EP2162787A1 - Semi-electroactive material containing organic compounds with positive or negative redox activity, method and kit for making such material, electrically controlled device and glazing using such semi-electroactive material - Google Patents
Semi-electroactive material containing organic compounds with positive or negative redox activity, method and kit for making such material, electrically controlled device and glazing using such semi-electroactive materialInfo
- Publication number
- EP2162787A1 EP2162787A1 EP08806090A EP08806090A EP2162787A1 EP 2162787 A1 EP2162787 A1 EP 2162787A1 EP 08806090 A EP08806090 A EP 08806090A EP 08806090 A EP08806090 A EP 08806090A EP 2162787 A1 EP2162787 A1 EP 2162787A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electroactive
- semi
- charges
- ionic
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 42
- 239000011263 electroactive material Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 7
- 230000000694 effects Effects 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 150000001768 cations Chemical class 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 238000005325 percolation Methods 0.000 claims abstract description 19
- 230000003381 solubilizing effect Effects 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 38
- 229920001577 copolymer Polymers 0.000 claims description 29
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 229920002223 polystyrene Polymers 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- -1 phenothiazine Chemical class 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229920001746 electroactive polymer Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008961 swelling Effects 0.000 claims description 10
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 230000007928 solubilization Effects 0.000 claims description 6
- 238000005063 solubilization Methods 0.000 claims description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003490 calendering Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000412 polyarylene Polymers 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- ZPTRYWVRCNOTAS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.[O-]S(=O)(=O)C(F)(F)F ZPTRYWVRCNOTAS-UHFFFAOYSA-M 0.000 claims description 2
- OHVSCUACGMLPGP-UHFFFAOYSA-N 1-methyl-10h-phenothiazine 5-oxide Chemical compound N1C2=CC=CC=C2S(=O)C2=C1C(C)=CC=C2 OHVSCUACGMLPGP-UHFFFAOYSA-N 0.000 claims description 2
- CJVYYDCBKKKIPD-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylbenzene-1,2-diamine Chemical compound CN(C)C1=CC=CC=C1N(C)C CJVYYDCBKKKIPD-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- GVTGSIMRZRYNEI-UHFFFAOYSA-N 5,10-dimethylphenazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3N(C)C2=C1 GVTGSIMRZRYNEI-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- YUWITRJKUGXRGB-UHFFFAOYSA-N bis(2-thiophen-3-ylethyl) decanedioate Chemical compound C1=CSC=C1CCOC(=O)CCCCCCCCC(=O)OCCC=1C=CSC=1 YUWITRJKUGXRGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical class [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 2
- OYSLMAQEMAJMCL-UHFFFAOYSA-N ethyl thiophene-3-carboxylate Chemical compound CCOC(=O)C=1C=CSC=1 OYSLMAQEMAJMCL-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 150000004693 imidazolium salts Chemical class 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 150000002990 phenothiazines Chemical class 0.000 claims description 2
- 229920002098 polyfluorene Polymers 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000004053 quinones Chemical class 0.000 claims description 2
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 150000008648 triflates Chemical class 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000005678 ethenylene group Chemical class [H]C([*:1])=C([H])[*:2] 0.000 claims 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims 1
- JOWXBGIZDALBJW-UHFFFAOYSA-N 3h-dioxepine Chemical compound C1OOC=CC=C1 JOWXBGIZDALBJW-UHFFFAOYSA-N 0.000 claims 1
- 229910006069 SO3H Inorganic materials 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 57
- 239000002033 PVDF binder Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 229920006370 Kynar Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- ALJHHTHBYJROOG-UHFFFAOYSA-N 7-(dimethylamino)phenothiazin-3-one Chemical compound C1=CC(=O)C=C2SC3=CC(N(C)C)=CC=C3N=C21 ALJHHTHBYJROOG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000763 evoking effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001798 poly[2-(acrylamido)-2-methyl-1-propanesulfonic acid] polymer Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- AKRWNTONLXDQJE-UHFFFAOYSA-N 2-thiophen-3-ylethyl octanoate Chemical compound CCCCCCCC(=O)OCCC=1C=CSC=1 AKRWNTONLXDQJE-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 description 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/1502—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect complementary cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
- Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- SEMI-ELECTROACTIVE MATERIAL COMPRISING ORGANIC COMPOUNDS WITH POSITIVE OR NEGATIVE REDOX ACTIVITY, METHOD AND KIT FOR PRODUCING SAID MATERIAL, ELECTROCOMMANDABLE DEVICE AND GLAZING USING SUCH SEMI-ELECTROACTIVE MATERIAL
- the present invention relates to an electroactive material also said semi-electroactive device for electrically controllable said variable optical properties and / or energy, said semi-electroactive material containing organic compounds with positive or negative redox activity, on a method and a kit of manufacture of this material, on an electrically controllable device comprising a self-supporting layer of polymer with complementary redox activity, namely respectively negative or positive and on glazings using such a semi-electroactive material.
- the electroactive material (or system) of the invention is sometimes referred to interchangeably as a semi-electroactive material (or system), evoking the fact that this material (or system) is capable of forming an electrochemical half-cell.
- Such a device can be defined generally as comprising the following stack of layers: a first substrate with a glass function;
- a second electronically conducting layer with an associated current supply A second electronically conducting layer with an associated current supply
- Electroactive systems with known layers comprise two separate layers of electroactive material by an electrolyte, the electroactive material of at least one of the two layers being electrochromic.
