Environmentally friendly solvent processable quinoid terpolymer and preparation and use thereof

Abstract

The application discloses a quinoid terpolymer which can be processed by an environment-friendly solvent and preparation and application thereof. The structure of the terpolymer is as follows: wherein m:n=75:27. The quinoid terpolymer belongs to a novel polymer, and has the advantages of simple preparation process, high industrial implementation and high yield. When the quinoid terpolymer is applied as a polymer semiconductor, the quinoid terpolymer can be processed by an environment-friendly solvent, and has a hole mobility as high as 2.09 cm 2 V –1 s –1 ​

Description

Technical Field

[0001] This invention relates to a quinone terpolymer, its preparation and application, and particularly to a quinone terpolymer that can be processed with environmentally friendly solvents, its preparation and application. Background Technology

[0002] Compared with traditional inorganic silicon materials, conjugated polymers (CPs) have attractive advantages such as good solution processability, excellent mechanical flexibility, diverse molecular design and tunable optoelectronic properties, which makes them promising for applications in organic field-effect transistors, organic solar cells, organic light-emitting diodes and other electronic devices.

[0003] Synthesize conjugated polymers with specific optical and electronic properties to make them highly versatile in organic photovoltaics (OPV), organic light-emitting diodes (OLED), organic photodetectors (OPD), organic field-effect transistors (OFET), and other applications.

[0004] In recent years, significant progress has been made in OFETs driven by improvements in material design, device structure, and processing technology. These advancements have enhanced charge carrier mobility, stability, and flexibility, making OFET applications increasingly feasible in flexible displays, wearable electronics, and low-cost, large-area electronic devices. However, the fabrication of high-performance OFETs still heavily relies on toxic halogenated solvents such as chloroform and chlorobenzene. Therefore, the development of conjugated polymers that can be processed using environmentally friendly solvents such as tetrahydrofuran (THF) and other non-halogenated, non-aromatic solvents is urgently needed. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a quinone terpolymer that can be processed with environmentally friendly solvents, its preparation, and its applications. The quinone terpolymer of this invention belongs to a novel polymer category. Its preparation process is simple, industrially feasible, and yields high output. When used as a polymer semiconductor, it can be processed using environmentally friendly solvents and exhibits a high viscosity of up to 2.09 cm⁻¹. 2 V – 1 s –1 Hole mobility.

[0006] One of the technical solutions of the present invention:

[0007] A quinone terpolymer that can be processed with environmentally friendly solvents is provided, and its chemical structural formula is as follows:

[0008]

[0009] in, m:n = 75:27.

[0010] The second technical solution of the present invention:

[0011] A method for preparing an environmentally friendly solvent-processable quinone terpolymer is provided, and the synthetic route is as follows:

[0012]

[0013] Preferably, the preparation method of the aforementioned environmentally friendly solvent-processable quinone terpolymer includes the following steps:

[0014] S1. Under the protection of an inert gas, compound 1 and compound 2 are mixed, heated and stirred to react. The mixture obtained from the reaction is concentrated by rotary evaporation under reduced pressure to obtain a crude product. The crude product is recrystallized from ethanol, filtered and the precipitated solid is collected. The solid is dried to obtain compound 3.

[0015] S2. Under inert gas protection, compounds 3 and 4 were dissolved in anhydrous DMF, and then anhydrous triethylamine was added. The mixture was heated and stirred to react. After the reaction was completed, the mixture was filtered and washed with ethyl acetate to obtain a pale yellow solid. The pale yellow solid was dried to obtain compound 5.

[0016] S3. Under inert gas protection, compounds 5, 11-(bromomethyl)tetradecane and potassium carbonate were dissolved in anhydrous DMF and reacted by heating and stirring. The solution was then extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation under reduced pressure to obtain the crude product. The crude product was separated and purified by silica gel column chromatography, and the purified solution was concentrated by rotary evaporation under reduced pressure and dried to obtain a bright yellow solid compound 6.

[0017] S4. Using compounds 6, T-SnMe3, and 2T-SnMe3 as raw materials, a Stille coupling polymerization reaction is carried out in a molar ratio of compound 6 / T-SnMe3 / 2T-SnMe3 = 100 / 75 / 25 to prepare the aforementioned quinone terpolymer PA-3T75-4T25, which can be processed by environmentally friendly solvents.

