Isoquinolinedione polymer and preparation method and application thereof

Abstract

The application discloses an isoquinolinedione polymer and a preparation method and application thereof. 80 The isoquinolinedione polymer is a polymer shown in formula I: in the formula I, R is selected from any one of linear or branched alkyl of C8-C30; Ar is selected from any one of compounds shown in formula (1)-formula (3): in the formula (1)-formula (3), * represents a substitution position; n represents a polymerization degree, and is 10-1000. The polymer is mainly prepared through substitution reaction and condensation reaction. The isoquinolinedione polymer has a wide ultraviolet-visible light absorption spectrum, stable thermal performance, good film forming performance, high hole transport performance, and can be applied to preparation of an organic field effect transistor device; and the preparation method is simple, and the yield is high.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials technology, specifically relating to an isoquinoline dione polymer and its preparation method and application. Background Technology

[0002] Organic field-effect transistors (OFETs) are an important branch of organic electronics, attracting widespread attention from researchers worldwide since their invention. OFETs possess numerous advantages, such as low cost, flexible and tunable electrical properties, and suitability for mass production, leading to their wide application in many fields, including flexible displays, RFID tags, electronic skin, sensors, and integrated circuits. These applications will have a significant impact on people's lives in the near future.

[0003] Organic field-effect transistors (OFETs) are active electronic devices based on different organic semiconductor materials. They regulate the current between the source and drain electrodes by controlling the gate voltage. Their main performance parameters include mobility (μ) and on / off ratio (Ig). on / I off ) and threshold voltage (V T Different polymer semiconductor materials can produce different transport types, including hole transport and electron transport, and thus different mobilities (μ) and on / off ratios (I). on / I off The higher these two values ​​are, the better the carrier transport performance of the corresponding field-effect transistor device. Threshold voltage (V) TH The threshold voltage (TV) is the minimum gate voltage required to turn on a field-effect transistor. The lower the threshold voltage, the better the energy-saving potential of the device.

[0004] Organic semiconductor materials that can be used to fabricate the transport layer of organic field-effect transistors (FETs) can be classified into the following categories: polymers, oligomers, and small organic molecules. Similar to the synthesis methods for small molecules and oligomers, the methods for synthesizing polymer semiconductor materials are simple and easy to implement, with high yields. However, unlike small molecules and oligomers, polymers have larger molecular weights, resulting in better film-forming properties and better molecular stacking. Therefore, they are easier to construct organic field-effect transistor devices with excellent carrier transport performance, thus showing broad application prospects. In recent years, there have been many reports on organic polymer semiconductor materials that can be used in FETs, and related polymers have been extensively studied and applied. However, the performance of current FETs still needs further improvement, and the types of organic semiconductor polymers also need corresponding innovation and expansion. These are crucial for further promoting the development of the organic field-effect transistor field. Summary of the Invention

[0005] The purpose of this invention is to provide an isoquinoline dione polymer, its preparation method, and its applications. The isoquinoline dione polymer of this invention possesses a broad ultraviolet-visible absorption spectrum, stable thermal properties, good film-forming properties, and high hole transport performance, making it suitable for fabricating organic field-effect transistor devices. Furthermore, the preparation method is simple and yields high output.

[0006] This invention provides a polymer of Formula I:

[0007]

[0008] In Formula I, R is selected from C8 to C9. 80 Any one of straight-chain or branched alkyl groups;

[0009] Ar is selected from any of the compounds shown in formulas (1) to (3):

[0010]

[0011] In equations (1)-(3), * indicates a substitution position;

[0012] n represents the degree of polymerization, which ranges from 10 to 1000.

[0013] In Formula I of this invention, n can specifically be 60, 67, 70, 60-70, 50-100, 60-200, 60-500 or 50-800.

[0014] In the polymer shown in Formula I, R can specifically be 2-decyltetradecyl.

[0015] The present invention also provides a method for preparing the polymer shown in Formula I above, characterized by comprising the following steps:

[0016] (1) Under acidic conditions, the compound shown in Formula II is reacted with the compound shown in Formula III to obtain the compound shown in Formula IV.