- the two electroactive materials are electrochromic materials, these may be identical or different.
- one of the electroactive materials is electrochromic and the other is not, it will act as a counterelectrode not participating in the process of coloring and discoloration of the system. Under the action of an electric current, the ionic charges of the electrolyte insert into one of the layers of electrochromic material and disinhibit the other layer of electrochromic material or counterelectrode to obtain a contrast of color.
- PEDOT poly (3,4-ethylenedioxythiophene)
- PEDOT poly (3,4-ethylenedioxythiophene)
- Such electroactive systems are not always satisfactory, in particular require a relatively high voltage (greater than 2V) to obtain an acceptable color contrast for the commercial operation of the electrically controllable device.
- the electroactive systems with known electroactive organic compounds comprise an active medium composed of a solvent in which at least two organic electroactive compounds are solubilized, one being an electrochromic material and the other being a counter-electrode material which can also be electrochromic.
- a polymer can be used as a thickener.
- Such systems work by reaction oxidation and reduction of electroactive compounds. Salt can also be added to facilitate charge transport and oxidation-reduction reactions.
- the applicant company has sought a solution to these problems, and has discovered on this occasion a new structure of polymer / organic hybrid electroactive system that allows coloring at a low voltage (less than 2V). Such a decrease in the coloration potential has the effect of increasing the durability of the electrically controllable device, the electroactive medium and the electronically conductive layers of this device being less electrochemically stressed.
- one of the electroactive compounds is in the form of a polymer layer, the segregation phenomena are avoided.
- an electrochemically active, inorganic or polymeric layer which is negative, that is to say which can be reduced and / or accept electrons and cations acting as compensation charges, such as an oxide layer; of tungsten, polyviologen or polythiophene such as PEDOT, or positive, ie which can oxidize and / or eject electrons and cations acting as compensation charges, such as nickel oxide layer or polyaniline; and an electrolyte containing at least one redox active material which may be a positive redox active material such as a metallocene, or a negative redox active material such as a viologen, depending on whether the electrochemically active polymer layer is negative or positive.
- US 6 178 034 B1 also discloses systems of the aforementioned type comprising an electrochromic polymer layer and an electrochromic non-polymer organic compound electrolytic layer. Lists of these polymers and compounds are presented herein but without description of any need to associate complementary staining components.
- the subject of the present invention is therefore a semi-electroactive material of electrically controllable device with variable optical / energy properties, characterized in that it comprises a self-supporting polymer matrix in which is inserted an electroactive system comprising or consisting of:
- At least one electroactive organic compound capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; or at least one electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges;
- ions acting as compensation charges are meant ions Li + , H + , etc., which can be inserted into or disinsert in the electroactive compounds at the same time as the electrons.
- An electroactive organic compound capable of oxidizing and / or ejecting electrons and cations acting as compensation charges means a compound with a positive redox activity, which may be an anodic electrochrome or a non-electrochromic compound. , playing then only the role of reservoir ionic charges or against electrode.
- An electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges means a compound with negative redox activity, which may be a cathodic electrochromic or a non-electrochromic compound, then playing only the role of reservoir ionic charges or against electrode.
- the ionic charges may be borne by the electroactive organic compound (s) and / or by at least one ionic salt and / or at least one solubilized acid in said liquid and / or said self-supporting polymer matrix.
- the solubilizing liquid may consist of a solvent or a mixture of solvents and / or at least one ionic liquid or molten salt at ambient temperature, the said ionic liquid or molten salt, or the said ionic liquids or molten salts then constituting a solubilization liquid.
- the electroactive organic compound (s) capable of being reduced and / or of accepting electrons and cations acting as compensation charges may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4-diperchlorate, 4 '- bipyridinium, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulfides, and all polymeric derivatives electroactive compounds of the electroactive compounds which have just been mentioned.
- bipyridiniums or viologenes such as 1,1'-diethyl-4-diperchlorate, 4 '- bipyridinium, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums,
- the one or more electroactive organic compounds capable of oxidizing and / or ejecting electrons and cations acting as compensation charges can be chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N N, N'-tetramethylphenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene violet bernthsen (MVB), Verdazyls, as well as all derivatives electroactive polymers of the electroactive compounds which have just been mentioned.
- metallocenes such as cobaltocenes, ferrocenes, N, N, N N N, N'-tetramethylphenylenediamine (TMPD)
- phenothiazines such as phenothiazine
- dihydrophenazines such
- the ionic salt (s) may be chosen from lithium perchlorate, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts.
- the acid (s) may be chosen from sulfuric acid (H 2 SO 4 ), triflic acid (CF 3 SO 3 H), phosphoric acid (H 3 PO 4 ) and polyphosphoric acid (H n + 2 P n 0 3n + i).
- concentration of the ionic salt (s) and / or acid (s) in the solvent or solvent mixture is in particular less than or equal to 5 moles / liter, preferably less than or equal to 2 moles / liter, more or less more preferred, less than or equal to 1 mole / liter.
- the or each solvent may be chosen from those having a boiling point of at least 95 ° C., preferably at least 150 ° C.
- the solvent (s) may be chosen from dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and N-methyl-2-pyrrolidone (1-methyl-2).
- pyrrolidinone gamma-butyrolactone, ethylene glycols, alcohols, ketones, nitriles and water.
