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CN-121975094-A - Low-voltage-driven high-band-gap yellow to transparent electrochromic polymer and preparation method and application thereof

CN121975094ACN 121975094 ACN121975094 ACN 121975094ACN-121975094-A

Abstract

The invention provides a low-voltage driven high-band-gap yellow to transparent electrochromic polymer, and a preparation method and application thereof. The high band gap yellow to transparent electrochromic polymer of the present invention is prepared by reacting 3, 4-bis (3-isobutoxy-2, 2-bis (isobutoxymethyl) propoxy) thiophene with a compound M2, M3 or M4 in the presence of N, N-dimethylacetamide, potassium carbonate, palladium acetate, and trimethylacetic acid. The high band gap yellow to transparent electrochromic polymer can be dissolved in organic solvents such as dichloromethane, ethyl acetate, dimethylbenzene, tetrahydrofuran and the like, can form a film on the surface of a conductive material through processes such as spraying, knife coating and the like, and the formed polymer film shows good electrochromic behavior, can show yellow to transparent conversion, has the advantages of low-voltage driving, high optical contrast, high response speed, good stability and the like, and can be used as a basic electrochromic material in the electrochromic field.

Inventors

  • ZHOU DEPING
  • WENG XIAODI
  • WANG JIE
  • ZHOU XUSHEN
  • JIANG WEIJIE
  • Zhao Bofei
  • SU PEILIN

Assignees

  • 中国人民解放军96911部队

Dates

Publication Date
20260505
Application Date
20251229

Claims (10)

  1. 1. A low voltage driven high bandgap yellow to transparent electrochromic polymer having the structural formula: wherein R is alkyl, n is a natural number between 8 and 100, ar is the following group M2, M3 or M4: 。
  2. 2. a method of preparing a high band gap yellow to transparent electrochromic polymer according to claim 1, comprising: reacting compound M1 with compound M2, M3 or M4 in the presence of N, N-dimethylacetamide, potassium carbonate, palladium acetate and trimethylacetic acid; The structural formula of the compound M1 is as follows: Wherein R is alkyl; The structural formula of the compounds M2, M3 and M4 is as follows: Wherein Ar is the following group M2, M3 or M4, respectively: 。
  3. 3. The process according to claim 2, wherein the molar ratio of compound M1 to compound M2, M3 or M4 is 1 (0.9-1.1).
  4. 4. The preparation method according to claim 2, wherein the molar ratio of the compound M1 to the potassium carbonate to the trimethylacetic acid to the palladium acetate is 1 (1-2): 0.1-0.25): 0.02-0.04.
  5. 5. The preparation method according to claim 2, wherein the reaction temperature is 90-140 ℃ and the reaction time is 48-96 h.
  6. 6. The method of manufacturing according to claim 2, further comprising: and (3) dripping the reaction liquid obtained by the reaction into cold methanol for precipitation, filtering, collecting the precipitate, drying, and sequentially adopting methanol, normal hexane and chloroform for Soxhlet extraction.
  7. 7. The method of claim 6, wherein the Soxhlet extraction time is 20 to 30 h.
  8. 8. A polymer film obtained by spraying or knife coating the high band gap yellow to transparent electrochromic polymer of claim 1.
  9. 9. The polymer film of claim 8, wherein the polymer film has a thickness of 200 to 600 nm a.
  10. 10. Use of a high band gap yellow to transparent electrochromic polymer according to claim 1 or a polymer film according to claim 8 in an electrochromic device.

Description

Low-voltage-driven high-band-gap yellow to transparent electrochromic polymer and preparation method and application thereof Technical Field The invention relates to the technical field of electrochromic materials, in particular to a low-voltage-driven high-band-gap yellow to transparent electrochromic polymer, and a preparation method and application thereof. Background The electrochromic material can reversibly change the optical performance under the action of external potential, and has great application potential in the aspects of self-adaptive camouflage, intelligent vehicle windows, anti-dazzle rearview mirrors and the like. Currently, electrochromic materials include transition metal oxides, viologen small molecules, conductive polymers, and the like. The conductive polymers have excellent electrochromic properties, such as vivid color display, easy color matching through structural modification, high contrast, quick switching response, good stability, easy coating and the like, which make them have great attraction to the research of the electrochromic field, wherein yellow and orange high band gap conductive polymers are important base materials of electrochromic materials. Therefore, the development of novel yellow and orange conductive polymers with excellent electrochromic properties has important significance for the research of electrochromic fields. In view of this, the present invention has been made. Disclosure of Invention The invention aims to provide a low-voltage-driven high-band-gap yellow-to-transparent electrochromic polymer, a preparation method and application thereof, and a polymer film prepared by using the polymer shows good electrochromic behavior, can show yellow-to-transparent conversion, and has the advantages of low-voltage driving, high optical contrast, high response speed, good stability and the like. The invention provides a low-voltage driven high band gap yellow to transparent electrochromic polymer, which has the following structural formula: Wherein R represents an alkyl group, preferably an isobutyl group, n represents a natural number between 8 and 100, preferably between 40 and 60, and Ar is the following group M2, M3 or M4: 。 The main chain intercalation of weak electron-donating units and the increase of the steric site resistance are two main ways to obtain high band gap polymers. In order to achieve yellow and orange color display, it is desirable that the polymer has a higher band gap, and in order to improve the stability of the polymer, the band gap improvement should be caused by steric hindrance effect rather than electron induction effect. Thus, electron rich groups should be included in the polymer structure and groups that disrupt the planar conjugation properties. Generally, the electron-rich group is mainly of thiophene structure, while the group breaking plane conjugation has benzene ring, naphthalene ring and the like, and the corresponding polymer generally has higher color-changing potential, so that the color-changing stability is poor. Thiophene is a five-membered heterocyclic aromatic compound containing sulfur. The hydrogen atoms on the thiophene ring are relatively active, wherein the alpha and beta positions of the sulfur atoms are two different reaction sites, which facilitates modification and modification of the structure of the thiophene to obtain molecules with better performance. The thiophene derivative is used as an organic conjugated unit, the conductive polymer formed by the thiophene derivative shows excellent performance in the field of organic electrochromic, and meanwhile, the conductive polymer formed by the thiophene derivative has a larger aromatic ring structure, so that the electrochemical oxidation potential of the conductive polymer is not high, and the thiophene derivative can be used as an ideal structural unit for designing and preparing high band gap electrochromic polymers such as yellow and orange. Based on the method, the large-size branched chain group is introduced into the dioxythiophene main chain, the polymer coplanarity is broken by utilizing the plane distortion characteristic of the dioxythiophene main chain, and meanwhile, the high band gap yellow to transparent electrochromic polymer with low voltage driving, high optical contrast and high stability is realized based on the strong electron donating property of the dioxythiophene. The invention also provides a preparation method of the high band gap yellow to transparent electrochromic polymer, which comprises the step of reacting 3, 4-bis (3-isobutoxy-2, 2-bis (isobutoxymethyl) propoxy) thiophene (compound M1) with a compound M2, M3 or M4 in the presence of N, N-dimethylacetamide, potassium carbonate, palladium acetate and trimethylacetic acid. The preparation method of the invention has the reaction route as follows: The structural formula of 3, 4-bis (3-isobutoxy-2, 2-bis (isobutoxymethyl) propoxy) thiophene (compound M1) is as follows: Wherein R re