[0017]

[0018] (2) In an inert atmosphere, the compound shown in Formula IV is reacted with the compound shown in Formula V to obtain the compound shown in Formula VI;

[0019]

[0020] (3) In an inert atmosphere, the compound shown in Formula VI is reacted with the compound shown in Formula VII to obtain the compound shown in Formula VIII;

[0021]

[0022] In equations VII and VIII, the definition of R is the same as that in equation I;

[0023] (4) Under an inert atmosphere and acidic conditions, the compound shown in formula VIII is reacted with the compound shown in formula IX, the compound shown in formula X or the compound shown in formula XI to obtain the compound shown in formula XII.

[0024]

[0025] In equation XII, the definition of R is the same as that in equation I;

[0026] (5) Under an inert atmosphere and under palladium catalyst catalysis, the compound shown in formula XII and the compound shown in formula XIII react to obtain the polymer shown in formula I.

[0027]

[0028] In equation XIII, R 2 Selected from methyl or n-butyl.

[0029] In the above preparation method, in step (1), the molar ratio of the compound shown in Formula II to the compound shown in Formula III can be 1.0:1.2 to 2.0, specifically 1.0:1.4, 1.0:1.5, 1.0:1.2 to 1.5 or 1.0:1.4 to 2.0;

[0030] The reaction temperature can be 70℃~100℃, specifically 90℃, 70℃~90℃, 90℃~100℃ or 80℃~90℃; the reaction time can be 1 hour~3 hours, specifically 2 hours, 1 hour~2 hours, 2 hours~3 hours or 1.5 hours~2.5 hours.

[0031] The reaction solvent is dilute sulfuric acid, and the mass percentage concentration of the dilute sulfuric acid can be 5% to 50%, specifically 7%, 7% to 50%, 5% to 30%, or 5% to 40%.

[0032] In the above preparation method, in step (2), the molar ratio of the compound shown in formula IV to the compound shown in formula V can be 1.0:1.0 to 4.0, specifically 1.0:1, 1.0:1.0 to 2, 1.0:1.0 to 3.0 or 1.0:2.0 to 3.0;

[0033] The reaction temperature can be 90℃~150℃, specifically 120℃, 90℃~120℃, 120℃~150℃ or 100℃~140℃; the reaction time can be 5 hours~10 hours, specifically 5 hours.

[0034] The reaction is carried out in the presence of a solvent, namely toluene.

[0035] In the above preparation method, in step (3), the molar ratio of the compound shown in formula VI to the compound shown in formula VII can be 1.0:1.0 to 2.0, specifically 1.0:1.19;

[0036] The reaction temperature can be 100℃~130℃, specifically 120℃, 100℃~120℃ or 120℃~130℃; the reaction time can be 3 hours~24 hours, specifically 6 hours.

[0037] The reaction is carried out in the presence of a solvent, which is a mixed solvent of toluene and acetic acid in a volume ratio of 1 to 5:1, specifically a mixed solvent of toluene and acetic acid in a volume ratio of 2:1.

[0038] In the above preparation method, in step (4), the molar ratio of the compound shown in formula IX, the compound shown in formula X, or the compound shown in formula XII to the compound shown in formula VIII can be 1.0:2.0 to 5.0, specifically 1.0:2.0 to 3.0, specifically 1:2.1;

[0039] The reaction temperature can be 100℃~150℃, specifically 120℃; the reaction time can be 3 hours~36 hours, specifically 24 hours, 3 hours~24 hours or 24 hours~36 hours.

[0040] The reaction is carried out in the presence of a solvent, which is a mixed solvent of toluene and acetic acid in a volume ratio of 1 to 5:1, specifically a mixed solvent of toluene and acetic acid in a volume ratio of 2:1.

[0041] In the above preparation method, in step (5), the molar ratio of the compound shown in formula XII to the compound shown in formula XIII can be 1.0:1.0;

[0042] The palladium catalyst is selected from tris(dibenzylacetone)palladium and / or tetra(triphenylphosphine)palladium. In a specific embodiment, the catalyst used in the reaction is tris(dibenzylacetone)palladium, and the selected ligand is tris(o-tolyl)phosphine.

