation reaction in step S2, the feeding molar ratio of the compound represented by formula (V) to the compound represented by formula (VII) is 1:2.2-2.5; the feeding molar ratio of the compound represented by formula (VI) to the compound represented by formula (VIII) is 1:2.2-2.5; the feeding molar ratio of the compound represented by formula (V) or (VI) to the organic acid is 1:0.10-0.40; the reaction temperature is 90-120 ℃, and the reaction time is 6-72 h; ​The aldol condensation reaction is carried out in an inert atmosphere, which is a nitrogen atmosphere or an argon atmosphere. The aldol condensation reaction is carried out in a solvent; the solvent is selected from at least one of tetrahydrofuran, toluene and chlorobenzene.

[0033] Further, in step S3: the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the palladium reagent is tris(dibenzylideneacetone)dipalladium; the ligand is tris(o-tolyl)phosphine; the feeding molar ratio of the compound represented by formula (IX), the compound represented by formula (X), the palladium reagent and the ligand in the reaction is 1:0.95-1.05:0.01-0.10:0.10-0.50; the reaction temperature is 90-120 ℃, and the reaction time is 0.01-48 h; the reaction is carried out in a solvent, and the solvent is selected from at least one of toluene and chlorobenzene.

[0034] An organic field effect transistor, wherein the organic semiconductor layer of the organic field effect transistor is prepared from the above-mentioned three-receptor polymer.

[0035] Further, the thickness of the organic semiconductor layer is 10-50 nm.

[0036] Example 2 Synthesis of polymer P8F-1 (polymer P8F-1 is: R 1 is 4-decyltetradecyl, R 2 is 4-octadecyl-docosyl; X = H, Y = F, Z = H), the synthesis route of P8F-1 is as shown in Figure 2

[0037] 1) Synthesis of compound 3 represented by formula (V) In a 100 mL round-bottom flask, compound 1 represented by formula (II) (2.49 g, 4.4 mmol), compound 2 represented by formula (IV) (1.06 g, 2.0 mmol), tris(dibenzylideneacetone)dipalladium (92 mg, 0.1 mmol), tris(o-methylphenyl)phosphine (122 mg, 0.4 mmol) and 45 mL toluene were sequentially added. The reaction system was heated to 120 ℃ under a nitrogen atmosphere and stirred for 24 h. After removing toluene under reduced pressure, extraction was performed with dichloromethane and water, then the organic phase was collected and dried with anhydrous Na2SO4. After spinning the solvent, purification was performed by silica gel column chromatography (eluent: ethyl acetate / petroleum ether = 1:4), and finally yellow solid product (i.e. compound 3 represented by formula (V)) 1.31 g was obtained, with a yield of 56%.

[0038] The structural characterization data of compound 3 represented by formula (V) are as follows: Mass spectrum: HRMS (m / z): [M+H]​+ 1172.77756.

[0039] Hydrogen spectrum: 1 H NMR (400 MHz, CD2Cl2) δ 7.24 (d, J = 9.2 Hz, 4H), 7.07 (s,2H), 3.84 (t, J = 7.5 Hz, 4H), 3.54 (s, 4H), 1.67 (d, J = 7.7 Hz, 4H), 1.24(s, 74H), 0.86 (t, J = 6.7 Hz, 16H).

[0040] Carbon spectrum: 13 C NMR (101 MHz, CDCl3) δ 174.20, 154.87, 152.25, 145.36,142.89, 134.16, 132.48, 132.40, 129.10, 128.24, 128.01, 127.26, 127.22,121.91, 121.80, 120.87, 120.52, 120.49, 116.65, 116.56, 116.38, 116.30,77.34, 77.02, 76.71, 42.49, 37.11, 35.96, 33.56, 31.93, 30.46, 30.13, 29.75,29.72, 29.66, 29.37, 26.67, 26.28, 26.25, 22.69, 14.10.

