Processes for producing electrochromic substrates and electrochromic articles made therefrom
The present invention provides a process for producing an electroactive substrate. The process includes providing a substrate having an oxidant layer on a surface thereof, exposing the surface containing the oxidant layer to a vapor containing an aryl or heteroaryl monomer that is polymerizable to form an electroactive polymer, and polymerizing the aryl or heteroaryl monomer in the presence of a volatile Lewis base to form a polyaryl or polyheteroaryl electroactive polymer film on the surface of the substrate. The invention also provides electroactive substrates formed by the process.
1. A process for producing an electrochromic substrate, the process including:
providing a substrate having an oxidant layer on a surface thereof, the oxidant layer containing an oxidant and an amphiphilic polymer;
exposing the surface containing the oxidant layer to a vapour containing an aryl or heteroaryl monomer that is polymerizable to form an electroactive polymer; and
polymerizing the aryl or heteroaryl monomer to form a polyaryl or polyheteroaryl electroactive polymer film on the surface of the substrate.
2. A process according to claim 1 , wherein providing a substrate having an oxidant layer on a surface thereof includes:
coating the surface with an oxidant solution, the solution containing the oxidant, the amphiphilic polymer, and a solvent;
removing the solvent to form the oxidant layer containing the oxidant and the amphiphilic polymer.
3. A process according to claim 1 , wherein polymerization of the aryl or heteroaryl monomer is carried out in the presence of a volatile Lewis base.
4. A process according to claim 1 , wherein the amphiphilic polymer is a poly(alkylene glycol) copolymer.
5. A process according to claim 4 , wherein the poly(alkylene glycol) copolymer is selected from the group consisting of: a random copolymer containing poly(ethylene glycol) and poly(propylene glycol) segments; and a block copolymer containing poly(ethylene glycol) and poly(propylene glycol) segments.
6. A process according to claim 5 , wherein the poly(alkylene glycol) copolymer is a poly(propylene glycol)-poly(ethylene glycol)-poly(propylene glycol) or a poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) triblock polymer.
7. A process according to claim 5 , wherein the poly(alkylene glycol) copolymer is a poly(ethylene glycol-ran-propylene glycol) random copolymer.
8. A process according to claim 3 , wherein the volatile Lewis base is selected from the group consisting of: amine containing compounds, carbonyl containing compounds, aromatic heterocyclic compounds, hydroxyl containing compounds, ether containing compounds, ammonia and water.
9. A process according to claim 8 , wherein the volatile Lewis base is an amine containing compound.
10. A process according to claim 9 , wherein the amine containing compound is selected from the group consisting of: methyl amine, cyclohexylamine, diethylamine, diisopropylamine, dipropylamine, dibutylamine, piperidine, triethylamine, diisopropylethylamine, allylmethylamine, 2,6-di-tert-butylpyridine, 2-pyrrollidone, 2-oxazolidone, pyrrollidine, 2-picoline, 4-picoline, 2,3-cyclohexenopyridine, 2-(methylamino)pyridine, tetrahydroquinoline, morpholine, tetrahydrofurfurylamine, piperazine, 1,2,3,4-tetrahydroisoquinoline, benzylamine, aniline, 1,8-bis(dismethylamino)-naphthalene, 2-(ethylamino)ethanol, N,N-dimethylethylene diamine, N,N′-dimethylethylene diamine, ethylene diamine, and 1,1-dimethyl-hydrazine.
11. A process according to claim 8 , wherein the volatile Lewis base is water.
12. A process according to claim 3 , wherein the vapor containing the monomer also contains the volatile Lewis base.
13. A process according to claim 3 , wherein the volatile Lewis base is contained in the oxidant layer.
14. A process according to claim 11 , wherein the step of exposing the surface containing the oxidant layer to a vapour containing an aryl or heteroaryl monomer is carried out in a vacuum chamber and the vapour pressure of the water is about 5 mBar to about 30 mBar (inclusive).
15. A process according to claim 11 , wherein the step of exposing the surface containing the oxidant layer to an aryl or heteroaryl monomer is carried out in a sealed chamber having a relative humidity of about 10% to about 70% at 33° C.
16. A process according to claim 1 , wherein the temperature of the substrate during formation of the polyaryl or polyheteroaryl electroactive polymer film is about 25 degrees Celsius to about 40 degrees Celsius.