[0043] The reaction temperature can be 90℃~130℃, specifically 120℃; the reaction time can be 0.5 hours~36 hours, specifically 1.5 hours.

[0044] The reaction solvent is either chlorobenzene or toluene, and the solvent actually used in the reaction is chlorobenzene.

[0045] In this invention, the inert atmosphere is selected from nitrogen or argon.

[0046] The present invention also provides a compound represented by formula XII:

[0047]

[0048] In Formula XII, R is defined in the same way as R in Formula I; Ar is selected in the same way as the Ar group in Formula I.

[0049] The compound represented by Formula I of this invention is used in the preparation of organic effect transistors.

[0050] The present invention further provides an organic field-effect transistor, wherein the organic semiconductor layer is made of the polymer shown in Formula I of claim 1.

[0051] In the above-mentioned organic field-effect transistor, the organic semiconductor layer is prepared by spin-coating the polymer shown in Formula I followed by annealing;

[0052] The annealing temperature can be 100-200℃; the time can be 5-30 minutes; specifically 20 minutes.

[0053] The present invention has the following advantages:

[0054] 1. This polymer is prepared based on a novel isoquinolinedione, with a high synthesis yield. The raw materials are simple to synthesize and some can be purchased in large quantities from commercial channels, making it suitable for large-scale preparation.

[0055] 2. This novel isoquinoline dione polymer has a broad UV-Vis absorption spectrum, stable thermal properties, and good film-forming properties, and can be used to prepare organic field-effect transistor devices.

[0056] 3. The organic field-effect transistor device using this novel isoquinoline dione polymer as the semiconductor layer exhibits high hole transport performance, with a maximum hole mobility reaching 1.08 cm⁻¹. 2 V -1 s -1 I on / I off 10 3 -10 4 It has great development potential. Attached Figure Description

[0057] Figure 1 This is a synthetic route diagram for the novel isoquinoline dione polymer shown in Formula I of this invention.

[0058] Figure 2 This is a synthetic route diagram of the novel isoquinoline dione polymers described in Examples 1 to 3 of the present invention.

[0059] Figure 3 The images show the UV-Vis absorption spectra of the novel isoquinoline dione polymers described in Examples 1-3 of this invention in their o-dichlorobenzene solutions.

[0060] Figure 4 The images show the UV-Vis absorption spectra of the novel isoquinoline dione polymers described in Examples 1-3 of this invention in the thin film state.

[0061] Figure 5 Thermogravimetric analysis curves and differential scanning calorimetry curves of the novel isoquinoline dione polymers described in Examples 1-3 of this invention are shown.

[0062] Figure 6 The figures are cyclic voltammetry curves of the novel isoquinoline dione polymers described in Examples 1-3 of this invention.

[0063] Figure 7 This is a schematic diagram of the organic field-effect transistor structure constructed in this invention. Al is the gate electrode, CYTOP is the dielectric layer, Au is the source electrode and drain electrode, PET is the substrate, and Polymer is the semiconductor layer.

[0064] Figure 8 The figures show the output transfer characteristic curves and output characteristic curves of the field-effect transistors of the novel isoquinoline dione polymers described in Examples 1-3 of this invention; wherein, |I DS 1 / 2 |[A] 1 / 2 :|current| 1 / 2 [ampere]1 / 2 V G [V]: Gate voltage [volts]; I DS [A]: Current [Ampere]; V DS [V]: Source-drain voltage [volts]; Figure 8 In the figure, (a), (b), (c), and (d) represent the transfer and output curves of hole transport in polymer P1, the transfer and output curves of electron transport in polymer P1, the transfer and output curves of hole transport in polymer P2, and the transfer and output curves of hole transport in polymer P3, respectively. Detailed Implementation

[0065] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0066] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0067] The reactant 4 used in the following examples was synthesized according to the literature Macromolecules, 2019, 52, 8238-8247. All other reaction substrates, solvents and catalysts used were commercially available.