[0018] Preferably, in the aforementioned method for preparing the quinone terpolymer that can be processed with environmentally friendly solvents, the heating and stirring reaction in step S1 is carried out at a temperature of 150-170°C for 10-15 hours.

[0019] Preferably, in the aforementioned method for preparing the quinone terpolymer that can be processed by environmentally friendly solvents, the heating and stirring reaction in step S2 is carried out at a temperature of 110-130°C for 10-15 hours.

[0020] Preferably, in the aforementioned method for preparing the quinone terpolymer that can be processed by environmentally friendly solvents, the heating and stirring reaction temperature in step S3 is 90-110°C, and the time is 10-15 hours.

[0021] Preferably, in the aforementioned method for preparing quinone terpolymers that can be processed with environmentally friendly solvents, the inert gas mentioned in S1, S2 and S3 is nitrogen.

[0022] Preferably, in the aforementioned method for preparing quinone terpolymers that can be processed with environmentally friendly solvents, the silica gel column chromatography described in S3 uses petroleum ether as the eluent.

[0023] Preferably, in the aforementioned method for preparing the quinone terpolymer processed by environmentally friendly solvents, the Stille coupling polymerization process is as follows: under an argon atmosphere, compound 6, T-SnMe3, 2T-SnMe3, tris(dibenzylacetone)dipalladium and tris(o-tolyl)phosphine are dissolved in ultra-dry chlorobenzene, the solution is heated to 130-140°C, and the reaction is carried out for 20-30 hours. At the end of the reaction, 2-trimethyltin thiophene is added for end-capping, and after reacting for 3-5 hours, 2-bromothiophene is added for end-capping. After the reaction is completed, the mixture is cooled to room temperature, precipitated with methanol, filtered, and the precipitate is successively subjected to Soxhlet extraction with methanol, acetone, ethyl acetate, chloroform and chlorobenzene. The polymer solution obtained by Soxhlet extraction is evaporated in a rotary evaporator, concentrated, precipitated with anhydrous methanol, filtered, and finally dried in a vacuum drying oven to obtain the final product.

[0024] The third technical solution of the present invention:

[0025] This invention provides an application of the aforementioned environmentally friendly solvent-processable quinone terpolymer as a polymer semiconductor.

[0026] The beneficial effects of this invention are:

[0027] 1. The polymer of the present invention is a quinone terpolymer that can be processed with environmentally friendly solvents, and its chemical structure is different from that of existing polymers.

[0028] 2. The preparation process of the quinone terpolymer of the present invention, which can be processed by environmentally friendly solvents, is simple and can be industrially promoted and implemented.

[0029] 3. When the polymer of the present invention is used as a polymer semiconductor material, it can be dissolved and processed using conventional chlorobenzene solvents, exhibiting good handling and air stability. Furthermore, the field-effect transistor devices possess excellent hole mobility, reaching 1.50 cm⁻¹. 2 V –1 s –1 On the other hand, it can be processed using the environmentally friendly solvent tetrahydrofuran, achieving a thickness as high as 2.09 cm. 2 V –1 s –1 The hole mobility is the highest among OFETs based on quinone polymers to date, and it is also one of the highest mobility values ​​among OFETs processed with environmentally friendly solvents with reliable test results. Attached Figure Description

[0030] Appendix Figure 1 This is a comparison of the polymer prepared in Example 1 of the present invention when processed with environmentally friendly solvents with reliable / unreliable polymers processed with environmentally friendly solvents over a period of fifteen years.

[0031] Appendix Figure 2 The peak intensity ratio of the nitrogen and sulfur atoms in the polymer obtained by X-ray photoelectron spectroscopy test of the polymer prepared in Example 1 of the present invention is consistent with the theoretical nitrogen / sulfur atom ratio (0.55) of the polymer, which proves that the polymer prepared in Example 1 of the present invention is a copolymer with the correct unit ratio. Detailed Implementation

[0032] The present invention will be further described below with reference to embodiments, but these embodiments are not intended to limit the scope of the invention.