- the ionic liquid or liquids may be chosen from imidazolium salts, such as 1-ethyl-3-methylimidazolium tetrafluoroborate (emim-BF 4 ), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (emim-CF 3 SO 3 ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (emim-N (CF 3 SO 2 ) 2 or emim-TSFI) and 1-butyl-3-methylimidazolium bis (trifluoromethylsulphonyl) imide (bmim-N ( CF 3 SO 2 ) 2 or bmim-TSFI).
- imidazolium salts such as 1-ethyl-3-methylimidazolium tetrafluoroborate (emim-BF 4 ), 1-ethyl-3-methylimidazolium trifluoromethanesulf
- the autosupported polymer matrix may consist of at least one polymer layer in which said liquid has penetrated to the core.
- the matrix polymer (s) and the liquid may be chosen so that the self-supporting active medium withstands a temperature corresponding to the temperature necessary for a subsequent lamination or calendering step, namely at a temperature of at least 80 ° C. in particular of at least 100 ° C.
- the polymer constituting at least one layer may be a homo- or copolymer in the form of a non-porous film capable of swelling in said liquid.
- the film has in particular a thickness of less than 1 mm, preferably of 10 to 500 ⁇ m, more preferably of 50 to 120 ⁇ m.
- the polymer constituting at least one layer may also be a homo- or copolymer in the form of a porous film, said porous film optionally being capable of swelling in the liquid comprising ionic charges and whose porosity after swelling is chosen for allow the percolation of the ionic charges in the thickness of the film impregnated with liquid.
- Said film then has a thickness of less than 1 mm, preferably less than 800 ⁇ m, more preferably 10 to 500 ⁇ m, and even more preferably 50 to 120 ⁇ m.
- the polymer or the polymers of the polymer matrix are advantageously chosen so as to be able to withstand laminating and calendering conditions, possibly under heating.
- the polymeric material constituting at least one layer may be chosen from:
- the homo- or copolymers having no ionic charges in which case they are borne by the electroactive organic compound (s) and / or by at least one solubilized ionic or acidic salt and / or by at least one ionic liquid or salt; melted; homo or copolymers comprising ionic charges, in which case additional charges making it possible to increase the percolation rate may be carried by the electroactive organic compound (s) and / or by at least one solubilized ionic or acidic salt and / or by minus an ionic liquid or molten salt; and
- Mixtures of at least one homo- or copolymer not bearing ionic charges and at least one homo- or copolymer containing ionic charges, in which case additional charges making it possible to increase the percolation rate may be carried by the or the electroactive organic compounds and / or by at least one ionic salt or solubilized acid and / or by at least one ionic liquid or molten salt.
- the polymer matrix may consist of a film based on a homo- or copolymer comprising ionic charges, capable of giving itself a film essentially capable of ensuring the desired percolation rate for the electroactive system or a speed of percolation greater than this and a homo- or copolymer with or without ionic charges, able to give by itself a film that does not necessarily ensure the desired percolation rate but essentially able to ensure the holding mechanically, the contents of each of these two homo- or copolymers being adjusted so that both the desired percolation rate and the mechanical strength of the resulting self-supporting organic active medium are ensured.
- the polymer or polymers of the polymer matrix not comprising ionic charges may be chosen from copolymers of ethylene, vinyl acetate and optionally at least one other comonomer, such as the ethylene-vinyl acetate copolymers (EVA); polyurethane (PU); polyvinyl butyral (PVB); polyimides (PI); polyamides (PA); polystyrene
- EVA ethylene-vinyl acetate copolymers
- PU polyurethane
- PVB polyvinyl butyral
- PI polyimides
- PA polyamides
- PS polyvinylidene fluoride
- PVDF polyvinylidene fluoride
- PEEK polyether ether ketones
- the polymers are chosen from the same family as they are prepared in the form of porous or non-porous films, the porosity being provided by the blowing agent used during the manufacture of the film.
- Preferred polymers in the case of the non-porous film include polyurethane (PU) or copolymers of ethylene-vinyl acetate (EVA).
- Preferred polymers in the case of the porous film include polyvinylidene fluoride.
- the polymer or polymers of the polymer matrix bearing ionic or polyelectrolyte charges may be chosen from sulphonated polymers which have been exchanged for H + ions of SO 3 H groups by the ions of the desired ionic charges, this ion exchange having taken place before and / or simultaneously with the swelling of the polyelectrolyte in the liquid having ionic charges.
- the sulphonated polymer may be chosen from sulphonated tetrafluoroethylene copolymers, sulphonated polystyrenes (PSS), sulphonated polystyrene copolymers, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), polyetheretherketones (PEEK ) sulphonated and sulphonated polyimides.
- PSS sulphonated polystyrenes
- PAMPS poly (2-acrylamido-2-methyl-1-propanesulfonic acid)
- PEEK polyetheretherketones
- the support may comprise from one to three layers.
- a stack of at least two layers may have been formed from electrolyte polymer layers and / or non-electrolytes before penetration to the heart of the liquid, then was inflated by said liquid.
- the two outer layers of the stack may be low-swelling layers to promote the mechanical strength of said material and the core layer is a high-swelling layer to promote the percolation rate of the ionic charges.
- the self-supporting polymer matrix may be nanostructured by the incorporation of nanoparticles of inorganic fillers or nanoparticles, in particular of SiO 2 nanoparticles, in particular by a few percent with respect to the mass of polymer in the support. This makes it possible to improve certain properties of said support such as the mechanical strength.