[0041] 2) Synthesis of compound 5a (compound 5a is shown in the following formula (IX)) Figure 2 compound 5a) Into a 100 mL round bottom flask, compound 3 (0.47 g, 0.4 mmol) of formula (V), compound 4 (0.79 g, 0.96 mmol) of formula (VII), p-toluenesulfonic acid (22 mg, 0.12 mmol) and 30 mL of toluene were sequentially added. The reaction system was heated to 110 °C under nitrogen atmosphere and stirred for 24 h. After removing toluene under reduced pressure, extraction was performed with dichloromethane and water, the organic phase was collected and dried with anhydrous Na2SO4. After spinning to dry the solvent, purification was performed by silica gel column chromatography (eluent: dichloromethane / petroleum ether = 1:6), and finally black solid product (i.e. compound 5a of formula (IX)) 0.67 g, yield 60% was obtained.

[0042] The structural characterization data of compound 5a of formula (IX) are as follows: Mass spectrum: HRMS (m / z): [M+H] + : 2782.86753.

[0043] Hydrogen spectrum: 1 H NMR (400 MHz, CD2Cl2) δ 8.72 (d, J = 11.7 Hz, 4H), 6.99 (s,2H), 6.70–6.55 (m, 2H), 3.77 (s, 8H), 1.35–1.19 (m, 220H), 0.87 (d, J = 7.0Hz, 24H).

[0044] Carbon spectrum: 13 C NMR (101 MHz, CDCl3) δ 166.88, 166.48, 155.28, 155.15,152.89, 152.51, 144.30, 141.83, 133.91, 132.80, 132.52, 132.44, 131.14,128.21, 128.10, 126.44, 125.06, 124.96, 122.75, 122.10, 118.10, 112.91,103.11, 102.88, 102.84, 102.62, 77.32, 77.00, 76.69, 42.79, 37.25, 33.60,31.97, 31.95, 30.80, 30.24, 30.21, 29.82, 29.80, 29.76, 29.74, 29.72, 29.69,29.42, 29.39, 26.77, 26.75, 26.26, 26.06, 22.71, 14.11.

[0045] 3) Synthesis of polymer P8F-1 In a 25 mL round bottom flask, compound 5a (278.4 mg, 0.10 mmol) of formula (IX), compound 6a (62.6 mg, 0.10 mmol) of formula (X), tris(dibenzylideneacetone)dipalladium (3.0 mg, 0.00328 mmol), tri(o-tolyl)phosphine (9.0 mg, 0.0296 mmol) and 5.0 mL chlorobenzene were added successively. After three cycles of freeze-thaw degassing-nitrogen filling, the system was heated to 110 °C and stirred for 48 h. After cooling to room temperature, the mixture was poured into 200 mL of a methanol / 6M hydrochloric acid mixed solution (volume ratio 20:1) and stirred for 2 h to disperse the polymer uniformly. The precipitate was collected by filtration and purified by Soxhlet extraction with methanol, acetone and n-hexane for 12 h each, and finally extracted with o-dichlorobenzene to obtain the target polymer (i.e. the polymer P8F-1 shown in the structure) 266.1 mg, yield: 91%.

[0046] Structural characterization data are as follows: Molecular weight: GPC: M n = 35.4 kDa, PDI = 2.19, n is 13; Elemental analysis: C 182 H 276 F8N6O4S5, calculated: C 74.75, H 9.51, N 2.97; found: C 73.46, H 9.32, N 2.77.

[0047] From the above, it is known that the compound is correct in structure, which is the polymer P8F-1.

[0048] Example 3 Synthesis of polymer P10F-1 (polymer P10F-1 is: formula (I) in which R 1 is 4-decyltetradecyl, R 2 is 4-octadecyl-docosyl; X = H, Y = F, Z = F, and its synthetic route is shown as Figure 2 ).

[0049] 1) Synthesis of compound 5a of formula (IX) Compound 5b is Figure 2 the compound shown as 5b in the present application, and the synthesis of compound 5a is carried out according to Example 2 of the present application.

[0050] 2) Synthesis of polymer P10F-1 In a 25 mL round bottom flask, compound 5a (278.4 mg, 0.10 mmol) of formula (IX), compound 6b (66.2 mg, 0.10 mmol) of formula (X), tris(dibenzylideneacetone)dipalladium (3.0 mg, 0.00328 mmol), tri(o-tolyl)phosphine (9.0 mg, 0.0296 mmol) and 5.0 mL of chlorobenzene were sequentially added. After three cycles of freeze-thaw degassing and nitrogen filling, the system was heated to 110 °C and stirred for 48 h. After cooling to room temperature, the mixture was poured into 200 mL of a methanol / 6M hydrochloric acid mixed solution (volume ratio of 20:1) and stirred for 2 h to uniformly disperse the polymer. The precipitate was collected by filtration and purified by Soxhlet extraction with methanol, acetone and n-hexane as the extraction solvents, each for 12 h, and finally extracted with o-dichlorobenzene to obtain the target polymer (i.e., the polymer P10F-1 shown in the structure) 275.3 mg, yield 93%.