[0033] Embodiments of the present invention

[0034] The reaction process of the chemical reaction included in the embodiments of the present invention is shown in the following formula:

[0035]

[0036] Example 1:

[0037] The synthesis path in this embodiment is shown in the above formula, and the steps are as follows:

[0038] 1) Compound 1 (40 mmol, 4.56 g) and Compound 2 (40 mL) were added to a 250 mL two-necked round-bottom flask. The mixture was then heated to 160 °C under nitrogen protection and stirred for 12 h. During the reaction, the solution changed from colorless and transparent to black. After the reaction was completed, the mixture was allowed to cool to room temperature and the solvent was removed by rotary evaporator to obtain the crude product. The crude product was dissolved in dichloromethane and then recrystallized from the dissolved crude product with ethanol. A pale yellow solid precipitated out. The solid was filtered and dried to finally obtain the pale yellow solid compound 3.

[0039] 2) In a 250 mL three-necked round-bottom flask, compound 3 (4.0 mmol, 0.79 g) and compound 4 (10 mmol, 1.0 g) were dissolved in 80 mL of anhydrous DMF solution under nitrogen protection. Then, 80 mL of anhydrous triethylamine was added, and the reaction solution was heated to 120 °C. The solution turned red, and after reacting for 12 h, an orange-yellow precipitate was formed. After the reaction was completed, the solution was cooled to room temperature, filtered, and washed three times with ethyl acetate or acetone. The filtered solid was then dried under vacuum to obtain a pale yellow solid compound 5.

[0040] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.3 g), 11-(bromomethyl)tricarane (15 mmol, 6.25 g), and potassium carbonate (25 mmol, 3.45 g) were dissolved in 60 ml of anhydrous DMF. Under nitrogen protection, the mixture was heated to 100 °C and stirred continuously for 12 hours. At the end of the reaction, the solution was dark red. The solution was cooled to room temperature, extracted with dichloromethane, dried with anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by rotary evaporation under reduced pressure to obtain the crude product. The crude product was dissolved in dichloromethane and purified by silica gel column chromatography (petroleum ether). The purified solution was concentrated by rotary evaporation under reduced pressure and dried to obtain a bright yellow solid compound 6.

[0041] 4) Compound 6 (200 μmol, 226 mg), T-SnMe3 (150 μmol, 61 mg), 2T-SnMe3 (50 μmol, 24 mg), catalyst tris(dibenzylacetone)palladium (8 mg), and tris(o-tolyl)phosphine (10 mg) were added to a two-necked flask and sealed. After purging with argon gas for 30 minutes, 8 mL of ultra-dry chlorobenzene was added. Then, the temperature was raised to 135 °C, and the solution was heated under reflux for 24 hours. At the end of the reaction, a small amount of 2-tributylene was added. Tin-thiophene end-capping was used to remove all bromine groups. After reacting for 3 hours, a small amount of 2-bromothiophene was added for end-capping to remove all trimethyltin groups. Finally, methanol was used for precipitation. The precipitate was successively extracted with methanol, acetone, ethyl acetate, chloroform and chlorobenzene using a Soxhlet extractor. The polymer solution obtained by Soxhlet extraction was evaporated in a rotary evaporator, concentrated, and then added to anhydrous methanol to precipitate. After filtration, it was dried in a vacuum drying oven to obtain the quinone terpolymer PA-3T75-4T25 processed with environmentally friendly solvents.

[0042] Example 2:

[0043] The synthesis steps in this embodiment are as follows:

[0044] 1) Compound 1 (40 mmol, 4.35 g) and Compound 2 (40 mL) were added to a 250 mL two-necked round-bottom flask. The reaction was then heated to 150 °C under nitrogen protection and stirred for 15 h. During the reaction, the solution changed from colorless and transparent to black. After the reaction was completed, the solution was allowed to cool to room temperature and the solvent was removed by rotary evaporator to obtain the crude product. The crude product was dissolved in dichloromethane and then recrystallized from the dissolved crude product with ethanol. A pale yellow solid precipitated out. The solid was filtered and dried to finally obtain the pale yellow solid compound 3.

[0045] 2) In a 250 mL three-necked round-bottom flask, compound 3 (4.0 mmol, 0.77 g) and compound 4 (10 mmol, 1.0 g) were dissolved in 80 mL of anhydrous DMF solution under nitrogen protection. Then, 80 mL of anhydrous triethylamine was added, and the reaction solution was heated to 110 °C. The solution turned red and reacted for 15 h. An orange-yellow precipitate was formed. After the reaction was completed, the solution was cooled to room temperature, filtered, and washed three times with ethyl acetate or acetone. The filtered solid was then dried under vacuum to obtain a pale yellow solid compound 5.