- the present invention also relates to a method for manufacturing a semi-electroactive material as defined above, characterized in that polymer granules are mixed with a solvent and, if it is desired to manufacture a porous polymer matrix, a pore-forming agent, pouring the resulting formulation on a support and after evaporation of the solvent, removing the pore-forming agent by washing in a suitable solvent for example if it was not removed during the evaporation of the above-mentioned solvent, the resulting self-supported film is removed, then the impregnation of said film is carried out by the solubilization liquid of the semi-electroactive system, and then, if necessary, draining is carried out.
- the immersion can then be carried out for a period of 2 minutes to 3 hours.
- Immersion can be carried out under heating, for example at a temperature of 40 to 80 ° C.
- Immersion can also be performed with the application of ultrasound to aid in the penetration of the solubilizing liquid into the matrix.
- the present invention also relates to a kit for manufacturing the electroactive material as defined above, characterized in that it consists of:
- the present invention also relates to an electrically controllable device comprising the following stack of layers:
- a second electronically conducting layer with an associated current supply A second electronically conducting layer with an associated current supply
- the electroactive system consists of the following stack of layers: a semi-electroactive material as defined above; and
- Cations acting as compensation charges can also be inserted or disinserted in the electroactive polymers of the self-supporting layer.
- the substrates with a glass function are chosen in particular from glass (float glass, etc.) and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthoate (PEN) and cycloolefin copolymers (COC).
- PMMA poly (methyl methacrylate)
- PC polycarbonate
- PET polyethylene terephthalate
- PEN polyethylene naphthoate
- COC cycloolefin copolymers
- the electronically conductive layers are in particular metal-type layers, such as layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) type layers, such as tin doped indium oxide (In 2 Os: Sn or ITO), antimony doped indium oxide (In 2 Os: S b ), tin oxide fluorine-doped (SnO 2 : F) and zinc oxide doped with aluminum (ZnO: Al); or TCO / metal / TCO multilayers, the TCO and the metal being in particular chosen from those enumerated above; or NiC r / metal / NiC r multilayers, the metal being in particular chosen from those enumerated above.
- TCO transparent conductive oxide
- the electroconductive materials are generally transparent oxides whose electronic conduction has been amplified by doping such as In 2 Os: Sn, In 2 Os: Sb, ZnO: Al or SnO 2 : F .
- Tin doped indium oxide In 2 O 3 : Sn or ITO
- one of the electroconductive materials may be metallic in nature.
- the polymer capable of being reduced and / or of accepting electrons and cations acting as compensation charges is chosen from among the polyviologenes is chosen in particular from polyviologenes, polymers containing units or groups bispyridinium, pyrylium, pyrazinium, or quinoxalium, polyarylenes and polyheteroarylenes such as polythiophenes such as for example poly (3,4-ethylenedioxythiophene) (PEDOT), poly [3,3-dimethyl-3,4-dihydro-2H-thieno-3, 4-b) dioxepine] (ProD0T-Me 2 ), polyisothianophtene, polyisothianaphthene (PITN), polyimides, polyquinones and polydisulfides.
- polyviologenes polymers containing units or groups bispyridinium, pyrylium, pyrazinium, or quinoxalium
- polyarylenes and polyheteroarylenes such as poly
- the polymer capable of oxidizing and / or ejecting electrons and cations acting as charges of compensation is chosen in particular from polyarylamines, such as polyanilines, polyarylenes, such as polyphenylenes or polyfluorenes, polyheteroarylenes such as polypyrroles, for instance poly (N-sulfonatopropoxy-3,4-propylenedioxypyrrole) (PProDOP-NPrS) ), polylindoles, thiophene copolymers such as poly [octanoic acid 2-thiophen-3-yl ethyl ester] (POTE), poly [decanedioic acid bis- (2-thiophen-3-yl-ethyl) ester] (PDATE), poly ⁇ 2- [3-thienylcarbonyl) oxy] ethyl-3-thiophene carboxylate ⁇ (PTOET), poly ⁇ 2,3-bis [3-thienylcarbonyl)
- a motor vehicle roof which can be activated autonomously, or a side window or a rear window for a motor vehicle or a rear-view mirror; - a windshield or a portion of the windshield of a motor vehicle, an airplane or a ship, an automobile roof;
- the electrically controllable device can operate in transmission or in reflection.
- the substrates may be transparent, flat or curved, clear or tinted in the mass, opaque or opacified, polygonal in shape or at least partially curved. At least one of the substrates may incorporate another feature, such as solar control, anti-reflective, or self-cleaning functionality.
- the present invention also relates to a method of manufacturing the electrically controllable device as defined above, characterized in that it assembles the various layers that compose it by calendering or laminating possibly under heating. In the case where the electrically controllable device is intended to constitute a glazing unit, the above method also comprises the mounting of the different layers in single or multiple glazing.
- PEDOT / PSS poly (3, 4-ethylenedioxythiophene) / polystyrene sulfonate sold under the name Baytron ® P by the Company "HC Stark”.
- PVDF Poly (vinylidene fluoride) In these examples, was carried out the deposition of wet formulations of PEDOT / PSS (Baytron ® P) following the CPC 105D recipe for "HC Stark” Company.
- the glass used in these examples is a glass provided with an electroconductive layer of SnC> 2: F, sold under the name "K-glass TM” by the company "Pilkington”.
- PVDF films used was poly powder (polyvinylidene fluoride) manufactured by my company "Arkema” under the name “Kynar ®” in 2501 or 2821.
