Quinoid terpolymer capable of being processed by environment-friendly solvent as well as preparation and application of quinone terpolymer

Abstract

The invention discloses a quinoneterpolymer capable of being processed by an environment-friendly solvent as well as preparation and application of the quinoneterpolymer. The structure of the copolymer is as follows: # imgabs 0 #, wherein # imgabs 1 # m: n = 75: 27. The quinoneterpolymer belongs to a novel polymer, the preparation process is simple, industrial implementation can be realized, and the yield is high; when being used as a polymer semiconductor, the polymer can be processed by using an environment-friendly solvent, and the hole mobility is up to 2.09 cm < 2 > V <-1 > s <-1 >.

Description

Technical Field

[0001] The invention relates to a quinone type terpolymer and preparation and application thereof, in particular to a quinone type terpolymer processable with an environmentally friendly solvent and preparation and application thereof. Background Art

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

[0003] The synthesis of conjugated polymers with specific optical and electronic properties makes them highly versatile in organic photovoltaics (OPVs), organic light-emitting diodes (OLEDs), organic photodetectors (OPDs), organic field-effect transistors (OFETs), and other applications.

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

[0005] In order to solve the above technical problems, the present invention provides a quinone-type terpolymer that can be processed with an environmentally friendly solvent and its preparation and application. The quinone-type terpolymer of the present invention is a new type of polymer, and its preparation process is simple, can be industrialized, and has a high yield; when used as a polymer semiconductor, it can be processed with an environmentally friendly solvent and has a high 2 V – 1 s –1 The hole mobility.

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

[0007] A quinone-type terpolymer that can be processed with an environmentally friendly solvent is provided, and its chemical structure is as follows:

[0008]

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

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

[0011] A method for preparing a quinone-type terpolymer that can be processed with an environmentally friendly solvent is provided, and the synthesis route thereof is as follows:

[0012]

[0013] Preferably, the method for preparing the aforementioned quinone-type terpolymer processable with an environmentally friendly solvent comprises the following steps:

[0014] S1. Under the protection of inert gas, compound 1 and compound 2 are mixed, heated and stirred to react, and the reaction mixture 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, and the solid is dried to obtain compound 3;

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

[0016] S3. Under the protection of inert gas, compound 5, 11-(bromomethyl)tricosane and potassium carbonate were dissolved in anhydrous DMF, and the reaction was heated and stirred; the solution was then extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation under reduced pressure to obtain a 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 compound 6, T-SnMe3 and 2T-SnMe3 as raw materials, a Stille coupling polymerization reaction is carried out at a molar ratio of compound 6 / T-SnMe3 / 2T-SnMe3=100 / 75 / 25 to prepare the quinone-type terpolymer PA-3T75-4T25 that can be processed by environmentally friendly solvents.

[0018] Preferably, in the aforementioned method for preparing the quinone-type terpolymer processable with an environmentally friendly solvent, the temperature of the heating and stirring reaction in S1 is 150-170° C. and the time is 10-15 hours.

[0019] Preferably, in the aforementioned method for preparing the quinone-type terpolymer processable with an environmentally friendly solvent, the temperature of the heating and stirring reaction in S2 is 110-130° C. and the time is 10-15 hours.

[0020] Preferably, in the aforementioned method for preparing the quinone-type terpolymer processable with an environmentally friendly solvent, the reaction temperature of the heating and stirring in S3 is 90-110° C. and the reaction time is 10-15 h.

[0021] Preferably, in the aforementioned method for preparing the quinone-type terpolymer processable with an environmentally friendly solvent, the inert gas described in S1, S2 and S3 is nitrogen.

[0022] Preferably, in the aforementioned method for preparing the quinone-type terpolymer processable with an environmentally friendly solvent, the eluent for the silica gel column chromatography described in S3 is petroleum ether.

