Electrochromic copolymers from precursors, method of making, and use thereof
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
H01B-001/12
C08G-075/06
C09D-005/24
C09D-181/02
B05D-005/06
출원번호
US-0416503
(2013-07-23)
등록번호
US-9944757
(2018-04-17)
국제출원번호
PCT/US2013/051558
(2013-07-23)
국제공개번호
WO2014/018472
(2014-01-30)
발명자
/ 주소
Sotzing, Gregory Allen
출원인 / 주소
THE UNIVERSITY OF CONNECTICUT
대리인 / 주소
Cantor Colburn LLP
인용정보
피인용 횟수 :
0인용 특허 :
27
초록
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.
대표청구항▼
1. A precursor mixture comprising: two precursors,wherein a first precursor is wherein Ar1 is a heteroaryl electron donor unit; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C122 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are i
1. A precursor mixture comprising: two precursors,wherein a first precursor is wherein Ar1 is a heteroaryl electron donor unit; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C122 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater; and wherein a second precursor is wherein Ar2 is a heteroaryl electron acceptor unit that is bis-(3,4-(2′,2′-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater. 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; andconverting 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 wherein Ar1 is a heteroaryl electron donor unit; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater; and wherein the second precursor is wherein Ar2 is a heteroaryl electron acceptor unit that is bis-(3,4-(2′,2′-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater,wherein the conjugated copolymer comprises a unit of YR1R2. 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 wherein Ar1 is bis-3,4-ethylenedioxythiophene; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater; and wherein the second precursor is wherein Ar1 is bis-(3,4-ethylenedioxythiophene)-2,1,3-benzothiadiazole; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater,wherein the conjugated copolymer comprises a unit of YR1R2. 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 wherein Ar1 is a heteroaryl electron donor unit; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater; and wherein a second precursor is wherein Ar2 is a heteroaryl electron acceptor unit that is bis-(3,4-ethylenedioxythiophene)-2,1,3-benzothiadiazole, bis-(3,4-(2′,2′-dimethylpropylenedioxy)thiophene)-2,1,3-benzothiadiazole, imidazole, triazine, tetrazine, quinoline, pyridine, thiadiazole, or derivatives thereof with the proviso that when Ar2 is bis-(3,4-ethylenedioxythiophene)-2,1,3-benzothiadiazole then Ar1 is bis-3,4-ethylenedioxythiophene; each occurrence of R1 and R2 is independently C3-C12 alkyl, C3-C12 haloalkyl, or aryl; X is O, S, (YR1R2)x, or (CRaRb)x wherein x is 0, 1, 2, 3, or 4, and Ra and Rb are independently hydrogen, C1-C12 alkyl, or C1-C12 haloalkyl; each occurrence of Y is independently Si, Ge, Sn, or Pb; and n is about 10 or greater,wherein the conjugated copolymer comprises a unit of YR1R2. 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.
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