[0046] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.4 g), 11-(bromomethyl)tricarane (15 mmol, 6.18 g), and potassium carbonate (25 mmol, 3.46 g) were dissolved in 60 ml anhydrous DMF. Under nitrogen protection, the mixture was heated to 90 °C and stirred continuously for 15 hours. At the end of the reaction, the solution was dark red. The solution was cooled to room temperature, extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation under reduced pressure to obtain the crude product. The crude product was dissolved in dichloromethane, separated and purified by silica gel column chromatography (petroleum ether), and the purified solution was concentrated by rotary evaporation under reduced pressure and dried to obtain a bright yellow solid compound 6.

[0047] 4) Compound 6 (200 μmol, 220 mg), T-SnMe3 (150 μmol, 60 mg), 2T-SnMe3 (50 μmol, 25 mg), catalyst tris(dibenzylacetone)palladium (8 mg), and tris(o-tolyl)phosphine (10 mg) were added to a two-necked flask and sealed. After purging with argon gas for 30 minutes, 10 mL of ultra-dry chlorobenzene was added. The temperature was then raised to 130 °C, and the solution was heated under reflux for 30 hours. At the end of the reaction, a small amount of 2-tributylene was added. Tin-thiophene end-capping was performed to remove all bromine groups. After reacting for 3 hours, a small amount of 2-bromothiophene was added for end-capping to remove all trimethyltin groups. Finally, methanol was used for precipitation. The precipitate was successively extracted with methanol, acetone, ethyl acetate, chloroform, and chlorobenzene using a Soxhlet extractor. The polymer solution obtained by Soxhlet extraction was evaporated in a rotary evaporator, concentrated, and then added to anhydrous methanol to precipitate. After filtration, it was dried in a vacuum drying oven to obtain the quinone terpolymer PA-3T75-4T25, which can be processed with environmentally friendly solvents.

[0048] Example 3:

[0049] The synthesis steps in this embodiment are as follows:

[0050] 1) In a 250 mL two-necked round-bottom flask, add compound 1 (40 mmol, 4.52 g) and compound 2 (40 mL), heat the reaction to 170 °C, and stir for 12 h. During the reaction, the solution changes from colorless and transparent to black. After the reaction is completed, wait for the reaction to cool to room temperature, and then remove the solvent using a rotary evaporator to obtain the crude product. Dissolve the crude product in dichloromethane, and then recrystallize the dissolved crude product with ethanol. A pale yellow solid precipitates out. Filter and dry the solid to finally obtain the pale yellow solid compound 3.

[0051] 2) In a 250 mL three-necked round-bottom flask, compound 3 (4.0 mmol, 0.76 g) and compound 4 (10 mmol, 1.1 g) were dissolved in 80 mL of anhydrous DMF solution under nitrogen protection. Then, 80 mL of anhydrous triethylamine was added, and the reaction solution was heated to 130 °C. The solution turned red and reacted for 10 h. An orange-yellow precipitate was formed. After the reaction was completed, the solution was cooled to room temperature, filtered, and washed three times with ethyl acetate or acetone. The solid obtained by vacuum drying was then used to obtain a pale yellow solid compound 5.

[0052] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.24 g), 11-(bromomethyl)tetradecane (15 mmol, 6.23 g), and potassium carbonate (25 mmol, 3.44 g) were dissolved in 60 ml of anhydrous DMF. Under nitrogen protection, the mixture was heated to 110 °C and stirred continuously for 10 hours. At the end of the reaction, the solution was dark red. The solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation under reduced pressure to obtain the crude product. The crude product was dissolved in dichloromethane, separated and purified by silica gel column chromatography (petroleum ether), and the purified solution was concentrated by rotary evaporation under reduced pressure and dried to obtain a bright yellow solid compound 6.

[0053] 4) Compound 6 (200 μmol, 223 mg), T-SnMe3 (150 μmol, 62 mg), 2T-SnMe3 (50 μmol, 25 mg), catalyst tris(dibenzylacetone)palladium (8 mg), and tris(o-tolyl)phosphine (10 mg) were added to a two-necked flask and sealed. After purging with argon gas for 30 minutes, 8 mL of ultra-dry chlorobenzene was added. Then, the temperature was raised to 140 °C, the solution was heated under reflux, and the reaction was carried out for 20 hours. At the end of the reaction, a small amount of 2-tributylene was added. The bromine groups were removed by end-capping with 2-bromothiophene. After reacting for 3 hours, a small amount of 2-bromothiophene was added to remove all trimethyltin groups. The precipitate was then precipitated with methanol. The precipitate was then subjected to Soxhlet extraction with methanol, acetone, ethyl acetate, chloroform and chlorobenzene in sequence. The polymer solution obtained by Soxhlet extraction was evaporated in a rotary evaporator and concentrated. Then it was added to anhydrous methanol to precipitate, filtered, and dried in a vacuum drying oven to obtain the quinone terpolymer PA-3T75-4T25, which can be processed with environmentally friendly solvents.