[0051] Structural characterization data are as follows: Molecular weight: GPC: M n = 32.2 kDa, PDI = 2.17, n is 11; Elemental analysis: C 182 H 274 F 10 N6O4S5, calculated: C 73.84, H 9.33, N 2.84; found: C 73.18, H 9.16, N 2.79.

[0052] From the above, it is known that the compound is correct in structure, which is polymer P10F-1.

[0053] Example 4 Synthesis of polymer P8F-2 (polymer P8F-2 is: formula (I) in which R 1 is 4-decyltetradecyl, R 2 is 4-octadecyl-docosyl; X = F, Y = H, Z = H, and its synthetic route is shown in Figure 2 ).

[0054] 1) Synthesis of compound 7 shown in formula (III) In a 250 mL round bottom flask, 6-bromo-5,7-difluoroindoline-2,3-dione (1.0 g, 3.8 mmol), potassium carbonate (2.64 g, 19.0 mmol), 1-iodo-4-decylltetradecane (2.65 g, 5.7 mmol), 60 mL THF and 60 mL N,N-dimethylformamide (DMF) were added successively. The reaction system was warmed to 50 °C under nitrogen atmosphere, and stirred for 12 h. After removing the solvent under reduced pressure, extraction was performed with dichloromethane and water, and the organic phase was collected and dried with anhydrous Na2SO4. Purification was performed by silica gel column chromatography (eluent: dichloromethane / petroleum ether = 1:1), and finally orange-red solid product (i.e. compound 7 shown in formula (III)) 1.82 g, yield 80% was obtained.

[0055] The structural characterization data of compound 7 shown in formula (III) are as follows: Mass spectrum: HRMS (m / z): [M+H] + : 598.30705.

[0056] Hydrogen spectrum: 1 H NMR (300 MHz, CD2Cl2) δ 7.25 (dd, J = 5.8, 1.4 Hz, 1H), 3.84–3.78 (m, 2H), 1.67 (t, J = 6.9 Hz, 2H), 1.26 (s, 38H), 0.91–0.83 (m, 7H).

[0057] Carbon spectrum: 13 C NMR (101 MHz, CD2Cl2) δ 181.52, 181.49, 181.46, 157.46,157.45, 157.31, 154.84, 146.51, 146.48, 144.02, 143.99, 134.08, 134.05,133.98, 133.95, 118.27, 118.23, 118.19, 118.16, 110.38, 110.15, 110.12,109.89, 108.34, 108.30, 108.09, 108.05, 53.91, 53.64, 53.37, 53.10, 52.83,43.07, 43.02, 37.02, 33.44, 31.93, 30.39, 30.06, 29.68, 29.65, 29.35, 26.57,25.72, 25.69, 22.68, 13.86.

[0058] 2) Synthesis of compound 8 shown in formula (VI) In a 100 mL round bottom flask, compound 7 shown in formula (III) (2.65 g, 4.4 mmol), compound 2 shown in formula (IV) (1.06 g, 2.0 mmol), tris(dibenzylideneacetone)dipalladium (92 mg, 0.1 mmol), tri(o-tolyl)phosphine (122 mg, 0.4 mmol) and 45 mL of toluene were added successively. The reaction system was heated to 120 °C under nitrogen atmosphere and stirred for 24 h. After removing toluene under reduced pressure, extraction was performed with dichloromethane and water, and then the organic phase was collected and dried over anhydrous Na2SO4. After spinning the solvent, purification was performed by silica gel column chromatography (eluent: dichloromethane / petroleum ether = 2:1), and finally red solid product (i.e. compound 8 shown in formula (VI)) 1.56 g was obtained with a yield of 63%.

[0059] The structural characterization data of compound 8 shown in formula (VI) are as follows: Mass spectrum: HRMS (m / z): [M+H] + : 1236.71793.