[0068] Example 1: Synthesis of polymer P1 (in Formula I, R = 2-decyltetradecyl, Ar = thiophene[3,2-b]thiophene, degree of polymerization n = 67) (its synthetic route is as follows) Figure 2 (As shown)

[0069] 1) Synthesis of 7-bromo-2-(2-decyltetradecyl)isoquinoline-1,3(2H,4H)-dione

[0070] Weigh out 10.0 g (55.5 mmol) of o-carboxyphenylacetic acid and 13.2 g (78.8 mmol) of potassium bromate, add 60 mL of ultrapure water and stir until homogeneous. After raising the system temperature to 90 °C, add sulfuric acid aqueous solution (50 mL concentrated sulfuric acid + 80 mL water) dropwise to the reaction system. After the addition is complete, react at 90 °C for 2 hours, then cool the reaction system to room temperature (25 °C). Filter the residue, wash it with water several times, recrystallize it with a mixture of ethyl acetate and n-hexane, filter it and set it aside for use. Weigh 5.40 g (20.9 mmol) of the product obtained in the previous step and dissolve it in 100 mL of toluene. Under nitrogen protection, add acetic anhydride (5.2 mL, 55.5 mmol) and heat to 120 °C to carry out the reaction. After 5 hours of reaction, terminate the reaction and cool the reaction to room temperature. Remove toluene by vacuum distillation and wash the obtained solid product with diethyl ether. After drying, weigh a certain amount (4.0 g, 16.6 mmol) and dissolve it in a mixed solvent (20 mL toluene + 10 mL acetic acid). After complete dissolution, add 7 g (19.7 mmol) of 2-decyltetradecyl-1-amine to the system and heat to 120 °C to carry out the reaction. After about 6 hours of reaction, add water to terminate the reaction. Extract with dichloromethane, dry, and then purify by column chromatography to obtain 4.78 g of the target product. Overall yield of the multi-step reaction: 50%.

[0071] The structural characterization data are as follows:

[0072] Mass spectrometry: HRMS (m / z): [M] + :576.3410.

[0073] Hydrogen spectrum: 1 H NMR (300MHz, CDCl3) δ (ppm): δ8.33 (d, J = 2.1Hz, 1H), 7.69 (d, J = 8.2Hz, 1H), 7.16 (d, J = 8.2Hz ,1H),3.98(s,2H),3.91(d,J=7.2Hz,2H),1.83(s,1H),1.24(m,40H),0.88(t,J=6.5Hz,6H).

[0074] Carbon spectrum: 13 C NMR(75MHz, CDCl3)δ(ppm):169.55,163.94,136.40,132.79,131.97,128.71,127.23,121.62,44.40 ,36.38,36.05,31.93,31.57,30.02,29.70,29.66,29.65,29.62,29.37,29.36,26.37,22.70,14.13.

[0075] 2) Synthesis of compound 5a

[0076] Using p-toluenesulfonic acid as a catalyst, thiophene[3,2-b]thiophene-2,5-dicarboxaldehyde (0.20 g, 1.02 mmol) and 7-bromo-2-(2-decyltetradecyl)isoquinoline-1,3(2H,4H)-dione (1.23 g, 2.14 mmol) were dissolved in toluene (20 mL) and acetic acid (10 mL). The mixture was heated to 120 °C and stirred for 24 hours. The mixture was cooled and extracted with dichloromethane, washed three times with deionized water, and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography yielded 1.07 g of a deep red solid, 80% yield.

[0077] The structural characterization data are as follows:

[0078] Mass spectrometry: HRMS (m / z): [M] + :1313.6126.

[0079] Hydrogen spectrum: 1 H NMR (300MHz, CDCl3) δ (ppm): 8.28 (s, 1H), 7.83 (s, 1H), 7.68 (d, J = 8.5Hz, 1H), 7.60 (d, J = 8.5H) z, 1H), 7.57 (s, 1H), 4.05 (d, J = 6.8Hz, 2H), 1.97 (s, 1H), 1.22 (m, 40H), 0.85 (t, J = 6.8Hz, 6H).

