Green polythiophene electrochromic materials, method for preparation thereof, and assembly comprising the same

Patent metadata

Field	Value
Publication number	US-9926406-B2
Application number	US-201414436701-A
Country	US
Kind code	B2
Filing date	Sep 5, 2014
Priority date	Dec 6, 2013
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

A novel soluble green polythiophene electrochromic material, poly[2,3-bis(3,4-dialkoxyphenyl)-5,8-bis(3,4-ethylenedioxythienyl)quinoxaline], as shown by formula (I),

wherein, n is an integer from 40 to 200, R=C m H 2m+1 , wherein m is an integer from 8 to 14.

First claim

The invention claimed is:

1. A green polythiophene electrochromic material, poly[2,3-bis(3,4-di(dodecyloxy)phenyl)-5,8-bis(3,4-ethylenedioxythienyl)quinoxaline], as shown by formula (II),

wherein, n is an integer from 40 to 200, having a number-average molecular weight of 50000-70000.

2. A method for preparing the green polythiophene electrochromic material of claim 1 , comprising;
Step 1: reacting catechol with alkyl bromide having a alkyl chain length of 8-14 carbon atoms in the presence of potassium hydroxide to give 1,2-dialkoxybenzene, compound 1;
Step 2: allowing compound 1 and oxalyl chloride to undergo an electrophilic substitution reaction in the presence of anhydrous aluminum chloride, to give 1,2-bis(3,4-dialkoxyphenyl)-1,2-done, compound 2;
Step 3: allowing 2,1,3-benzothiadiazole and bromine to undergo halogenation, to give 4,7-dibromo-2,1,3-benzothiadiazole, compound 3;
Step 4: allowing compound 3 and sodium borohydride to undergo a reduction reaction, to give 3,6-dibromo-o-phenylenediamine, compound 4;
Step 5: reacting compound 2 with compound 4 under the catalyzation of p-toluenesulfonic acid, to give 2,3-bis(3,4-dialkoxyphenyl)-5,8-dibromoquinoxaline, compound 5;
Step 6: reacting 3,4-ethylenedioxythiophene with n-butyllithium and tributyltin chloride, to give 2-tributyltin-3,4-ethylenedioxythiophene, compound 6;
Step 7: allowing compound 5 and compound 6 to undergo a stille coupling reaction under the catalyzation of bis(triphenylphosphine)palladium dichloride or palladium acetate, to give 2,3-bis(3,4-dialkoxyphenyl)-5,8-bis(3,4-ethylenedioxythienyl)quinoxaline, compound 7;
Step 8: polymerizing compound 7 under catalytic oxidation from ferric trichloride, to give poly[2,3-bis(3,4-dialkoxyphenyl)-5,8-bis(3,4-ethylenedioxythienyl)quinoxaline], compound 8.

3. The method of claim 2 , wherein, in step 1, the ratio of catechol to alkyl bromide in mole is from 1:2 to 1:4, the reaction solvent is ethanol, the reaction temperature is from 60 to 80° C., and the reaction time is from 4 to 10 hours.

4. The method of claim 2 , wherein, in step 2, the ratio of compound 1 to anhydrous aluminum chloride in mole is from 1:1 to 1:1.2, the ratio of compound 1 to oxalyl chloride in mole is from 1:0.5 to 1:0.6, the reaction solvent is carbon disulfide, the reaction temperature is 0° C., and the reaction time is from 18 to 24 hours.

5. The method of claim 2 , wherein, in step 3, the ratio of 2,1,3-benzothiadiazole to bromine in mole is from 1:2 to 1:4, the reaction solvent is an aqueous hydrobromic acid solution at a mass concentration 14%, the reaction temperature is from 80 to 100° C., and the reaction time is from 8 to 12 hours.

6. The method of claim 2 , wherein, in step 4, the ratio of compound 3 to sodium borohydride in mole is from 1:5 to 1:10, the reaction solvent is ethanol, and the reaction temperature is room temperature.

7. The method of claim 2 , wherein, in step 5, the ratio of compound 2 to compound 4 in mole is from 1:1 to 1:12, the catalyst is p-toluenesulfonic acid in an amount of 5-10 wt % of compound 4, the reaction solvent is trichloromethane or ethanol, the reaction temperature is from 60 to 80° C., and the reaction time is from 10 to 12 hours.

8. The method of claim 2 , wherein, in step 6, the ratio of 3,4-ethylenedioxythiophene to n-butyllithium in mole is from 1:1 to 1:1.2, the reaction is conducted at −78° C. with stirring for 0.5-1 hour, the ratio of 3,4-ethylenedioxythiophene to tributyltin chloride in mole is from 1:1 to 1:1.2, and the reaction is conducted at room temperature for 16-24 hours.

9. The method of claim 2 , wherein, in step 7, the ratio of compound 5 to compound 6 in mole is from 1:2 to 1:2.5, the reaction solvent is anhydrous tetrahydrofuran, the catalyst is bis(triphenylphosphine)palladium dichloride or palladium acetate in an amount of 5-10 wt % of compound 5, the reaction temperature is from 70 to 100° C., and the reaction time is from 24 to 48 hours.

10. The method of claim 2 , wherein, in step 8, the ratio of compound 7 to ferric trichloride in mole is from 1:3 to 1:5, and the reaction is conducted at room temperature with stirring for 24-48 hours.

11. Use of the green polythiophene electrochromic material of claim 1 for preparing a uniform electrochromic film, comprising
dissolving poly[2,3-bis(3,4-di(dodecyloxy)phenyl)-5,8-bis(3,4-ethylenedioxythienyl)quinoxaline]in trichloromethane to prepare a solution of 2-3 mg/ml, and
spraying the solution directly onto a surface of an ITO glass with an airbrush to form the uniform electrochromic film.

12. An assembly comprising the green polythiophene electrochromic material of claim 1 .

13. The assembly of claim 12 , wherein said assembly is an electrochromic film.

14. An assembly comprising the green polythiophene electrochromic material of claim 1 .

15. The assembly of claim 14 , wherein said assembly is an electrochromic film.

Assignees

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

Inventors

• Xu Chunye
• Mi Sai
• Zheng Jianming

Classifications

• C09K9/02

  Organic tenebrescent materials · CPC title

• C08G2261/3247

  containing combinations of different heteroatoms other than nitrogen and oxygen or nitrogen and sulfur · CPC title

• C08G2261/11

  Homopolymers · CPC title

• C08G2261/43

  Chemical oxidative coupling reactions, e.g. with FeCl3 · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title