[0054] Example 4:

[0055] The polymer PA-3T75-4T25 prepared in Examples 1-3 of this invention can be processed based on chlorobenzene / tetrahydrofuran solution to prepare organic field-effect transistor devices according to existing processes, and the obtained electronic products have excellent hole mobility.

[0056] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. An environmentally friendly solvent processable quinoid terpolymer characterized in that, The chemical structural formula is as follows: ； Where R= , m:n=75:

25.

2. A process for the production of the environmentally friendly solvent processable quinoid terpolymer according to claim 1, characterized in that The synthesis path is as follows: 。 3. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 2, characterized in that, The method comprises the following steps: S1. Under the protection of inert gas, compound 1 and compound 2 are mixed and heated and stirred to react, the reaction mixture is concentrated by rotary evaporation under reduced pressure to obtain a crude product, the crude product is recrystallized with ethanol, and then filtered and solid precipitated is collected, and the solid is dried to obtain compound 3; S2. Under the protection of inert gas, compound 3 and compound 4 are dissolved in anhydrous DMF, and then anhydrous triethylamine is added, and heated and stirred to react; after the reaction is completed, filtration is performed, and the obtained yellowish solid is washed with ethyl acetate to obtain a yellowish solid, which is dried to obtain compound 5; S3. Under the protection of inert gas, compound 5, 11-(bromomethyl)tricosane and potassium carbonate are dissolved in anhydrous DMF, and heated and stirred to react; then the solution is extracted with dichloromethane, dried with anhydrous magnesium sulfate, filtered, and the obtained filtrate is concentrated by rotary evaporation under reduced pressure to obtain a crude product, which is separated and purified by silica gel column chromatography, and the obtained purified solution is concentrated by rotary evaporation under reduced pressure and dried to obtain a light yellow solid compound 6; S4. Compound 6, T-SnMe3 and 2T-SnMe3 are used as raw materials, and a Stille coupling polymerization reaction is performed according to a molar ratio of compound 6 / T-SnMe3 / 2T-SnMe3 = 100 / 75 / 25, so that the environmentally friendly solvent processable quinone type terpolymer PA-3T75-4T25 is prepared.

4. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that: The temperature of the heated and stirred reaction in S1 is 150-170 DEG C, and the time is 10-15 h.

5. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that: The temperature of the heated and stirred reaction in S2 is 110-130 DEG C, and the time is 10-15 h.

6. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that: The temperature of the heated and stirred reaction in S3 is 90-110 DEG C, and the time is 10-15 h.

7. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that: The inert gas in S1, S2 and S3 is nitrogen.

8. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that: The silica gel column chromatography in S3 uses petroleum ether as an eluent.

9. The process for the production of an environmentally friendly solvent processable quinoid terpolymer according to claim 3, characterized in that, The Stille coupling polymerization reaction process is as follows: under an argon atmosphere, compound 6, T-SnMe3, 2T-SnMe3, tris(dibenzylideneacetone)dipalladium and tri(ortho-tolyl)phosphine are dissolved in super-dry chlorobenzene, the solution is heated to 130-140 DEG C, and the reaction is performed for 20-30 h; when the reaction is completed, 2-trimethyltin thiophene is added to terminate the reaction, and the reaction is performed for 3-5 h; then 2-bromothiophene is added to terminate the reaction; after the reaction is completed, the mixture is cooled to room temperature, and the mixture is precipitated with methanol, filtered, and the obtained precipitate is successively subjected to Soxhlet extraction with methanol, acetone, ethyl acetate, chloroform and chlorobenzene, the polymer solution obtained by Soxhlet extraction is evaporated in a rotary evaporator, concentrated, precipitated with anhydrous methanol, filtered, and finally dried in a vacuum drying oven to obtain the product.

10. The environmentally friendly solvent processable quinone type terpolymer according to claim 1 is used as a polymer semiconductor. ​

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