- PVDF Vinyl ® 2501
- dibutyl phthalate 12 g
- acetone 12 g
- the formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water.
- a semi-electroactive solution was prepared by mixing 0.23 g of ferrocene and 0.27 g of sodium perchlorate. lithium in 40 ml of propylene carbonate. The solution was stirred for 1 hour.
- the self-supported semi-electroactive medium was obtained by immersing the PVDF film about 80 microns thick in diethyl ether for 5 minutes and then in the semi- electroactive solution for 5 minutes.
- the PVDF film impregnated with semi-electroactive solution was then wiped between two absorbent papers before being deposited on a bare K-glass glass plate.
- a double-sided adhesive frame was used as a seal and the K-glass plate coated with PEDOT / PSS was deposited on the semi-electroactive film to terminate the electrochromic device.
- the electrochromic device thus manufactured has a light transmission of 42% in the decolorized state, at a voltage of 1.5V and 13.5% in the colored state at a voltage of -1.5V. After 1000 cycles of discoloration and coloration the performance of the electrochromic device remained unchanged.
- - SnO2 layer glass F coated with a layer of PEDOT / PSS; - semi-electroactive system: ferrocene + lithium trifluoromethanesulfonate + propylene carbonate
- An electrochromic device was made using a bare K-glass plate and a K-glass plate on which a layer of PEDOT / PSS had been deposited.
- PVDF Self-supporting film by mixing 3.5 g of PVDF (Kynar ® 2821), 6.5 g of dibutyl phthalate and 12 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water.
- a semi-electroactive solution was prepared by mixing 0.23 g of ferrocene and 0.39 g of lithium trifluoromethanesulfonate in 40 ml of propylene carbonate. The solution was stirred for 1 hour.
- the self-supported semi-electroactive medium was obtained by immersing the PVDF film about 80 microns thick in diethyl ether for 5 minutes and then in the semi- electroactive solution for 5 minutes.
- the PVDF film impregnated with semi-electroactive solution was then wiped between two absorbent papers before being deposited on a bare K-glass glass plate.
- a double-sided adhesive frame was used as a seal and the K-glass plate coated with PEDOT / PSS was deposited on the semi-electroactive film to terminate the electrochromic device.
- the electrochromic device thus manufactured has a light transmission of 45% in the decolorized state at a voltage of 1.5V and 15% in the colored state at a voltage of -1.5V. After 100 cycles of discoloration and coloration the performance of the electrochromic device remained unchanged.
- An electrochromic device was manufactured using two K-glass plates on each of which a PEDOT / PSS layer had been deposited (wet 180 micron deposit). Before assembly, the PEDOT / PSS layers were reduced in a solution of acetonitrile and lithium perchlorate at 1M.
- An electrolyte solution was prepared by solubilizing 0.27 g of lithium perchlorate in 40 ml of propylene carbonate. The solution was stirred for 1 hour.
- the self-supporting electrolyte was obtained by dipping for 5 minutes the PVDF film about 80 microns thick 5 minutes in diethyl ether and then 5 minutes in the electrolyte solution.
- the PVDF film impregnated with electrolyte solution was then wiped between two absorbent papers before being deposited on one of the two K-glass plates covered with PEDOT / PSS.
- a double-sided adhesive frame was used as a seal and the second K-glass plate covered with PEDOT / PSS was deposited on the self-supported electrolyte film to terminate the electrochromic device.
- the electrochromic device thus manufactured has a light transmission of 18% in the decolorized state under a voltage of OV and 10.5% in the colored state under a voltage of -2V.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The semi-electroactive material of the invention includes a self-sustained polymer matrix in which is inserted an electroactive system including or made of: at least one electroactive organic compound capable of oxidation and/ejecting electrons and cations serving as compensation charges; or at least one electroactive organic compound capable of reduction and/or accepting electrons and cations serving as compensation charges; and ionic charges; and a liquid for solubilizing said semi-electroactive system, wherein said liquid does not solubilize the self-sustained polymer matrix, the latter being selected so as to provide a percolation path for the ionic charges, which results, upon the application of a dielectric current, in oxidation and reduction reactions of said electroactive organic compounds which are necessary for obtaining a colour contrast.
Description
MATERIAU SEMI-ELECTROACTIF RENFERMANT DES COMPOSES ORGANIQUES A ACTIVITE REDOX POSITIVE OU NEGATIVE, PROCEDE ET KIT DE FABRICATION DE CE MATERIAU, DISPOSITIF ELECTROCOMMANDABLE ET VITRAGES UTILISANT UN TEL MATERIAU SEMI-ELECTROACTIFSEMI-ELECTROACTIVE MATERIAL COMPRISING ORGANIC COMPOUNDS WITH POSITIVE OR NEGATIVE REDOX ACTIVITY, METHOD AND KIT FOR PRODUCING SAID MATERIAL, ELECTROCOMMANDABLE DEVICE AND GLAZING USING SUCH SEMI-ELECTROACTIVE MATERIAL
La présente invention porte sur un matériau électroactif dit également semi-électroactif pour dispositif électrocommandable dit à propriétés optiques et/ou énergétiques variables, ledit matériau semi- électroactif renfermant des composés organiques à activité redox positive ou négative, sur un procédé et un kit de fabrication de ce matériau, sur un dispositif électrocommandable comportant une couche autosupportée de polymère à activité redox complémentaire, à savoir respectivement négative ou positive et sur des vitrages utilisant un tel matériau semi-électroactif.The present invention relates to an electroactive material also said semi-electroactive device for electrically controllable said variable optical properties and / or energy, said semi-electroactive material containing organic compounds with positive or negative redox activity, on a method and a kit of manufacture of this material, on an electrically controllable device comprising a self-supporting layer of polymer with complementary redox activity, namely respectively negative or positive and on glazings using such a semi-electroactive material.