[0060] Hydrogen spectrum: 1 H NMR (300 MHz, CDCl3) δ 7.60 (s, 2H), 7.32 (d, J = 8.7 Hz, 2H),3.89 (t, J = 7.4 Hz, 4H), 1.71 (s, 4H), 1.23 (s, 78H), 0.85 (t, J = 6.5 Hz,12H).

[0061] Carbon spectrum: 13 C NMR (101 MHz, CDCl3) δ 181.04, 157.81, 156.58, 155.41,154.09, 152.78, 145.69, 143.11, 134.31, 134.22, 127.07, 121.22, 121.14,120.95, 120.57, 120.42, 120.27, 117.32, 117.28, 109.29, 109.01, 77.34, 77.02,76.71, 43.21, 37.04, 33.49, 31.92, 30.43, 30.10, 29.71, 29.65, 29.36, 26.64,25.94, 25.92, 22.67, 14.09.

[0062] 3) Synthesis of compound 9 shown in formula (VIII) In a 250 mL round bottom flask, 6-bromo-7-fluoro-l-(4-octadecyl docosyl)indoline-2,3-dione (2.42 g, 3.0 mmol), 20 mL hydrazine hydrate and 30 mL 1,4-dioxane were added successively. The reaction system was heated to 110 °C and stirred for 24 h. After the reaction was completed, the solvent was removed under reduced pressure, extracted with dichloromethane and water, and then the organic phase was collected and dried over anhydrous Na2SO4. After the solvent was rotary evaporated, the product was separated and purified by silica gel column chromatography (eluent: dichloromethane / petroleum ether = 1:1), and finally a yellowish solid product (i.e. compound 9 shown in formula (VIII)) 1.85 g was obtained with a yield of 78%.

[0063] The structural characterization data of compound 9 shown in formula (VIII) are as follows: Mass spectrum: HRMS (m / z): [M+H] + : 790.58787.

[0064] Hydrogen spectrum: 1 H NMR (400 MHz, CDCl3) δ 7.21–7.16 (m, 1H), 6.90 (d, J = 7.8 Hz,1H), 3.81 (t, J = 7.6 Hz, 2H), 3.50 (s, 2H), 1.62 (s, 2H), 1.23 (d, J = 16.6Hz, 71H), 0.90–0.85 (m, 6H).

[0065] Carbon spectrum: 13 C NMR (101 MHz, CDCl3) δ 174.01, 145.14, 142.72, 132.56,132.47, 126.51, 126.47, 126.07, 120.97, 120.94, 109.37, 109.17, 77.33, 77.02,76.70, 42.43, 42.38, 37.11, 35.79, 35.78, 33.54, 31.94, 30.45, 30.11, 29.72,29.67, 29.37, 26.64, 26.22, 26.19, 22.70, 14.11.

[0066] 4) Synthesis of compound 5b shown in formula (IX) (compound 5b is the compound shown in formula 5b in the specification) Figure 2 ) In a 100 mL round-bottom flask, compound 8 of formula (VI) (0.50 g, 0.4 mmol), compound 9 of formula (VIII) (0.76 g, 0.96 mmol), p-toluenesulfonic acid (22 mg, 0.12 mmol) and 30 mL of toluene were sequentially added. The reaction system was heated to 110 °C under a nitrogen atmosphere and stirred for 24 h. After removing toluene under reduced pressure, extraction was performed with dichloromethane and water, the organic phase was collected and dried with anhydrous Na2SO4. After spinning the solvent, purification was performed by silica gel column chromatography (eluent: dichloromethane / petroleum ether = 1:6), and finally black solid product (i.e. compound 5b of formula (IX)) 0.74 g, yield 66% was obtained.

[0067] The structural characterization data of compound 5b of formula (IX) are as follows: Mass spectrum: HRMS (m / z): [M+H] + : 2782.86199.

[0068] Hydrogen spectrum: 1 H NMR (300 MHz, CDCl3) δ 8.89–8.76 (m, 4H), 7.38 (s, 2H), 6.88(dd, J = 8.6, 6.3 Hz, 2H), 3.97–3.72 (m, 8H), 1.77–1.60 (m, 8H), 1.26 (d, J =5.7 Hz, 220H), 0.87 (td, J = 6.6, 4.1 Hz, 24H).