[0080] Carbon spectrum: 13 C NMR (75MHz, CDCl3) δ (ppm): 164.08, 162.83, 147.31, 144.56, 136.39, 135.73, 133.37, 132.14, 131.90, 125.76, 123.29,122.47,118.10,44.68,36.39,31.95,31.64,30.11,30.05,29.73,29.69,29.40,26.42,22.71,14.13.

[0081] 3) Synthesis of polymer P1

[0082] In a 25 mL flask, compound 5a (263.0 mg, 0.2 mmol), (3,3'-difluoro-[2,2'-bisthiophene]-5,5'-diyl)bis(trimethyltin) (105.6 mg, 0.2 mmol), tris(dibenzylacetone)dipalladium (9.2 mg, 0.01 mmol), and tris(o-tolyl)phosphine (24.4 mg, 0.08 mmol) were dissolved in 8 mL of chlorobenzene. The mixture was thawed and degassed using a refrigerated pump and purged with argon three times. The mixture was then heated to 120 °C and stirred for 1.5 h. The filtered polymer solid was purified by Soxhlet extraction with methanol, acetone, hexane, dichloromethane, and chloroform. Extraction with 1,2-dichlorobenzene yielded 222 mg of the final polymer, in 82% yield.

[0083] The structural characterization data are as follows:

[0084] Molecular weight: GPC:M n =90.5kDa, PDI=2.48.

[0085] Elemental analysis: C 82 H 110 F2N2O4S4, calculated values: C, 72.74; H, 8.19; N, 2.07; detected values: C, 72.58; H, 8.06; N, 2.13.

[0086] The above indicates that the compound has the correct structure and is a polymer P1.

[0087] Example 2: Synthesis of polymer P2 (in Formula I, R = 2-decyltetradecyl, Ar = 2,2'-bithiophene, degree of polymerization n = 70) (the synthetic route is as follows) Figure 2 (As shown)

[0088] The synthesis of compound 4 was carried out in accordance with Example 1.

[0089] 1) Synthesis of compound 5b

[0090] Using p-toluenesulfonic acid as a catalyst, [2,2'-bithiophene]-5,5'-dicarboxaldehyde (0.30 g, 1.35 mmol) and 7-bromo-2-(2-decyltetradecyl)isoquinoline-1,3(2H,4H)-dione (1.63 g, 2.83 mmol) were dissolved in toluene (20 mL) and acetic acid (10 mL). The mixture was heated to 120 °C and stirred for 24 hours. The mixture was cooled and extracted with dichloromethane, washed three times with deionized water, and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography yielded 1.41 g of a deep red solid, 78% yield.

[0091] The structural characterization data are as follows:

[0092] Mass spectrometry: HRMS (m / z): [M] + :1339.6285.

[0093] Hydrogen spectrum: 1 H NMR (300MHz, CDCl3) δ (ppm): 8.43 (s, 1H), 8.04 (s, 1H), 7.75 (s, 2H), 7.61 (d, J = 4.1Hz, 1H), 7. 56 (d, J = 4.1 Hz, 1H), 4.08 (d, J = 7.2 Hz, 2H), 1.98 (s, 1H), 1.25 (m, 40H), 0.85 (t, J = 5.9 Hz, 6H). Carbon spectrum: 13 C NMR (75MHz, CDCl3) δ (ppm): 164.22, 163.00, 146.89, 141.85, 138.65, 136.33, 135.67, 133.69, 132.10, 125.61, 125.40,123.12,121.97,116.23,44.50,36.32,31.95,31.58,30.11,29.74,29.71,29.39,26.38,22.71,14.13.