Dans ce qui suit, le matériau (ou système) électroactif de l'invention est parfois désigné indifféremment par matériau (ou système) semi-électroactif, évoquant le fait que ce matériau (ou système) est apte à former une demi-cellule électrochimique.In what follows, the electroactive material (or system) of the invention is sometimes referred to interchangeably as a semi-electroactive material (or system), evoking the fact that this material (or system) is capable of forming an electrochemical half-cell.
Un tel dispositif peut être défini d'une manière générale comme comportant l'empilement suivant de couches : — un premier substrat à fonction verrière ;Such a device can be defined generally as comprising the following stack of layers: a first substrate with a glass function;
— une première couche électroniquement conductrice avec une amenée de courant associée ;A first electrically conductive layer with an associated current supply;
- un système électroactif ;an electroactive system;
— une deuxième couche électroniquement conductrice avec une amenée de courant associée ; etA second electronically conducting layer with an associated current supply; and
- un second substrat à fonction verrière.a second substrate with a glass function.
Les systèmes électroactifs à couches connus comportent deux couches de matériau électroactif séparées
par un électrolyte, le matériau électroactif d'au moins l'une des deux couches étant électrochrome. Dans le cas où les deux matériaux électroactifs sont des matériaux électrochromes, ceux-ci peuvent être identiques ou différents. Dans le cas où l'un des matériaux électroactifs est électrochrome et l'autre ne l'est pas, celui-ci aura le rôle de contre-électrode ne participant pas aux processus de coloration et de décoloration du système. Sous l'action d'un courant électrique, les charges ioniques de l' électrolyte s'insèrent dans l'une des couches de matériau électrochrome et se désinsèrent de l'autre couche de matériau électrochrome ou de contre- électrode pour obtenir un contraste de couleur.Electroactive systems with known layers comprise two separate layers of electroactive material by an electrolyte, the electroactive material of at least one of the two layers being electrochromic. In the case where the two electroactive materials are electrochromic materials, these may be identical or different. In the case where one of the electroactive materials is electrochromic and the other is not, it will act as a counterelectrode not participating in the process of coloring and discoloration of the system. Under the action of an electric current, the ionic charges of the electrolyte insert into one of the layers of electrochromic material and disinhibit the other layer of electrochromic material or counterelectrode to obtain a contrast of color.
Comme exemple courant de système électroactif à couches et polymère, on peut citer l'empilement suivant de couches :As a common example of an electroactive system with layers and polymer, mention may be made of the following stack of layers:
- poly (3, 4-éthylènedioxythiophène) (PEDOT) ;poly (3,4-ethylenedioxythiophene) (PEDOT);
- électrolyte ;- electrolyte;
- poly (3, 4-éthylènedioxythiophène) (PEDOT). De tels systèmes électroactifs ne sont pas toujours satisfaisants, en particulier nécessitent une tension relativement élevée (supérieure à 2V) pour l'obtention d'un contraste de couleur acceptable pour l'exploitation commerciale du dispositif électrocommandable .poly (3,4-ethylenedioxythiophene) (PEDOT). Such electroactive systems are not always satisfactory, in particular require a relatively high voltage (greater than 2V) to obtain an acceptable color contrast for the commercial operation of the electrically controllable device.
Les systèmes électroactifs à composés organiques électroactifs connus comportent un milieu actif composé d'un solvant dans lequel est solubilisé au moins deux composés électroactifs organiques l'un étant un matériau électrochrome l'autre étant un matériau de contre-electrode pouvant lui aussi être électrochrome. Afin de solidifier le milieu actif, un polymère peut être utilisé comme épaississant. De tels systèmes fonctionnent par réaction
d'oxydation et de réduction des composés électroactifs. Un sel peut aussi être ajouté pour faciliter le transport des charges et les réactions d' oxydo-réductions .The electroactive systems with known electroactive organic compounds comprise an active medium composed of a solvent in which at least two organic electroactive compounds are solubilized, one being an electrochromic material and the other being a counter-electrode material which can also be electrochromic. In order to solidify the active medium, a polymer can be used as a thickener. Such systems work by reaction oxidation and reduction of electroactive compounds. Salt can also be added to facilitate charge transport and oxidation-reduction reactions.
De tels systèmes permettent d'obtenir des contrastes tout à fait intéressants avec une tension relativement faibles (inférieure à 2V) , surtout dans le cas où les composés électroactifs sont électrochromes à colorations complémentaires. En revanche, le milieu actif est sous forme liquide ou gélifiée ce qui peut conduire à des phénomènes de ségrégation de phase inacceptable optiquement .Such systems make it possible to obtain quite interesting contrasts with a relatively low voltage (less than 2V), especially in the case where the electroactive compounds are electrochromic with complementary staining. On the other hand, the active medium is in liquid or gelled form, which can lead to phenomena of optically unacceptable phase segregation.