[0023] Preferably, the preparation method of the aforementioned quinone-type terpolymer that can be processed by environmentally friendly solvents, the Stille coupling polymerization reaction process is as follows: under an argon atmosphere, compound 6, T-SnMe3, 2T-SnMe3, tri(dibenzylideneacetone)dipalladium and tri(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-trimethyltinthiophene is added for end-capping. After 3-5 hours of reaction, 2-bromothiophene is added for end-capping; after the reaction is completed, it is cooled to room temperature, the mixture is precipitated with methanol, filtered, and the obtained precipitate is extracted with methanol, acetone, ethyl acetate, chloroform and chlorobenzene in turn. The polymer solution obtained by Soxhlet extraction is evaporated from the solvent in a rotary evaporator, concentrated, precipitated with anhydrous methanol, filtered, and finally dried in a vacuum drying oven.

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

[0025] Provided is an application of the aforementioned quinone-type terpolymer processable by an environmentally friendly solvent as a polymer semiconductor.

[0026] Beneficial effects of the present invention:

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

[0028] 2. The preparation process of the quinone-type terpolymer that can be processed by environmentally friendly solvents is simple and can be promoted and implemented industrially.

[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, and can exhibit good operation and air stability, and the field effect transistor device has an excellent hole mobility of up to 1.50 cm 2 V –1 s –1 On the other hand, it can be processed using the environmentally friendly solvent tetrahydrofuran, achieving a maximum of 2.09cm 2 V –1 s –1 The hole mobility is the highest among OFETs made from quinone polymers to date, and is also one of the highest mobilities among OFETs processed with environmentally friendly solvents and with confidence in the test results. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Attached Figure 1 Comparison of the results of credible / incredible polymers when the polymer prepared in Example 1 of the present invention is processed using an environmentally friendly solvent and when the polymer is processed using an environmentally friendly solvent within fifteen years.

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

[0032] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0033] Embodiments of the present invention

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

[0035]

[0036] Embodiment 1:

[0037] The synthesis path of 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, and then the mixture was 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 reaction mixture was cooled to room temperature, and then the solvent was removed by a rotary evaporator to obtain a crude product; the crude product was dissolved in dichloromethane, and then the dissolved crude product was recrystallized with ethanol, and a light yellow solid was precipitated. The solid was filtered and dried to finally obtain a light 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 and nitrogen was passed through; then 80 mL of anhydrous triethylamine was added, and the reaction solution was heated to 120°C, the solution turned red, and reacted for 12 hours, and an orange-yellow precipitate was generated; after the reaction was completed, the temperature was lowered to room temperature, filtered, and rinsed with ethyl acetate or acetone three times, and then the solid obtained by filtration was vacuum dried to finally obtain a light yellow solid compound 5;

[0040] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.3 g), 11-(bromomethyl)tricosane (15 mmol, 6.25 g) and potassium carbonate (25 mmol, 3.45 g) were dissolved in 60 ml of anhydrous DMF, nitrogen was passed through, the temperature was raised to 100 ° C and the reaction was stirred for 12 hours; at the end of the reaction, the solution was dark red, the solution was cooled to room temperature, the solution was extracted with dichloromethane, and then dried with anhydrous magnesium sulfate and filtered; the filtrate was concentrated by rotary evaporation under reduced pressure to obtain a crude product, the crude product was dissolved with dichloromethane, and 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;

[0041] 4) Compound 6 (200 μmol, 226 mg), T-SnMe3 (150 μmol, 61 mg), 2T-SnMe3 (50 μmol, 24 mg), catalyst tri(dibenzylideneacetone)dipalladium (8 mg) and tri(o-tolyl)phosphine (10 mg) were added to a two-necked bottle and sealed. After passing argon for 30 minutes, 8 mL of ultra-dry chlorobenzene was added; then the temperature was raised to 135°C, the solution was heated to reflux, and the reaction was carried out for 24 hours. At the end of the reaction, a small amount of 2-tributyl The tin thiophene is capped to remove all bromine groups. After reacting for 3 hours, a small amount of 2-bromothiophene is added to cap the reaction to remove all trimethyltin groups. Finally, methanol is used for precipitation, and the precipitate is extracted with methanol, acetone, ethyl acetate, chloroform and chlorobenzene in sequence. The polymer solution obtained by Soxhlet extraction is evaporated in a rotary evaporator, concentrated, and then added to anhydrous methanol for precipitation. The precipitate is filtered and dried in a vacuum drying oven to obtain the quinone-type terpolymer PA-3T75-4T25 processed by an environmentally friendly solvent.

