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CN-122011343-A - Epindole diketone polymer and preparation method and application thereof

CN122011343ACN 122011343 ACN122011343 ACN 122011343ACN-122011343-A

Abstract

The invention belongs to the technical field of electrochromic materials, and discloses an epindole diketone polymer and a preparation method and application thereof. The invention provides an epiindoledione polymer, which is characterized in that epiindoledione is used as a heterocyclic monomer with unique structure and easy functionalization, and the molecular structure of the epiindoledione polymer contains amide and a conjugated aromatic system at the same time, and has good electron transmission capability and adjustable electrochemical activity. The film prepared by the compound is orange in a neutral state, transparent in an oxidation state, and has an optical contrast ratio of 37% in a 408nm wavelength range, a coloring time of 0.96s and a fading time of 2.94s. The optical contrast after 1250 cycles under the step voltage of 0V and 1.0V can still keep 25% of the original contrast, and the electrochromic material has strong chemical stability, high sensitivity and short response time.

Inventors

  • FENG MENGLONG
  • HUANG ZHUO
  • LUO DELIANG
  • TAO MING
  • WANG JIANJUN
  • WAN QI
  • LI WEIJUN

Assignees

  • 杭州百合辉柏赫颜料有限公司
  • 浙江工业大学

Dates

Publication Date
20260512
Application Date
20260327

Claims (10)

  1. 1. An epindole polymer characterized by having a structure according to formula I: A formula I; Wherein, the value range of n in the formula I is 16-20.
  2. 2. A process for the preparation of an epindole polymer according to claim 1 comprising the steps of: mixing a first monomer, a second monomer and a palladium catalyst with an organic solvent in a protective atmosphere, and performing a Stille coupling reaction to obtain an epiindoledione polymer; wherein the first monomer has a structure as shown in formula II: A formula II; The second monomer has a structure shown in a formula III: Formula III.
  3. 3. The method of preparation of claim 2, wherein the palladium catalyst comprises one or more of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium dichloride, [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride.
  4. 4. The method according to claim 2 or 3, wherein the molar ratio of the first monomer, the second monomer and the palladium catalyst is 1:1:0.05 to 1:1:0.1.
  5. 5. The preparation method according to claim 4, wherein the Stille coupling reaction conditions comprise a reaction temperature of 90-130 ℃ and a reaction time of 48-72 h.
  6. 6. The method of producing according to claim 2, wherein the method of producing the first monomer comprises the steps of: (1) The para-bromoaniline and ethyl chloroacetate undergo substitution reaction to obtain (4-bromophenyl) glycine ethyl ester; (2) The (4-bromophenyl) glycine ethyl ester and diethyl oxalate undergo condensation reaction to obtain diethyl 2- ((4-bromophenyl) amino) malonate; (3) Nucleophilic addition-elimination reaction of diethyl 2- ((4-bromophenyl) amino) malonate and p-bromoaniline to obtain diethyl 2, 3-bis ((4-bromophenyl) amino) fumarate; (4) 2, 3-bis ((4-bromophenyl) amino) diethyl fumarate reacts with crude oil to obtain 6-bromo-3- ((4-bromophenyl) amino) -4-oxo-1, 4-dihydroquinoline-2-carboxylic acid ethyl ester; (5) Cyclized condensation reaction is carried out on 6-bromo-3- ((4-bromophenyl) amino) -4-oxo-1, 4-dihydroquinoline-2-ethyl formate and polyphosphoric acid to obtain 2, 8-dibromo-5, 11-dihydrodibenzo [ b, g ] [1,5] naphthyridine-6, 12-dione; (6) The substitution reaction of 2, 8-dibromo-5, 11-dihydrodibenzo [ b, g ] [1,5] naphthyridine-6, 12-dione and 1-bromo-2-propyl heptane is carried out to obtain a first monomer.
  7. 7. The method according to claim 6, wherein the first monomer is produced by: The molar ratio of the p-bromoaniline to the ethyl chloroacetate in the step (1) is 1:1-1:1.2, and the substitution reaction conditions in the step (1) comprise the reaction temperature of 70-100 ℃ and the reaction time of 8-12 h; The molar ratio of the (4-bromophenyl) glycine ethyl ester to the diethyl oxalate in the step (2) is 1:1-1:1.2, and the condensation reaction conditions in the step (2) comprise the reaction temperature being room temperature and the reaction time being 24-72 h; The mol ratio of the diethyl 2- ((4-bromophenyl) amino) malonate to the p-bromoaniline in the step (3) is 1:1-1:1.2, and the nucleophilic addition-elimination reaction conditions in the step (3) comprise the reaction temperature of 60-100 ℃ and the reaction time of 2-8 h; The ratio of the mass of the diethyl 2, 3-bis ((4-bromophenyl) amino) fumarate to the volume of the crude oil in the step (4) is 1 g:3-15 mL, and the reaction conditions in the step (4) comprise the reaction temperature of 240-280 ℃ and the reaction time of 0.5-1 h; The mass ratio of the 6-bromo-3- ((4-bromophenyl) amino) -4-oxo-1, 4-dihydroquinoline-2-ethyl formate to the polyphosphoric acid in the step (5) is 1:15-20, and the cyclized condensation reaction conditions in the step (5) comprise the reaction temperature of 140-160 ℃ and the reaction time of 2-4 h; The molar ratio of the 2, 8-dibromo-5, 11-dihydrodibenzo [ b, g ] [1,5] naphthyridine-6, 12-dione to the 1-bromo-2-propyl heptane in the step (6) is 1:10-1:15, and the substitution reaction conditions in the step (6) comprise the reaction temperature of 120-140 ℃ and the reaction time of 2-4 h.
  8. 8. The method of producing according to claim 2, wherein the method of producing the second monomer comprises the steps of: And (3) carrying out substitution reaction on the 2- (2-ethylhexyl) cyclopentabithiophene, n-butyllithium and tributyl tin chloride to obtain a second monomer.
  9. 9. The preparation method of the second monomer according to claim 8, wherein in the preparation method of the second monomer, the molar ratio of the 2- (2-ethylhexyl) cyclopentadithiophene to the n-butyllithium is 1:2-2.2, the molar ratio of the 2- (2-ethylhexyl) cyclopentadithiophene to the tributyl tin chloride is 1:2-2.2, and the substitution reaction condition comprises that the reaction temperature is room temperature and the reaction time is 16-18 h.
  10. 10. Use of an epiindoledione polymer of claim 1 or an epiindoledione polymer prepared by a method of any one of claims 2-9 in electrochromic materials.