17. A process according to claim 1 , wherein the polyaryl or polyheteroaryl electroactive polymer is selected from the group consisting of:
polyaryl polymers, such as polyphenylene, polyphenylenesulfide, polyaniline, polyquinone, polyfluorene, polyanthraquinone, poly-1,4-phenylene vinylene (PPV), and 2-methoxy-5-ethylhexyloxy poly-1,4-phenylene vinylene (MEH-PPV);
polyheteroaryl polymers, such as polythiophene (PTh), polypyrrole (PPy), polyfuran (Pfu), polycarbazole (PCz), poly-3,4-ethylenedioxythiophene (PEDOT), poly(3,4-propylene dioxythiophene (PropOT), poly-3,4-(2,2-dimethylpropylene)dioxythiophene (PropOT-Me 2 ), poly-3,4-ethylenedioxypyrrole (PEDOP), poly-3,4-propylenedioxypyrrole (PropOP), poly-N-(3-sulfonatopropoxy)-3,4-propylenedioxpyrrole (PPropOP-NPS), poly-1,2-bis(2-ethylenedioxythienyl)vinylene (PBEDOT-V), poly-1,2-bis(2-propylenedioxythienyl)vinylene (PPropOT-V), poly-2,5-bis(2-ethylenedioxythienyl)pyridine (PBEDOT-Pyr), poly-1,4-bis(2-ethylendioxythienyl)-2,5-didodecyloxybenzene (PBEDOT-B(OC 12 H 25 ) 2 ), poly-3-methylthiophene (P3MTh), poly-2,5-(2-ethylenedioxythienyl)furan (PBEDOT-Fu), poly-4,4′-(2-ethylenedioxythienyl)biphenyl (PBETDOT-BP), poly-3,6-(2-ethylenedioxythienyl)carbazole (PBEDOT)-Cz), poly-3-butylthiophene (P3BTh), alkyl poly-3,4-ethylenedioxythiophene (PEDOT-alkyl), aryl poly-3,4-ethylenedioxythiophene (PEDOT-aryl), poly-2,5-(2-thienyl)pyrrole (PSNS), polyviologen (PV), poly-metal phthalocyanines (PM Phth), poly-5,5′-biethylenedioxythiophene (PBiEDOT), poly-1,2-(2-ethylene dioxythienyl)cyanovinylene (PBEDOT-CNV), poly-1,2-(2-thienyl)cyanovinylene (PBTh-CNV), poly[2,5-bis(2ethylenedioxythienyl)-diphenylpyridopyrazine] (PBEDOT-PyrPyr(Ph) 2 ), polythiopehenvinylene, polythiazole, poly(p-pyridine), poly(p-pyridalvinylene), and polyindole;
and derivatives of any of the aforementioned.
18. A process according to claim 17 , wherein the polyaryl or polyheteroaryl electroactive polymer is a poly-3,4-alkylenedioxythiophene.
19. A process according to claim 18 , wherein the poly-3,4-alkylenedioxythiophene is poly-3,4-ethylenedioxythiophene (PEDOT).
20. A process according to claim 18 , wherein the poly-3,4-alkylenedioxythiophene is poly-3,4-propylenedioxythiophene (PRODOT).
21. A process according to claim 1 , wherein the oxidant is a metal salt.
22. A process according to claim 21 , wherein the metal salt is the salt of an arylsulphonic acid.
23. A process according to claim 22 , wherein the metal salt is iron(III) tosylate.
24. A process according to claim 1 , wherein the amphiphilic polymer is a hydrated amphiphilic polymer.
25. A process according to claim 24 , wherein the hydrated amphiphilic polymer contains water in an amount of about 0.01 wt % to about 2 wt % (inclusive).
26. An electrochromic substrate produced by any one of the processes of claims 1 to 25 .
27. An electrochromic device including an electrochromic substrate according to claim 26 .
28. An electrochromic device including:
a first electrochromic substrate formed according to a process of any one of claims 1 to 25 ;
a second electrochromic substrate spaced from the first electrochromic substrate, at least one of the first and second electrochromic substrates being transparent; and
a substantially transparent ion conducting layer containing an electrolyte in contact with the first and second electrochromic substrates.
29. An electrochromic device, the device including:
a first substantially transparent electrochromic substrate formed according to a process of any one of claims 1 to 25 ;
a second electrochromic substrate spaced from the first electrochromic substrate, the second electrochromic substrate including a substrate, a reflective layer and an electrochromic film over the reflective layer; and
a substantially transparent ion conducting layer containing an electrolyte in contact with the first and second electrochromic substrates.
30. An electrochromic mirror for a motor vehicle, the mirror including an electrochromic device in a housing, the electrochromic device including:
a substantially transparent first electrochromic substrate having a substantially transparent electrochromic polymer film on its inward surface;
a second electrochromic substrate positioned in spaced-apart relationship with the first electrochromic substrate, the second electrochromic substrate having a reflective layer on a surface thereof and an electrochromic film on the reflective layer;
a seal positioned toward a peripheral edge of each of the first and second electrochromic substrates and forming a sealed cavity therebetween;
an electrolyte located within said cavity and in contact with the electrochromic polymer film of the first electrochromic substrate and the electrochromic film of the second electrochromic substrate;
means for applying a potential to the first and second electrochromic substrates to controllably cause a variation in the amount of light reflected from the mirror, wherein the first electrochromic substrate is formed in accordance with a process of any one of claims 1 to 25 .