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CN-116903645-B - Bithiophene derivative, preparation method and application thereof, electrochromic film and preparation method thereof

CN116903645BCN 116903645 BCN116903645 BCN 116903645BCN-116903645-B

Abstract

The invention relates to the technical field of electrochromic films, in particular to a bithiophene derivative, a preparation method and application thereof, and an electrochromic film and a preparation method thereof. The invention generates tin-base dithiophene through the reaction of bithiophene and tributyltin chloride, generates boron-esterification bithiophene through the reaction of bithiophene and isopropanol pinacol borate, generates 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene through the reaction of tin-base bithiophene or boron-esterification bithiophene and 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene, and finally prepares bithiophene derivative through the reaction of the product, aluminum lithium hydride and hydrogenated diimine boron generated by dimethoxyethane. The derivative can be applied to an electrochromic film, and the electrochromic film with high response speed and fluoride ion detection capability is successfully prepared by carrying out electrochemical polymerization on the bithiophene derivative.

Inventors

  • LI WEIJUN
  • ZHANG LING
  • WANG JIAHAO
  • ZHANG CHENG
  • LI YUFEI

Assignees

  • 平湖市浙江工业大学新材料研究院
  • 浙江工业大学

Dates

Publication Date
20260505
Application Date
20230612

Claims (10)

  1. 1. A kind of bithiophene derivative, the structure is characterized by comprising the following steps:
  2. 2. a process for the preparation of a bithiophene derivative as claimed in claim 1 comprising the steps of: (1) Preparation of 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene: In a protective atmosphere, mixing bithiophene, tetrahydrofuran, n-butyllithium solution and tributyl tin chloride for reaction to obtain tin bithiophene; (b) In a protective atmosphere, mixing tin-modified bithiophene, 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene, tetrakis (triphenylphosphine) palladium and N, N-dimethylformamide, and reacting to obtain 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene; In a protective atmosphere, mixing bithiophene, tetrahydrofuran, n-butyllithium solution and isopropanol pinacol borate for reaction to obtain boron esterified bithiophene; (II) mixing boron esterified bithiophene, 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene, potassium carbonate, tetrakis (triphenylphosphine) palladium, water and dioxane in a protective atmosphere, and reacting to obtain 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene; (2) Preparation of bithiophene derivatives: (A) Mixing and reacting a dimethoxyethane solution of lithium aluminum hydride, a dimethoxyethane solution of dimyristol boron fluoride and benzene in a protective atmosphere to obtain dimyristol boron hydride; (B) Mixing hydrogenated dimidiate boron, 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene and tetrahydrofuran, and reacting to obtain the bithiophene derivative.
  3. 3. The preparation method of the bithiophene derivative according to claim 2, wherein the dosage ratio of tetrahydrofuran to bithiophene in the step (a) is 1-5 ml/1 mmol, the molar ratio of n-butyllithium to bithiophene is 0.95-1.1:1, the molar ratio of tributyltin chloride to bithiophene is 0.95-1.3:1, and the concentration of the n-butyllithium solution is 1.4-1.8 mol/L; the reaction temperature in the step (a) is 20-28 ℃ and the reaction time is 10-16 h; The molar ratio of tin-modified dithiophene to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene in the step (b) is 2.5-4:1, the dosage ratio of N, N-dimethylformamide to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 10-15 mL:1mmol, and the molar ratio of tetrakis (triphenylphosphine) palladium to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 0.03-0.08:1; The reaction temperature in the step (b) is 100-140 ℃ and the reaction time is 10-14 h.
  4. 4. The preparation method of the bithiophene derivative according to claim 2 or 3, wherein the dosage ratio of tetrahydrofuran to bithiophene in the step (I) is 1-5 mL, the molar ratio of n-butyllithium to bithiophene is 0.95-1.1:1, the molar ratio of isopropanol pinacol borate to bithiophene is 1-2.1:1, and the concentration of the n-butyllithium solution is 1.4-1.8 mol/L; the reaction temperature in the step (I) is 20-28 ℃ and the reaction time is 10-16 h; The molar ratio of the boronized dithiophene to the 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene in the step (II) is 2.5-4:1, the molar ratio of the potassium carbonate to the 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 20-45:1, the molar ratio of the tetrakis (triphenylphosphine) palladium to the 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 0.03-0.08:1, the dosage ratio of the water to the 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 2-8 mL:1mmol, and the dosage ratio of the dioxane to the 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 5-10 mL:1mmol; the reaction temperature in the step (II) is 100-140 ℃ and the reaction time is 10-14 h.
  5. 5. The preparation method of the bithiophene derivative according to claim 4, wherein in the step (A), the molar ratio of lithium aluminum hydride to dimetyl boron fluoride is 1:3-5, the dosage ratio of dimethoxyethane to lithium aluminum hydride in a dimethoxyethane solution of lithium aluminum hydride is 4-10 mL:1mmol, the dosage ratio of dimethoxyethane to dimetyl boron fluoride in a dimethoxyethane solution of dimetyl boron fluoride is 800-850 mL:1mol, and the dosage ratio of benzene to dimetyl boron fluoride is 20-30 mL:123.09mmol; the temperature of the reaction in the step (A) is 20-28 ℃ and the time is 1-3 h.
  6. 6. The method for preparing a bithiophene derivative according to claim 2 or 5, wherein in the step (B), the molar ratio of hydrogenated dimidiate to 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene is 1:3-5, and the dosage ratio of tetrahydrofuran to 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene is 45-60 ml:1g; and (C) in the step (B), the reaction temperature is 30-50 ℃ and the reaction time is 60-70 h.
  7. 7. Use of the bithiophene derivative according to claim 1 in electrochromic films and fluoride ion detection.
  8. 8. An electrochromic film, wherein the polymerized monomer of the electrochromic film is the bithiophene derivative of claim 1.
  9. 9. The method for preparing an electrochromic film according to claim 8, comprising the steps of: and mixing the bithiophene derivative, tetrabutylammonium hexafluorophosphate and an electrolytic solvent, and performing electrochemical polymerization to obtain the electrochromic film.
  10. 10. The preparation method of the catalyst according to claim 9, wherein the dosage ratio of the tetrabutyl hexafluorophosphoric acid to the electrolytic solvent is 0.08-0.2 mol:1L, and the dosage ratio of the bithiophene derivative to the electrolytic solvent is 0.8-2 mol:1L; The electrolytic solvent comprises dichloromethane and acetonitrile, wherein the volume ratio of the dichloromethane to the acetonitrile is 5-8:2-4; the sweeping speed of the electrochemical polymerization is 90-110 mV/s, the voltage range is 0-1.4V, and the cycle number is 8-12.