La Société déposante a recherché une solution à ces problèmes, et a découvert à cette occasion une nouvelle structure de système électroactif hybride polymère/organique qui permet une coloration à une basse tension (inférieure à 2V) . Une telle diminution du potentiel de coloration a pour effet une augmentation de la durabilité du dispositif électrocommandable, le milieu électroactif ainsi que les couches électroniquement conductrices de ce dispositif étant moins sollicités électrochimiquement . De plus, un des composés électroactifs étant sous forme d'une couche polymère, les phénomènes de ségrégation sont évités.The applicant company has sought a solution to these problems, and has discovered on this occasion a new structure of polymer / organic hybrid electroactive system that allows coloring at a low voltage (less than 2V). Such a decrease in the coloration potential has the effect of increasing the durability of the electrically controllable device, the electroactive medium and the electronically conductive layers of this device being less electrochemically stressed. In addition, since one of the electroactive compounds is in the form of a polymer layer, the segregation phenomena are avoided.
On connaît par la demande internationale PCT WO96/13754 et le brevet US 6,178,034 Bl, un dispositif électrochrome comprenant une électrode conductrice et une contre-électrode conductrice entre lesquelles sont disposéesPCT International Application No. WO96 / 13754 and US Pat. No. 6,178,034 B1 disclose an electrochromic device comprising a conductive electrode and a conductive counter-electrode between which are arranged
- une couche électrochimiquement active, inorganique ou polymère, qui est négative, c'est-à-dire qui peut se réduire et/ou accepter des électrons et des cations jouant le rôle de charges de compensation, tel qu'un couche d'oxyde de tungstène, de polyviologène ou de
polythiophène tel que le PEDOT, ou positive, c'est à dire qui peut s'oxyder et/ou éjecter des électrons et des cations jouant le rôle de charges de compensation, tel que couche d'oxyde de nickel ou de polyaniline ; et — un électrolyte contenant au moins une matière active redox qui peut être une matière active redox positive tel qu'un métallocène, ou une matière active redox négative tel qu'un viologène, selon que la couche polymère électrochimiquement active est négative ou positive.an electrochemically active, inorganic or polymeric layer, which is negative, that is to say which can be reduced and / or accept electrons and cations acting as compensation charges, such as an oxide layer; of tungsten, polyviologen or polythiophene such as PEDOT, or positive, ie which can oxidize and / or eject electrons and cations acting as compensation charges, such as nickel oxide layer or polyaniline; and an electrolyte containing at least one redox active material which may be a positive redox active material such as a metallocene, or a negative redox active material such as a viologen, depending on whether the electrochemically active polymer layer is negative or positive.
Or, il apparaît que l'association d'un polythiophène tel que le PEDOT avec un viologène dans l' électrolyte comme évoqué dans US 6 178 034 Bl ne donne aucun contraste de couleur sous l'action d'un courant électrique.However, it appears that the combination of a polythiophene such as PEDOT with a viologen in the electrolyte as evoked in US 6 178 034 B1 gives no color contrast under the action of an electric current.
On connaît également par US 6 178 034 Bl des systèmes du type précité comportant une couche de polymère électrochrome et une couche électrolytique à composé organique non polymère électrochrome. Des listes de ces polymères et de ces composés sont présentées dans ce document mais sans description d'une quelconque nécessité d'associer des composants à coloration complémentaire.US 6 178 034 B1 also discloses systems of the aforementioned type comprising an electrochromic polymer layer and an electrochromic non-polymer organic compound electrolytic layer. Lists of these polymers and compounds are presented herein but without description of any need to associate complementary staining components.
La présente invention a donc pour objet un matériau semi-électroactif de dispositif électrocommandable à propriétés optiques/énergétiques variables, caractérisé par le fait qu' il comprend une matrice polymère autosupportée dans laquelle est inséré un système électroactif comprenant ou constitué par:The subject of the present invention is therefore a semi-electroactive material of electrically controllable device with variable optical / energy properties, characterized in that it comprises a self-supporting polymer matrix in which is inserted an electroactive system comprising or consisting of:
- au moins un composé organique électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; ou
- au moins un composé organique électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; etat least one electroactive organic compound capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; or at least one electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges; and
- des charges ioniques ; ainsi qu'un liquide de solubilisation dudit système semi- électroactif, ledit liquide ne solubilisant pas ladite matrice polymère autosupportée, cette dernière étant choisie pour assurer un chemin de percolation des charges ioniques, ceci permettant, sous l'action d'un courant diélectrique, des réactions d'oxydation et de réduction desdits composés organiques électroactifs, lesquelles sont nécessaires pour obtenir un contraste de couleur.- ionic charges; and a liquid for solubilizing said semi-electroactive system, said liquid not solubilizing said self-supporting polymer matrix, the latter being chosen to ensure a percolation path of the ionic charges, this allowing, under the action of a dielectric current, oxidation and reduction reactions of said electroactive organic compounds, which are necessary to obtain a color contrast.
Par « cations jouant le rôle de charges de compensation », on entend des ions Li+, H+, etc., qui peuvent s'insérer ou se désinsérer dans les composés électroactifs en même temps que les électrons.By "cations acting as compensation charges" are meant ions Li + , H + , etc., which can be inserted into or disinsert in the electroactive compounds at the same time as the electrons.
Par composé organique électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation, on entend un composé à activité redox positive, lequel peut être un électrochrome à coloration anodique ou un composé non électrochrome, jouant alors seulement le rôle de réservoir de charges ioniques ou de contre-électrode .An electroactive organic compound capable of oxidizing and / or ejecting electrons and cations acting as compensation charges means a compound with a positive redox activity, which may be an anodic electrochrome or a non-electrochromic compound. , playing then only the role of reservoir ionic charges or against electrode.
