Blue electrochromic compound, preparation method and subassembly thereof

Patent metadata

Field	Value
Publication number	US-9714256-B2
Application number	US-201414651005-A
Country	US
Kind code	B2
Filing date	Nov 7, 2014
Priority date	Dec 17, 2013
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

One class of blue thiophene electrochromic compounds include 3,4-(2,2-bis(2-oxo-3-phenylpropyl))propylenedioxythiophene, 3,4-(2,2-bis(2-oxo-3-phenylbutyl))propylenedioxythiophene, and 3,4-(2,2-bis(2-oxo-3-phenylamyl))propylenedioxythiophene. The thiophene electrochromic compounds can change color between blue and transparency. The thiophene compounds can be electropolymerized on the surface of the ITO glass to form a film. The film has characteristics of low driving voltage (within ±1V), fast response time, and large transmittance difference between colored-state and bleached-state (up to 77.5%). The thiophene electrochromic compounds can be used in the electrochromic window, rearview mirror, electrochomeric display, and the like.

First claim

The invention claimed is:

1. A method for preparing blue thiophene electrochromic compound as shown by formula (I),

wherein, n is 1, 2, or 3, comprising:
step 1: halogenating thiophene and bromine with the ratio of thiophene to bromine in mole from 1:4 to 1:6 in the presence of a reaction solvent of chloroform or dichloromethane at a reaction temperature of 60 to 80° C. for 24 to 48 hours, to give tetrabromothiophene;
step 2: reducing tetrabromothiophene with zinc powder with the ratio of tetrabromothiophene to zinc powder in mole from 1:5 to 1:8 in the presence of a mixed solution of acetic acid and water in which the volume ratio of acetic acid to water is 2:1-3:1 at room temperature for from 12 to 24 hours, to give 3,4-dibromothiophene;
step 3: etherifying 3,4-dibromothiophene with sodium methoxide with the ratio of 3,4-dibromothiophene to sodium methoxide in mole from 1:3 to 1:5 in the presence of a catalyst CuI that is in an amount of 10-25 mol % of 3,4-dibromothiophene at a reaction temperature of 60 to 80° C. for 48 to 72 hours, to give 3,4-dimethoxythiophene;
step 4: trans-etherifying-3,4-dimethoxythiophene with dibromoneopentyl glycol with the ratio of 3,4-dimethoxythiophene to dibromoneopentyl glycol in mole from 1:1.5 to 1:3 in the presence of a catalyst p-toluenesulfonic acid that in an amount of 10-15 mol % of 3,4-dimethoxythiophenein a reaction solvent of trichloromethane or toluene at a reaction temperature of 100 to 130° C. for 18 to 24 hours, to give 3,4-(2,2-dibromomethyl)propylenedioxythiophene;
step 5: etherifying 3,4-(2,2-dibromomethyl)propylenedioxythiophene with benzenemethanol, phenylethanol, and phenylpropanol, respectively in the presence of NaH at a temperature of 90-95° C. for 16-24 hrs, to give 3,4-(2,2-bis(2-oxo-3-phenylpropyl))propylenedioxythiophene, 3,4-(2,2-bis(2-oxo-3-phenylbutyl))propylenedioxythiophene, and 3,4-(2,2-bis(2-oxo-3-phenylamyl))propylenedioxythiophene, wherein the ratio of 3,4-(2,2-dibromomethyl)propylenedioxythiophene to benzenemethanol, phenylethanol, or phenylpropanol in mole is from 1:2 to 1:4, the ratio of 3,4-(2,2-dibromomethyl)propylenedioxythiophene to NaH in mole is from 1:4 to 1:8.

2. The method of claim 1 , wherein, in step 5, the ratio of 3,4-(2,2-dibromomethyl)propylenedioxythiophene:benzenemethanol, phenylethanol, or phenylpropanol:NaH in mole is 1:2-4:4-8.

Assignees

• Boe Technology Group Co Ltd
• Univ Science & Tech China

Inventors

• Xu Chunye
• Mi Sai
• Zheng Jianming

Classifications

• C09K9/02

  Organic tenebrescent materials · CPC title

• C09K2211/1092

  containing sulfur as the only heteroatom · CPC title

• C07D495/04 Primary

  Ortho-condensed systems · CPC title

• C09K2211/1007

  Non-condensed systems · CPC title

• C09K2211/1096

  containing other heteroatoms · CPC title