[0094] 2) Synthesis of polymer P2

[0095] In a 25 mL flask, compound 5b (268.0 mg, 0.2 mmol), (3,3'-difluoro-[2,2'-bisthiophene]-5,5'-diyl)bis(trimethyltin) (105.6 mg, 0.2 mmol), tris(dibenzylacetone)dipalladium (9.2 mg, 0.01 mmol), and tris(o-tolyl)phosphine (24.4 mg, 0.08 mmol) were dissolved in 8 mL of chlorobenzene. The mixture was thawed and degassed using a refrigerated pump and purged with argon for three cycles. The mixture was then heated to 120 °C and stirred for 1.5 h. The filtered polymer solid was purified by Soxhlet extraction with methanol, acetone, hexane, dichloromethane, and chloroform. Extraction with 1,2-dichlorobenzene yielded 220 mg of the final polymer, in 80% yield.

[0096] The structural characterization data are as follows:

[0097] Molecular weight: GPC:M n =96.9kDa, PDI=1.80.

[0098] Elemental analysis: C 84 H 112 F2N2O4S4, calculated values: C, 73.11; H, 8.18; N, 2.03; detected values: C, 72.96; H, 8.06; N, 2.10.

[0099] The above indicates that the compound has the correct structure and is a polymer P2.

[0100] Example 3: Synthesis of polymer P3 (in Formula I, R = 2-decyltetradecyl, Ar = (trans)-1,2-bis(thiophen-2-yl)ethylene, degree of polymerization n = 60) (the synthetic route is as follows) Figure 2 (As shown)

[0101] The synthesis of compound 4 was carried out in accordance with Example 1.

[0102] 1) Synthesis of compound 5c

[0103] Using p-toluenesulfonic acid as a catalyst, (trans)-5,5'-(ethylene-1,2-diyl)bis(thiophene-2-carboxaldehyde) (0.30 g, 1.21 mmol) and 7-bromo-2-(2-decyltetradecyl)isoquinoline-1,3(2H,4H)-dione (1.46 g, 2.54 mmol) were dissolved in toluene (20 mL) and acetic acid (10 mL). The mixture was heated to 120 °C and stirred for 24 hours. The mixture was cooled and extracted with dichloromethane, washed three times with deionized water, and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography yielded 1.14 g of a deep red solid, 69% yield.

[0104] The structural characterization data are as follows:

[0105] Mass spectrometry: HRMS (m / z): [M] + :1365.6425.

[0106] Hydrogen spectrum: 1 H NMR (300MHz, CDCl3) δ (ppm): 8.39 (s, 1H), 7.97 (s, 1H), 7.71 (s, 2H), 7.54 (d, J = 3.7Hz, 1H), 7.34 (s, 1H), 7.20 (d, J = 3.7Hz, 1H), 4.07 (d, J = 7.1Hz, 2H), 1.98 (s, 1H), 1.21 (m, 40H), 0.85 (t, J = 6.1Hz, 6H). Carbon spectrum: 13 C NMR (75MHz, CDCl3) δ (ppm): 164.16, 163.05, 152.13, 141.79, 138.03, 136.29, 135.80, 133.86, 132.05, 127.40, 125. 57,124.20,123.13,121.80,116.01,44.52,36.32,31.95,31.61,30.10,29.73,29.69,29.39,26.43,22.71,14.14.

[0107] 2) Synthesis of polymer P3

[0108] In a 25 mL orbicular flask, compounds 5C (273.0 mg, 0.2 mmol), (3,3'-difluoro-[2,2'-bisthiophene]-5,5'-diyl)bis(trimethyltin) (105.6 mg, 0.2 mmol), tris(dibenzylacetone)dipalladium (9.2 mg, 0.01 mmol), and tris(o-tolyl)phosphine (24.4 mg, 0.08 mmol) were dissolved in 8 mL of chlorobenzene. The mixture was thawed and degassed using a refrigerated pump and purged with argon for three cycles. The mixture was then heated to 120 °C and stirred for 1.5 h. The filtered polymer solid was purified by Soxhlet extraction with methanol, acetone, hexane, dichloromethane, and chloroform. Extraction with 1,2-dichlorobenzene yielded 211 mg of the final polymer, 75% yield.

[0109] The structural characterization data are as follows:

[0110] Molecular weight: GPC:M n =83.8kDa, PDI=1.83.

[0111] Elemental analysis: C 86 H 114 F2N2O4S4, calculated values: C, 73.46; H, 8.17; N, 1.99; detected values: C, 73.35; H, 8.23; N, 2.08.