[0069] Carbon spectrum: 13 C NMR (101 MHz, CDCl3) δ 165.68, 165.51, 154.06, 153.70,151.44, 151.25, 143.32, 140.90, 140.19, 131.26, 131.17, 130.50, 127.43,125.73, 124.17, 121.66, 114.15, 113.96, 113.50, 113.35, 76.30, 75.98, 75.67,41.82, 36.25, 32.59, 32.56, 30.95, 30.93, 29.80, 29.21, 28.80, 28.77, 28.74,28.72, 28.67, 28.40, 28.37, 25.74, 25.18, 21.68, 13.09.

[0070] 5) Synthesis of polymer P8F-2 In a 25 mL round bottom flask, compound 5b (278.4 mg, 0.10 mmol) of formula (IX), compound 6a (62.6 mg, 0.10 mmol) of formula (X), tris(dibenzylideneacetone)dipalladium (3.0 mg, 0.00328 mmol), tri(o-tolyl)phosphine (9.0 mg, 0.0296 mmol) and 5.0 mL chlorobenzene were added successively. After three cycles of freeze-thaw degassing-nitrogen filling, the system was heated to 110 °C and stirred for 48 h. After cooling to room temperature, the mixture was poured into 200 mL of a methanol / 6M hydrochloric acid mixed solution (volume ratio 20:1) and stirred for 2 h to disperse the polymer uniformly. The precipitate was collected by filtration and purified by Soxhlet extraction with methanol, acetone and n-hexane for 12 h each, and finally extracted with o-dichlorobenzene to obtain the target polymer (i.e. the polymer P8F-2 shown in the structure) 277.8 mg, yield 95%.

[0071] Structural characterization data are as follows: Molecular weight: GPC: M n = 55.9 kDa, PDI = 2.07, n is 20; Elemental analysis: C 182 H 276 F8N6O4S5, calculated: C 74.75, H 9.51, N 2.97; found: C 74.03, H 9.32, N 2.84.

[0072] From the above, it is known that the compound is correct in structure, which is polymer P8F-2.

[0073] Example 5 Synthesis of polymer P10F-2 (polymer P10F-2 is: formula (I) in which R 1 is 4-decyltetradecyl, R 2 is 4-octadecyl-docosyl; X = F, Y = H, Z = F, and its synthetic route is shown in Figure 2 ).

[0074] 1) Synthesis of compound 5b of formula (IX) The synthesis of compound 5b was carried out according to Example 3 of the present application.

[0075] 2) Synthesis of polymer P10F-2 In a 25 mL round-bottom flask, compound (IX) 5b (278.4 mg, 0.10 mmol), compound (X) 6b (66.2 mg, 0.10 mmol), tris(dibenzylacetone)dipalladium (3.0 mg, 0.00328 mmol), tris(o-methylphenyl)phosphine (9.0 mg, 0.0296 mmol), and 5.0 mL of chlorobenzene were added sequentially. After three cycles of freeze-degassing and nitrogen filling, the system was heated to 110 °C and stirred for 48 h. After cooling to room temperature, the mixture was poured into 200 mL of a methanol / 6M hydrochloric acid mixture (volume ratio 20:1) and stirred for 2 h to ensure uniform polymer dispersion. The precipitate was collected by filtration and purified by Soxhlet extraction. The extraction solvents were methanol, acetone and n-hexane in sequence, each for 12 h. Finally, it was extracted with o-dichlorobenzene to obtain 278.3 mg of the target polymer (i.e., polymer P10F-2 with the structure shown in the figure), with a yield of 94%.

[0076] The structural characterization data are as follows: Molecular weight: GPC: M n = 51.8 kDa, PDI = 2.25, n is 18; Elemental analysis: C 182 H 274 F 10 N6O4S5, calculated values: C 73.84, H 9.33, N 2.84; measured values: C 72.46, H 9.16, N 2.80.

[0077] The above indicates that the compound has the correct structure and is a polymer P10F-2.

[0078] Example 6 Spectroscopic properties of polymers P8F-1, P10F-1, P8F-2 and P10F-2.