Description

Epindole diketone polymer and preparation method and application thereof Technical Field The invention relates to the technical field of electrochromic materials, in particular to an epindole diketone polymer and a preparation method and application thereof. Background Electrochromic (Electrochromism) refers to a phenomenon that the optical properties (such as reflectivity, transmissivity and absorptivity) of a material are changed stably and reversibly under the action of an external electric field, and the phenomenon is mainly represented by color change. This process is typically due to oxidation-reduction reactions within the material, accompanied by intercalation/deintercalation of ions and migration of electrons. The electrochromic material is widely applied to the fields of intelligent windows, automatic anti-glare rearview mirrors, self-adaptive camouflage, electronic display equipment and the like due to the characteristics of rich color change and strong stability. Currently, a variety of electrochromic polymer systems have been intensively studied and implemented for use. For example, polypyrrole is widely used in smart windows and displays due to its good conductivity and electrochemical stability, polyaniline is one of the most well-studied electrochromic materials due to its polymorphic reversible color change behavior and simple synthesis process, and in addition, polythiophenes (such as poly (3, 4-ethylenedioxythiophene), PEDOT) also exhibit great potential in flexible electronic devices due to their excellent electrochromic properties and high contrast. However, although these materials are mature in performance, it is still of great importance to develop electrochromic polymers with new structures, higher stability or wider color mixing ranges. Disclosure of Invention The invention aims to provide an epiindoledione polymer, a preparation method and application thereof, and aims to expand the structural diversity of electrochromic materials and improve the performance of the electrochromic materials. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides an epiindoledione polymer which has a structure shown in a formula I: A formula I; Wherein, the value range of n in the formula I is 16-20. The invention also provides a preparation method of the epindole diketone polymer, which comprises the following steps: mixing a first monomer, a second monomer and a palladium catalyst with an organic solvent in a protective atmosphere, and performing a Stille coupling reaction to obtain an epiindoledione polymer; wherein the first monomer has a structure as shown in formula II: A formula II; The second monomer has a structure shown in a formula III: Formula III. Further, in the preparation method, the palladium catalyst includes one or more of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium dichloride, [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride. Further, in the preparation method, the molar ratio of the first monomer to the second monomer to the palladium catalyst is 1:1:0.05-1:1:0.1. Further, in the preparation method, the Stille coupling reaction conditions comprise a reaction temperature of 90-130 ℃ and a reaction time of 48-72 h. Further, in the preparation method, the preparation method of the first monomer includes the steps of: (1) The para-bromoaniline and ethyl chloroacetate undergo substitution reaction to obtain (4-bromophenyl) glycine ethyl ester; (2) The (4-bromophenyl) glycine ethyl ester and diethyl oxalate undergo condensation reaction to obtain diethyl 2- ((4-bromophenyl) amino) malonate; (3) Nucleophilic addition-elimination reaction of diethyl 2- ((4-bromophenyl) amino) malonate and p-bromoaniline to obtain diethyl 2, 3-bis ((4-bromophenyl) amino) fumarate; (4) 2, 3-bis ((4-bromophenyl) amino) diethyl fumarate reacts with crude oil to obtain 6-bromo-3- ((4-bromophenyl) amino) -4-oxo-1, 4-dihydroquinoline-2-carboxylic acid ethyl ester; (5) Cyclized condensation reaction is carried out on 6-bromo-3- ((4-bromophenyl) amino) -4-oxo-1, 4-dihydroquinoline-2-ethyl formate and polyphosphoric acid to obtain 2, 8-dibromo-5, 11-dihydrodibenzo [ b, g ] [1,5] naphthyridine-6, 12-dione; (6) The substitution reaction of 2, 8-dibromo-5, 11-dihydrodibenzo [ b, g ] [1,5] naphthyridine-6, 12-dione and 1-bromo-2-propyl heptane is carried out to obtain a first monomer. Further, in the preparation method of the first monomer: The molar ratio of the p-bromoaniline to the ethyl chloroacetate in the step (1) is 1:1-1:1.2, and the substitution reaction conditions in the step (1) comprise the reaction temperature of 70-100 ℃ and the reaction time of 8-12 h; The molar ratio of the (4-bromophenyl) glycine ethyl ester to the diethyl oxalate in the step (2) is 1:1-1:1.2, and the condensation reaction conditions in the step (2) comprise the reaction temperature being room tempera