[0112] The above indicates that the compound has the correct structure and is a polymer, P3.

[0113] Example 4: Optical absorption properties of polymers P1-P3

[0114] Figure 3 and Figure 4 The images show the UV-Vis absorption spectra of the polymers prepared in Examples 1-3 of this invention in their o-dichlorobenzene solution and thin film states, respectively.

[0115] Figure 3 The absorption curves show that polymers P1 to P3 exhibit broad absorption in the UV-Vis region, with absorption shoulders appearing next to the strongest absorption peak, indicating that the three polymers have good packing properties in solution. Meanwhile... Figure 4 The absorption curves shown indicate that these three polymers have a strong stacking effect in the film.

[0116] Example 5: Thermal properties of polymers P1-P3

[0117] Figure 5These are the thermogravimetric curves and differential scanning calorimetric curves of polymers P1-P3 prepared in Examples 1-3.

[0118] Figure 5 The thermogravimetric curves shown indicate that the decomposition temperatures of the three polymers are all around 370 degrees Celsius. Simultaneously, the corresponding differential scanning calorimetry (DSC) curves show that the three polymers did not exhibit significant endothermic or exothermic behavior during the heating and cooling processes, indicating that these three polymers possess excellent thermal stability.

[0119] Example 6: Electrochemical properties of polymers P1-P3

[0120] Figure 6 These are the cyclic voltammetry curves of the three polymers P1-P3 prepared in Examples 1-3.

[0121] Figure 6 Cyclic voltammetry results show that the initial oxidation potentials of polymers P1, P2, and P3 are 1.08, 1.13, and 1.25 V, respectively. Based on these results, the calculated HOMO energy levels are -5.48, -5.53, and -5.65 eV, while their initial reduction potentials are -0.82, -0.84, and -0.80 V, respectively. Their LUMO energy levels can be estimated to be -3.58, -3.56, and -3.60 eV, respectively.

[0122] Example 7: Fabrication and performance of field-effect transistors of polymers P1-P3.

[0123] Figure 7 The diagram shows a schematic of the fabricated polymer field-effect transistor (PFMT) device structure. As shown, polyethylene terephthalate (PET) is used as the substrate, and gold is used as the source and drain electrodes. The semiconductor layer is prepared by spin-coating a polymer solution and then annealed at 140°C for 20 minutes. Similarly, a perfluorinated (1-butenyl vinyl ether) polymer is spin-coated onto the surface of the polymer layer to obtain a dielectric layer, which is then annealed at 100°C for 5 minutes. Finally, aluminum is deposited as the gate electrode using a vapor deposition method.

[0124] Figure 8 The figures show the transfer and output curves of field-effect transistors fabricated based on three polymers. All three polymers exhibit good carrier transport capabilities. The mobility is derived from the following formula:

[0125] I DS =C i μ(W / 2L)(V G -V T ) 2

[0126] Among them, I DSIt is the source-leakage current, C i V is the capacitance per unit area of ​​the gate dielectric layer, μ is the charge carrier mobility, W and L are the channel width and length, respectively, and V G It is the gate voltage, V T This is the threshold voltage. The device performance of the polymer field-effect transistors fabricated in the above examples is shown in Table 1.

[0127] At least 10 organic field-effect transistor devices were fabricated using three polymers P1-P3 as transport layers, all of which showed excellent device stability. Specific test values ​​are shown in Table 1.

[0128] Table 1. Field-effect transistor performance of P1-P3 polymers

[0129]

[0130] All the experimental data above demonstrate that these novel isoquinoline dione polymers are excellent organic polymer semiconductor materials. This invention is not limited to the three reported polymer materials P1-P3; by changing different substituents R and different bridging aromatic compounds Ar, many other novel isoquinoline dione derivatives and their corresponding polymers can be obtained. Furthermore, the synthetic route of this invention is simple and easy to implement, the synthetic steps are reasonable, the yield is high, and it is suitable for large-scale preparation. This has important guiding and reference significance for the design and synthesis of organic semiconductor materials with high mobility.

