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US 2022/0396728 A1Published application
Electrochromic materials; preparation and use thereof
AssigneeUniversity of Connecticut
InventorsGregory Allen Sotzing, Robert Adrian Daniels
Life of this patent
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Abstract
Disclosed herein are new electrochromic materials, including small molecule, oligomeric, and polymeric electrochromic materials, and compositions comprising the electrochromic materials and a salt. Further disclosed are electrochromic devices prepared from the electrochromic materials and electrochromic material compositions. Also disclosed are melt processable polymeric electrochromic materials, melt processable compositions comprising the melt processable polymeric electrochromic material, and a salt; and devices prepared therefrom.
Claims22
An electrochromic material composition, comprising
- a salt;
- a small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), or (III), a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), or (VI-A), or a combination thereof;
- and
- optionally a plasticizer, a solvent, or a combination thereof;
- wherein
- wherein
- each X1 independently is O, S, or NR;
- R is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, and yet more specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
- each R1 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl;
- each Z1 independently is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- Ar is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, terphenyl, or triphenylene;
- each Z2 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- q is 0, 1, 2, 3, or 4, specifically 0, 1, or 2;
- Ar1 and Ar2 each independently is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, pyridyl, terphenyl, or triphenylene;
- each X2 independently is O, S, or NR;
- each R2 and R3 independently is
- C1-20 alkylene, specifically C1-10 alkylene, more specifically C1-6 alkylene, or
- a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, specifically 2-10 carbon atoms, and more specifically 2-6 carbon atoms, or
- a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, specifically 1 or 2 Q1 groups, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
- a is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- b is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- and
- n is about 10,000 to about 100,000 g/mol.
20 more elements
A method comprising,
- heating an electrochromic material composition to form a melt;
- and
- extruding or molding the melt to form a melt processed electrochromic material composition,
- wherein the molding is injection molding, blow molding, rotational molding, or compression molding and the extruding is cast film extrusion;
- the electrochromic material composition comprises
- a salt;
- a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), or (VI-A), or a combination thereof;
- and
- wherein
- each Z1 independently is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- each Z2 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- q is 0, 1, 2, 3, or 4, specifically 0, 1, or 2;
- Ar1 and Ar2 each independently is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, pyridyl, terphenyl, or triphenylene;
- each X2 independently is O, S, or NR, R is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, and yet more specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
- each R2 and R3 independently is
- C1-20 alkylene, specifically C1-10 alkylene, more specifically C1-6 alkylene, or
- a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, specifically 2-10 carbon atoms, and more specifically 2-6 carbon atoms, or
- a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, specifically 1 or 2 Q1 groups, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
- a is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol %;
- b is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol %;
- and
- n is about 10,000 to about 100,000 g/mol.
19 more elements
A method of forming an electrochromic film, comprising,
- providing a solution or homogeneous suspension comprising a salt;
- a solvent;
- a small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), or (III), a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), or (VI-A), or a combination thereof and optionally a plasticizer;
- and
- forming an electrochromic film from the solution or suspension,
- wherein the small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), (III), and polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), (VI-A) have the structures:
- wherein
- each X1 independently is O, S, or NR;
- R is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, and yet more specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
- each R1 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl;
- each Z1 independently is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- Ar is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, terphenyl, or triphenylene;
- each Z2 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- q is 0, 1, 2, 3, or 4, specifically 0, 1, or 2;
- Ar1 and Ar2 each independently is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, pyridyl, terphenyl, or triphenylene;
- each X2 independently is O, S, or NR;
- each R2 and R3 independently is
- C1-20 alkylene, specifically C1-10 alkylene, more specifically C1-6 alkylene, or
- a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, specifically 2-10 carbon atoms, and more specifically 2-6 carbon atoms, or
- a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, specifically 1 or 2 Q1 groups, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
- a is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- b is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- and
- n is about 10,000 to about 100,000 g/mol.
21 more elements
A method of preparing a copolymer electrochromic material, comprising
- reacting a first polyester with a second polyester in a transesterification process to form a copolymer electrochromic material, wherein the copolymer electrochromic material is of formula (IV), (V), (V-A), (VI), or (VI-A)
- wherein
- each Z1 independently is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- each Z2 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- q is 0, 1, 2, 3, or 4, specifically 0, 1, or 2;
- Ar1 and Ar2 each independently is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, pyridyl, terphenyl, or triphenylene;
- each X2 independently is O, S, or NR, R is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, and yet more specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, wherein at least one X2 is O;
- each R2 and R3 independently is
- C1-20 alkylene, specifically C1-10 alkylene, more specifically C1-6 alkylene, or
- a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, specifically 2-10 carbon atoms, and more specifically 2-6 carbon atoms, or
- a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, specifically 1 or 2 Q1 groups, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
- a is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol %;
- b is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol %;
- and
- n is about 10,000 to about 100,000 g/mol.
12 more elements
An electrochromic device comprising:
- an electrochromic layer comprising an electrochromic material composition, and
- an electrolyte layer,
- wherein the electrochromic layer is adjacent to the electrolyte layer;
- wherein the electrochromic material composition is a small molecule organic electrochromic material of formula (I), (I-A), (II), (II-A), or (III), a polymer or copolymer electrochromic of formula (IV), (V), (V-A), (VI), or (VI-A), or a combination thereof;
- wherein
- wherein
- each X1 independently is O, S, or NR;
- R is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, and yet more specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
- each R1 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl;
- each Z1 independently is H, C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- Ar is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, terphenyl, or triphenylene;
- each Z2 independently is C1-20 alkyl, specifically C1-10 alkyl, more specifically C1-6 alkyl, halogen, nitro, cyano, hydroxyl, C6-C12 aryl, C3-C20 cycloalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 haloalkyl, amino, C1-C12 alkylamino, or C1-C12 diaminoalkyl;
- q is 0, 1, 2, 3, or 4, specifically 0, 1, or 2;
- Ar1 and Ar2 each independently is an aromatic group, specifically anthracene, benzophenone, 2,1,3-benzothiadiazole, biphenyl, dibenzofuran, dibenzothiophene, diphenylfulvene, 1,3-diphenylisobenzofuran, 2,2′-dipyridyl, 4,4′-dipyridyl, fluorene, fluorenone, naphthyl, 2-nitrobiphenyl, phenanthrene, phenyl, pyrene, pyridyl, terphenyl, or triphenylene;
- each X2 independently is O, S, or NR;
- each R2 and R3 independently is
- C1-20 alkylene, specifically C1-10 alkylene, more specifically C1-6 alkylene, or
- a poly(alkylene ether), a poly(alkylene glycol) comprising ethyleneoxy, propyleneoxy, and butyleneoxy repeating units containing 2-20 carbon atoms, specifically 2-10 carbon atoms, and more specifically 2-6 carbon atoms, or
- a C4-40 alkylene chain wherein the chain comprises 1, 2, 3, or 4 Q1 groups within the backbone of the chain, specifically 1 or 2 Q1 groups, wherein each Q1 independently is O, S, —O(C═O)—, —(O═C)O—, —S(C═O)—, or —(O═C)S—;
- a is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- b is about 1 to about 99 mol %, specifically about 5 to about 95 mol %, and more specifically about 40 to about 60 mol % (for color neutral);
- and
- n is about 10,000 to about 100,000 g/mol;
- and
- wherein the electrochromic material composition optionally further comprises a plasticizer, a solvent, or a combination thereof.
22 more elements
Dependencies are inferred from the claim text.