[0042] Embodiment 2:

[0043] The synthesis steps of 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, and then the reaction temperature was raised to 150 ° C. under nitrogen protection, and the reaction was stirred for 15 h. During the reaction, the solution changed from colorless and transparent to black. After the reaction was completed, the reaction temperature was waited to cool to room temperature, and the solvent was removed by a rotary evaporator to obtain a crude product; the crude product was dissolved in dichloromethane, and then the dissolved crude product was recrystallized with ethanol, and a light yellow solid was precipitated. The solid was filtered and dried to finally obtain a light 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 and nitrogen was passed through; 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 generated. After the reaction was completed, the temperature was lowered to room temperature, filtered, and rinsed with ethyl acetate or acetone three times. The solid obtained by filtration was then vacuum dried to finally obtain a light yellow solid compound 5;

[0046] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.4 g), 11-(bromomethyl)tricosane (15 mmol, 6.18 g) and potassium carbonate (25 mmol, 3.46 g) were dissolved in 60 ml of anhydrous DMF, nitrogen was passed through, the temperature was raised to 90°C and the reaction was continued with stirring for 15 hours; at the end of the reaction, the solution was dark red, the solution was cooled to room temperature, extracted with dichloromethane, and then dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by reduced pressure rotary evaporation to obtain a crude product, the crude product was dissolved with dichloromethane, and separated and purified by silica gel column chromatography (petroleum ether), and the purified solution was concentrated by reduced pressure rotary evaporation 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 tri(dibenzylideneacetone)dipalladium (8 mg) and tri(o-tolyl)phosphine (10 mg) were added to a two-necked bottle and sealed. After passing argon for 30 minutes, 10 mL of ultra-dry chlorobenzene was added, and then the temperature was raised to 130°C, and the solution was heated to reflux and reacted for 30 hours. At the end of the reaction, a small amount of 2-tributyl The tin thiophene is capped to remove all bromine groups. After reacting for 3 hours, a small amount of 2-bromothiophene is added to cap the reaction to remove all trimethyltin groups. Finally, methanol is used for precipitation. The precipitate is extracted with methanol, acetone, ethyl acetate, chloroform and chlorobenzene in sequence. The polymer solution obtained by Soxhlet extraction is evaporated in a rotary evaporator and concentrated. Then, it is added to anhydrous methanol for precipitation, filtered, and dried in a vacuum drying oven to obtain the quinone-type terpolymer PA-3T75-4T25 that can be processed with environmentally friendly solvents.

[0048] Embodiment 3:

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

[0050] 1) Compound 1 (40 mmol, 4.52 g) and compound 2 (40 mL) were added to a 250 mL two-necked round-bottom flask, the reaction temperature was raised to 170 ° C, and the reaction was stirred for 12 h. During the reaction, the solution changed from colorless and transparent to black. After the reaction was completed, the reaction temperature was cooled to room temperature, and the solvent was removed by a rotary evaporator to obtain a crude product. The crude product was dissolved in dichloromethane, and then the dissolved crude product was recrystallized with ethanol. A light yellow solid was precipitated, and the solid was filtered and dried to finally obtain a light 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 and nitrogen was passed through; 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 generated. After the reaction was completed, the temperature was lowered to room temperature, filtered, and rinsed with ethyl acetate or acetone three times. The solid obtained by filtration was then vacuum dried to finally obtain a light yellow solid compound 5;