Description

Bithiophene derivative, preparation method and application thereof, electrochromic film and preparation method thereof Technical Field The invention relates to the technical field of electrochromic films, in particular to a bithiophene derivative, a preparation method and application thereof, and an electrochromic film and a preparation method thereof. Background Electrochromic refers to the fact that under the action of an applied voltage, oxidation-reduction reaction occurs due to charge injection and extraction, and meanwhile, the optical absorption of electrolyte ions changes in the visible light-near infrared region, and the change is macroscopically represented by reversible changes of color and transmittance. Electrochromic materials are increasingly attracting attention as a new functional material. As the organic conductive polymer electrochromic material is taken as an important component, researchers find that problems such as slow response speed limit further development and application along with continuous and deep research. In order to accelerate the response time of the conductive polymer electrochromic material, a strategy is generally adopted, starting from the regulation of the polymer aggregation state structure, and at present, in order to shorten the response time of the polymer electrochromic material, a loose accumulation structure can be constructed by introducing long alkoxy chains, so that more migration channels are provided, and the aim of shortening the response time is fulfilled. Tridentate boron is widely used in fluoride ion sensors because it has an empty p-orbital that is prone to combine with fluoride ions to form a stable octahedral structure. Therefore, how to use the characteristics to provide a functional side chain of the boron dimi-long alkoxy and apply the functional side chain to an electrochromic film, so that the film can realize fluoride ion detection while the response speed is improved, and the technical problem to be solved in the field is urgent. Disclosure of Invention The invention aims to provide a bithiophene derivative, a preparation method and application thereof, and an electrochromic film and a preparation method thereof, so as to solve the problems in the prior art. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a bithiophene derivative, which has the following structure: the invention also provides a preparation method of the bithiophene derivative, which comprises the following steps: (1) Preparation of 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene: In a protective atmosphere, mixing bithiophene, tetrahydrofuran, n-butyllithium solution and tributyl tin chloride for reaction to obtain tin bithiophene; (b) In a protective atmosphere, mixing tin-modified bithiophene, 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene, tetrakis (triphenylphosphine) palladium and N, N-dimethylformamide, and reacting to obtain 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene; In a protective atmosphere, mixing bithiophene, tetrahydrofuran, n-butyllithium solution and isopropanol pinacol borate for reaction to obtain boron esterified bithiophene; (II) mixing boron esterified bithiophene, 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene, potassium carbonate, tetrakis (triphenylphosphine) palladium, water and dioxane in a protective atmosphere, and reacting to obtain 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene; (2) Preparation of bithiophene derivatives: (A) Mixing and reacting a dimethoxyethane solution of lithium aluminum hydride, a dimethoxyethane solution of dimyristol boron fluoride and benzene in a protective atmosphere to obtain dimyristol boron hydride; (B) Mixing hydrogenated dimidiate boron, 1, 4-bithiophene-2, 5-bis- (6-hexynyl) -benzene and tetrahydrofuran, and reacting to obtain the bithiophene derivative. Preferably, the dosage ratio of tetrahydrofuran to bithiophene in the step (a) is 1-5 mL/1 mmol, the molar ratio of n-butyllithium to bithiophene is 0.95-1.1:1, the molar ratio of tributyltin chloride to bithiophene is 0.95-1.3:1, and the concentration of the n-butyllithium solution is 1.4-1.8 mol/L; the reaction temperature in the step (a) is 20-28 ℃ and the reaction time is 10-16 h; The molar ratio of tin-modified dithiophene to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene in the step (b) is 2.5-4:1, the dosage ratio of N, N-dimethylformamide to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 10-15 mL:1mmol, and the molar ratio of tetrakis (triphenylphosphine) palladium to 1, 4-diiodo-2, 5-bis- (6-hexynyl) -benzene is 0.03-0.08:1; The reaction temperature in the step (b) is 100-140 ℃ and the reaction time is 10-14 h. Preferably, the dosage ratio of tetrahydrofuran to bithiophene in the step (I) is 1-5 mL/1 mmol, the molar ratio of n-butyllithium to bithiophene is 0.95-1.1:1, the molar ratio of isopropanol pinacol borate to bithiophene is 1-2.1:1, and the concentration of the n-butyllithiu