[0079] Figure 3 and Figure 4 The UV-Vis absorption spectra of the polymers P8F-1, P10F-1, P8F-2 and P10F-2 chlorobenzene solutions and films prepared in Examples 2, 3, 4 and 5 of this invention are shown.

[0080] Depend on Figure 3 It can be seen that the polymer of the present invention exhibits strong absorption in the ultraviolet-visible region and the near-infrared region, indicating that the polymer molecule of the present invention has strong intramolecular charge transfer.

[0081] Depend on Figure 4 It can be seen that the polymer of the present invention exhibits strong ordered aggregation in the film.

[0082] Example 6, Thermal properties of polymers P8F-1, P10F-1, P8F-2 and P10F-2 Figure 5 are the thermogravimetric curves of polymers P8F-1, P10F-1, P8F-2 and P10F-2 prepared in Examples 2, 3, 4 and 5 of the present application, respectively.

[0083] It can be seen from Figure 5 that the decomposition temperature (5% loss) of polymers P8F-1, P10F-1, P8F-2 and P10F-2 of the present application are all 420 ℃, indicating that the polymers of the present application have good thermal stability.

[0084] Example 7, Preparation and properties of field effect transistors of polymers P8F-1, P10F-1, P8F-2 and P10F-2

[0085] Figure 6 , Figure 7 , Figure 8 and Figure 9 are the schematic diagrams of transfer curves and output curves of field effect transistors prepared from polymers P8F-1, P10F-1, P8F-2 and P10F-2 in Examples 2-5 of the present application. Among them, |I DS 1 / 2 |[A] 1 / 2 represents |current| 1 / 2 [ampere] 1 / 2 ; V G [V] represents gate voltage [volt]; I DS [A] represents current [ampere]; V DS [V] represents source-drain voltage [volt]; from Figures 6-9 it can be seen that the OFETs prepared from the polymers of the present application have excellent bipolar transport performance. The carrier mobility can be calculated from the equation: I DS = (W / 2L)C i μ(V G – V T ) 2 (sat., V DS = V G – V T ) wherein I DS is the drain current, μ is the carrier mobility, V G is the gate voltage, V T is the threshold voltage, W is the channel width (1400 microns), L is the channel length (40 microns), C i is the insulator capacitance. (I DS , sat) 1 / 2 is used to calculate VG Plotting and linear regression, the slope of the regression line can be calculated from the carrier mobility, and the intercept of the regression line with the X axis is V T The device performance of the PFETs prepared in the above examples of the present application is shown in Table 1.

[0086] The on / off ratio can be calculated from the ratio of the maximum and minimum source-drain current. Figure 6 、 Figure 7 、 Figure 8 and Figure 9 The maximum and minimum source-drain current.

[0087] More than 10 OFET devices were made with the polymers P8F-1, P10F-1, P8F-2 and P10F-2 as the semiconducting layer, and these devices showed stable performance. The representative performance parameters are shown in Table 1. Table 1 Performance of field effect transistor devices The electron mobility of P10F-2 reached 4.08 cm 2 V -1 s -1 , and the hole mobility reached 5.51 cm 2 V -1 s -1 .

[0088] The above experimental results show that the tri-acceptor polymer based on bis-isatin shown in formula (I) provided by the present application is an excellent semiconducting material. Figure 10 The structure of the tri-acceptor polymer based on bis-isatin provided by the present application is shown in the figure.

[0089] The present application is not limited to the reported P8F-1, P10F-1, P8F-2 and P10F-2 three polymer materials, and a series of novel tri-acceptor polymers based on bis-isatin can be obtained by changing different substituents R1, R2 and X, Y and Z. The synthesis route given by the present application is simple and easy to operate, and the synthesis steps are less. This has important guiding significance for further research and development of high-performance tri-acceptor polymer semiconducting materials.

[0090] The embodiments of the present application are described in detail above, and the principles and implementation modes of the present application are described by applying specific examples. The above description of the embodiments is only used to help understand the method of the present application and its core idea; at the same time, for those skilled in the art, according to the idea of the present application, the specific implementation mode and application range will be changed; in summary, the content of the specification should not be understood as a limitation of the present application.

