Electrochromic copolymers from precursors, method of making, and use thereof

• US 9,944,757 B2
• Filed: 07/23/2013
• Issued: 04/17/2018
• Est. Priority Date: 07/23/2012
• Status: Active Grant

• Current Assignee: University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Sotzing, Gregory Allen
• Primary Examiner(s): Kopec, Mark
• Assistant Examiner(s): Thomas, Jaison P
• Application Number:
  US14/416,503
• Publication Number:
  US 20150232622A1
• Time in Patent Office: 1,729 Days
• CPC Class Codes: B05D 5/06 to obtain multicolour or other optical effects B05D5/02 takes precedence
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C07F 7/2208 Compounds having tin linked only to carbon, hydrogen and/or halogen
• CPC Class Codes: C08G 2261/124 alternating
• CPC Class Codes: C08G 2261/1424 containing ether groups, including alkoxy
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/3246 containing nitrogen and sulfur as heteroatoms
• CPC Class Codes: C08G 2261/344 containing heteroatoms
• CPC Class Codes: C08G 2261/414 Stille reactions
• CPC Class Codes: C08G 2261/54 electrochromatic
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: C08G 75/06 from cyclic thioethers
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C09D 181/02 Polythioethers; Polythioether-ethers
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01B 1/124 Intrinsically conductive polymers

Abstract

This invention relates to electrochromic copolymers having a specific color transition prepared from precursors containing Si, Ge, Sn, or Pb, methods of producing such copolymers and precursors, and applications utilizing the copolymers to prepare electrochromic devices.

Claims

1. A precursor mixture comprising:

two precursors,

wherein a first precursor is

2. The precursor mixture of claim 1, wherein Ar¹ is 3,4-ethylenedioxythiophene, bis-3,4-ethylenedioxythiophene, thiophene, furan, pyrrole, indole, or derivatives thereof;

and Ar² is bis-(3,4-(2′

,2′

-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof.

3. The precursor mixture of claim 1, wherein Y is Si and X is O.

4. The precursor mixture of claim 1, wherein R¹ and R² are independently n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

5. The precursor mixture of claim 1, wherein R¹ and R² are independently n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

6. The precursor mixture of claim 1, wherein when converted by oxidative reaction process results in a conjugated copolymer exhibiting a black color.

7. A method of preparing a conductive copolymer film, comprising:

coating a substrate with a precursor mixture according to claim 1; and

converting the precursor mixture to a conductive conjugated copolymer;

wherein the coating is prepared by any one of the following processes;

compression molding, melt coating, ink jet printing, screen printing, roll to roll printing processes, spin coating, meniscus and dip coating, spray coating, brush coating, spray casting, doctor blade application, or curtain casting.

8. A conjugated copolymer comprising a copolymer prepared by converting a precursor mixture comprising two precursors to the conjugated copolymer,

wherein the first precursor is

9. The conjugated copolymer of claim 8, wherein Ar¹ is 3,4-ethylenedioxythiophene, bis-3,4-ethylenedioxythiophene, thiophene, furan, pyrrole, indole, or derivatives thereof;

and Ar² is bis-(3,4-(2′

,2′

-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof.

10. The conjugated copolymer of claim 8, wherein Y is Si and X is O.

11. The conjugated copolymer of claim 8, wherein R¹ and R² are independently n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

12. The conjugated copolymer of claim 8, wherein R¹ and R² are independently n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

13. The conjugated copolymer of claim 8, wherein the conversion is by an oxidative reaction process.

14. The conjugated copolymer of claim 8, wherein the conjugated copolymer exhibits a black color.

15. An article prepared comprising the conductive conjugated copolymer of claim 8.

16. A conjugated copolymer comprising a copolymer prepared by converting a precursor mixture comprising two precursors to the conjugated copolymer,

wherein the first precursor is

17. The conjugated copolymer of claim 16, wherein Y is Si and X is O.

18. An article prepared comprising the conductive conjugated copolymer of claim 16.

19. A method of preparing a conductive conjugated copolymer, comprising:

converting a precursor mixture comprising two precursors to the conductive conjugated copolymer,

wherein a first precursor is

20. The method of claim 19, wherein the converting is via chemical oxidation, electrochemical oxidation, or bromine conversion.

21. The method of claim 20, wherein the oxidative conversion occurs in solid state.

22. The method of claim 19, wherein Ar¹ is 3,4-ethylenedioxythiophene, bis-3,4-ethylenedioxythiophene, thiophene, furan, pyrrole, indole, or derivatives thereof;

and Ar¹ is bis-(3,4-(2′

,2′

-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof.

23. The method of claim 19, wherein Y is Si and X is O.

24. The method of claim 19, wherein R¹ and R² are independently n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

25. The method of claim 19, wherein R¹ and R² are independently n-butyl, t-butyl, n-pentyl, 3-methylbutyl, sec-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-septyl, n-octyl, or the perfluorinated groups thereof.

26. The method of claim 19, wherein the conjugated copolymer exhibits a black color.