Claims

1. The polymer shown in Formula I: In the formula I, R is selected from any one of C8-C 80 linear or branched alkyl groups; Ar is selected from any of the compounds shown in formulas (1) to (3): In equations (1) to (3), * indicates a substitution position; n represents the degree of aggregation, which ranges from 10 to 1000.

2. The polymer of claim 1, having the formula I, wherein R is 2-decyltetradecyl.

3. The method for preparing the polymer of Formula I according to claim 1 or 2, characterized in that, Includes the following steps: (1) Under acidic conditions, the compound shown in Formula II is reacted with the compound shown in Formula III to obtain the compound shown in Formula IV; (2) In an inert atmosphere, the compound shown in Formula IV is reacted with the compound shown in Formula V to obtain the compound shown in Formula VI; (3) In an inert atmosphere, the compound shown in Formula VI is reacted with the compound shown in Formula VII to obtain the compound shown in Formula VIII; In equations VII and VIII, the definition of R is the same as that in equation I; (4) Under an inert atmosphere and acidic conditions, the compound shown in formula VIII is reacted with the compound shown in formula IX, the compound shown in formula X, or the compound shown in formula XI to obtain the compound shown in formula XII. In equation XII, the definition of R is the same as that in equation I; (5) Under an inert atmosphere and under palladium catalyst catalysis, the compound shown in formula XII and the compound shown in formula XIII react to obtain the polymer shown in formula I. In formula XIII, R 2 is selected from methyl or n-butyl.

4. The production method according to claim 3, characterized by, In step (1), the molar ratio of the compound represented by formula II to the compound represented by formula III is 1.0:1.2~2.0; The reaction temperature is 70℃~100℃; the reaction time is 1 hour~3 hours; The reaction solvent is dilute sulfuric acid, and the mass percentage concentration of the dilute sulfuric acid is 5-50%. In step (2), the molar ratio of the compound represented by formula IV to the compound represented by formula V is 1.0:1.0~4.0; The reaction temperature is 90℃~150℃; the reaction time is 5 hours~10 hours; The reaction is carried out in the presence of a solvent, namely toluene.

5. The production method according to claim 3 or 4, characterized by, In step (3), the molar ratio of the compound represented by formula VI to the compound represented by formula VII is 1.0:1.0~2.0; The reaction temperature is 100℃~130℃; the reaction time is 3 hours~24 hours; The reaction is carried out in the presence of a solvent, which is a mixture of toluene and acetic acid in a volume ratio of 1 to 5:

1.

6. The production method according to claim 3 or 4, characterized by, In step (4), the molar ratio of the compound represented by formula IX, the compound represented by formula X, or the compound represented by formula XI to the compound represented by formula VIII is 1.0:2.0~5.0; The reaction temperature is 100℃~150℃; the reaction time is 3 hours~36 hours; The reaction is carried out in the presence of a solvent, wherein the solvent is a mixture of toluene and acetic acid in a volume ratio of 1 to 5:

1. In step (5), the molar ratio of the compound represented by formula XII to the compound represented by formula XIII is 1.0:1.0; The palladium catalyst is selected from tris(dibenzylideneacetone)palladium and / or tetra(triphenylphosphine)palladium, and the selected ligand is tris(o-tolyl)phosphine; The reaction temperature is 90℃~130℃; the reaction time is 0.5 hours~36 hours; The reaction solvent is chlorobenzene and / or toluene.

7. The compound shown in formula XII: In Formula XII, R is defined the same as R in Formula I of claim 1 or 2; Ar is selected in the same way as the Ar group in Formula I of claim 1 or 2.

8. The use of the compound of Formula I as described in claim 1 in the preparation of organic effect transistors.

9. An organic field effect transistor, characterized by Its organic semiconductor layer is made of the polymer shown in Formula I as described in claim 1.

10. The OFET according to claim 9, wherein The organic semiconductor layer is prepared by spin-coating the polymer shown in Formula I followed by annealing. The annealing temperature is 100~200℃; the time is 5~30 minutes.

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