[0052] 3) In a 250 ml double-necked flask, compound 5 (5 mmol, 2.24 g), 11-(bromomethyl)tricosane (15 mmol, 6.23 g) and potassium carbonate (25 mmol, 3.44 g) were dissolved in 60 ml of anhydrous DMF, nitrogen was passed through, the temperature was raised to 110°C and the reaction was continued with stirring 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 a crude product, the crude product was dissolved in dichloromethane, and 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 tri(dibenzylideneacetone)dipalladium (8 mg) and tri(o-tolyl)phosphine (10 mg) were added to a two-necked bottle and sealed. After passing argon for 30 minutes, 8 mL of ultra-dry chlorobenzene was added; then the temperature was raised to 140°C, the solution was heated to reflux, and the reaction was carried out for 20 hours. At the end of the reaction, a small amount of 2-tributyl The polymer solution was end-capped with thiophene to remove all bromine groups. After 3 hours of reaction, a small amount of 2-bromothiophene was added to end-cap and all trimethyltin groups were removed. Methanol was used for precipitation. The precipitate was extracted 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 for precipitation, filtered, and dried in a vacuum drying oven to obtain the quinone-type terpolymer PA-3T75-4T25 that can be processed with environmentally friendly solvents.

[0054] Embodiment 4:

[0055] The polymer PA-3T75-4T25 prepared in Examples 1-3 of the present invention can be processed based on a chlorobenzene / tetrahydrofuran solution, and an organic field effect transistor device can be prepared according to the existing process. The obtained electronic product has excellent hole mobility.

[0056] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A quinone-type terpolymer processable with an environmentally friendly solvent, characterized in that: Its chemical structure is as follows: in, m:n=75:

27.

2. A method for preparing a quinone-type terpolymer processable with an environmentally friendly solvent according to claim 1, characterized in that: The synthesis path is as follows:

3. The method for preparing a quinone-type terpolymer processable by an environmentally friendly solvent according to claim 2, characterized in that: The steps include: S1. Under the protection of inert gas, compound 1 and compound 2 are mixed, heated and stirred to react, and the reaction mixture 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, and the solid is dried to obtain compound 3; S2. Under the protection of inert gas, compound 3 and compound 4 were dissolved in anhydrous DMF, and then anhydrous triethylamine was added, and the reaction was heated and stirred; after the reaction was completed, the mixture was filtered and washed with ethyl acetate to obtain a light yellow solid, which was dried to obtain compound 5; S3. Under the protection of inert gas, compound 5, 11-(bromomethyl)tricosane and potassium carbonate were dissolved in anhydrous DMF, and the reaction was heated and stirred; the solution was then extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation under reduced pressure to obtain a 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; S4. Using compound 6, T-SnMe3 and 2T-SnMe3 as raw materials, a Stille coupling polymerization reaction is carried out at a molar ratio of compound 6 / T-SnMe3 / 2T-SnMe3=100 / 75 / 25 to prepare the quinone-type terpolymer PA-3T75-4T25 that can be processed by environmentally friendly solvents.

4. The method for preparing the quinone-type terpolymer processable by an environmentally friendly solvent according to claim 3, characterized in that: The temperature of the heating and stirring reaction in S1 is 150-170°C and the time is 10-15h.

5. The method for preparing the quinone-type terpolymer processable by environmentally friendly solvents according to claim 3, characterized in that: The temperature of the heating and stirring reaction in S2 is 110-130°C and the time is 10-15h.

6. The method for preparing the quinone-type terpolymer processable by an environmentally friendly solvent according to claim 3, characterized in that: The reaction temperature of the heating and stirring in S3 is 90-110°C and the time is 10-15h.

7. The method for preparing the quinone-type terpolymer processable by environmentally friendly solvents according to claim 3, characterized in that: The inert gas described in S1, S2 and S3 is nitrogen.

8. The method for preparing the quinone-type terpolymer processable by environmentally friendly solvents according to claim 3, characterized in that: The silica gel column chromatography described in S3 has petroleum ether as the eluent.

9. The method for preparing a quinone-type terpolymer processable by an environmentally friendly solvent 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, tri(dibenzylideneacetone)dipalladium and tri(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-trimethyltinthiophene is added for end-capping. After the reaction is carried out for 3-5 hours, 2-bromothiophene is added for end-capping. After the reaction is completed, the mixture is cooled to room temperature, and the mixture is precipitated with methanol and filtered. The obtained precipitate is extracted with methanol, acetone, ethyl acetate, chloroform and chlorobenzene in sequence. 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.

10. Use of the environmentally friendly solvent processable quinone-type terpolymer according to claim 1 as a polymer semiconductor.

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