Claims

1. A tri-acceptor polymer, characterized in that, The structure of the three-receptor polymer is shown as formula (I): ， In formula (I), R 1 and R 2 are each independently selected from one of a linear or branched alkyl group of C5-C 80 , X, Y and Z are each independently selected from one of fluorine or hydrogen, and n is 5 to 200.

2. The tri-acceptor polymer of claim 1, wherein In formula (I), R 1 and R 2 are each independently selected from one of a linear or branched alkyl group of C 10 -C 30 n is 10 to 30.

3. The tri-acceptor polymer of claim 2, wherein In formula (I), R 1 is 4-decyltetradecyl, R 2 is 4-octadecyl-docosyl, n is 11, 13, 18 or 20.

4. A method for preparing the tri-accepting polymer according to any one of claims 1 to 3, characterized by, The method comprises the following steps: S1, under the condition of a palladium catalyst, performing Stille coupling reaction of a compound shown as formula (II) and a compound shown as formula (IV), to obtain a compound shown as formula (V); performing Stille coupling reaction of a compound shown as formula (III) and a compound shown as formula (IV), to obtain a compound shown as formula (VI) after the reaction is completed; In formula (II) and formula (V), X is hydrogen; in formula (III) and formula (VI), X is fluorine; S2, under the condition of an organic acid, performing aldol condensation reaction of the compound shown as formula (V) and a compound shown as formula (VII), or performing aldol condensation reaction of the compound shown as formula (VI) and a compound shown as formula (VIII), to obtain a compound shown as formula (IX) after the reaction; In formula (VII), Y is fluorine; In formula (VIII), Y is hydrogen; In formula (IX), X is selected from one of hydrogen or fluorine; S3, under the condition of a palladium reagent and a ligand catalyst, performing reaction of the compound shown as formula (IX) and a compound shown as formula (X) in an inert atmosphere, to obtain the three-receptor polymer shown as formula (I); In formula (X), Z is selected from one of hydrogen or fluorine.

5. The preparation method according to claim 4, characterized in that, The palladium catalyst in step S1 is tetrakis(triphenylphosphine)palladium; In the Stille coupling reaction in step S1, the feeding molar ratio of the compound shown as formula (II) to the compound shown as formula (IV) is 1:2.2-2.5; the feeding molar ratio of the compound shown as formula (III) to the compound shown as formula (IV) is 1:2.2-2.5; the amount of the palladium catalyst is 1%-10% of the feeding molar amount of the compound shown as formula (II) or (III); the reaction temperature is 90-120 ℃, and the reaction time is 6-24 h.

6. The production method according to claim 5, wherein The Stille coupling reaction is performed in an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the Stille coupling reaction is performed in a solvent; and the solvent is at least one selected from the group consisting of tetrahydrofuran, toluene and chlorobenzene.

7. The preparation method according to claim 4, characterized in that, The organic acid in step S2 is at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; In the aldol condensation reaction in step S2, the feeding molar ratio of the compound shown as formula (V) to the compound shown as formula (VII) is 1:2.2-2.5; the feeding molar ratio of the compound shown as formula (VI) to the compound shown as formula (VIII) is 1:2.2-2.5; the feeding molar ratio of the compound shown as formula (V) or (VI) to the organic acid is 1:0.10-0.40; the reaction temperature is 90-120 ℃, and the reaction time is 6-72 h; The aldol condensation reaction is performed in an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; The aldol condensation reaction is performed in a solvent; and the solvent is at least one selected from the group consisting of tetrahydrofuran, toluene and chlorobenzene.

8. The preparation method according to claim 4, characterized in that, In step S3, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the palladium reagent is tris(dibenzylideneacetone)dipalladium; the ligand is tri(o-tolyl)phosphine; the molar ratio of the compound of formula (IX), the compound of formula (X), the palladium reagent and the ligand in the reaction is 1:0.95-1.05:0.01-0.10:0.10-0.50; the reaction temperature is 90-120 ℃, and the reaction time is 0.01-48 h; the reaction is carried out in a solvent selected from at least one of toluene and chlorobenzene.

9. An organic field effect transistor, characterized by The organic semiconductor layer of the organic field effect transistor is prepared from the three-receptor polymer according to any one of claims 1-3.

10. The OFET according to claim 9, wherein the organic semiconductor layer is a single layer. The thickness of the organic semiconductor layer is 10-50 nm.

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