Par composé organique électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation, on entend un composé à activité redox négative, lequel peut être un électrochrome à coloration cathodique ou un composé non électrochrome, jouant alors seulement le rôle de réservoir de charges ioniques ou de contre-électrode.An electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges means a compound with negative redox activity, which may be a cathodic electrochromic or a non-electrochromic compound, then playing only the role of reservoir ionic charges or against electrode.
Les charges ioniques peuvent être portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique et/ou au moins un acide solubilisé dans
ledit liquide et/ou par ladite matrice polymère autosupportée .The ionic charges may be borne by the electroactive organic compound (s) and / or by at least one ionic salt and / or at least one solubilized acid in said liquid and / or said self-supporting polymer matrix.
Le liquide de solubilisation peut être constitué par un solvant ou un mélange de solvants et/ou par au moins un liquide ionique ou sel fondu à température ambiante, ledit liquide ionique ou sel fondu ou lesdits liquides ioniques ou sels fondus constituant alors un liquide de solubilisation portant des charges ioniques, lesquelles représentent tout ou partie des charges ioniques dudit système semi-électroactif.The solubilizing liquid may consist of a solvent or a mixture of solvents and / or at least one ionic liquid or molten salt at ambient temperature, the said ionic liquid or molten salt, or the said ionic liquids or molten salts then constituting a solubilization liquid. carrying ionic charges, which represent all or part of the ionic charges of said semi-electroactive system.
Le ou les composés organiques électroactifs capables de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation peuvent être choisis parmi les bipyridiniums ou viologènes tels que le diperchlorate de 1, l' -diéthyl-4, 4' - bipyridinium, les pyraziniums, les pyrimidiniums, les quinoxaliniums, les pyryliums, les pyridiniums, les tétrazoliums, les verdazyls, les quinones, les quinodiméthanes, les tricyanovinylbenzènes, le tétracyanoéthylène, les polysulfures et les disulfures, ainsi que tous les dérivés polymériques électroactifs des composés électroactifs qui viennent d'être mentionnés. A titre d'exemples des dérivés polymériques ci-dessus, on peut citer les polyviologènes . Le ou les composés organiques électroactifs capables de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation peuvent être choisis parmi les métallocènes, tels que les cobaltocènes, les ferrocènes, la N, N, N', N'- tétraméthylphénylènediamine (TMPD) , les phénothiazines telles que la phénothiazine, les dihydrophénazines telles que la 5, 10-dihydro-5, 10-diméthylphénazine, la méthylphénothiazone réduite (MPT) , le violet de méthylène bernthsen (MVB) , les verdazyls, ainsi que tous les dérivés
polymériques électroactifs des composés électroactifs qui viennent d'être mentionnés.The electroactive organic compound (s) capable of being reduced and / or of accepting electrons and cations acting as compensation charges may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4-diperchlorate, 4 '- bipyridinium, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulfides, and all polymeric derivatives electroactive compounds of the electroactive compounds which have just been mentioned. As examples of the above polymeric derivatives, mention may be made of polyviologenes. The one or more electroactive organic compounds capable of oxidizing and / or ejecting electrons and cations acting as compensation charges can be chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N N, N'-tetramethylphenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene violet bernthsen (MVB), Verdazyls, as well as all derivatives electroactive polymers of the electroactive compounds which have just been mentioned.
Le ou les sels ioniques peuvent être choisis parmi le perchlorate de lithium, les sels trifluorométhanesulfonates ou triflates, les sels de trifluorométhanesulfonylimide et les sels d'ammonium.The ionic salt (s) may be chosen from lithium perchlorate, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts.
Le ou les acides peuvent être choisis parmi l'acide sulfurique (H2SO4), l'acide triflique (CF3SO3H), l'acide phosphorique (H3PO4) et l'acide polyphosphorique (Hn+2 Pn 03n+i) . La concentration du ou des sels ioniques et/ou de l'acide ou des acides dans le solvant ou le mélange de solvants est notamment inférieure ou égale à 5 moles/litre, de préférence inférieure ou égale à 2 moles/litre, de façon encore davantage préférée, inférieure ou égale à 1 mole/litre.The acid (s) may be chosen from sulfuric acid (H 2 SO 4 ), triflic acid (CF 3 SO 3 H), phosphoric acid (H 3 PO 4 ) and polyphosphoric acid (H n + 2 P n 0 3n + i). The concentration of the ionic salt (s) and / or acid (s) in the solvent or solvent mixture is in particular less than or equal to 5 moles / liter, preferably less than or equal to 2 moles / liter, more or less more preferred, less than or equal to 1 mole / liter.
Le ou chaque solvant peut être choisi parmi ceux ayant un point d'ébullition au moins égal à 95°C, de préférence au moins égal à 1500C.The or each solvent may be chosen from those having a boiling point of at least 95 ° C., preferably at least 150 ° C.
Le ou les solvants peuvent être choisis parmi le diméthylsulfoxyde, le N, N-diméthylformamide, le N, N- diméthylacétamide, le carbonate de propylène, le carbonate d'éthylène, la N-méthyl-2-pyrrolidone (l-méthyl-2- pyrrolidinone) , la gamma-butyrolactone, les éthylène glycols, les alcools, les cétones, les nitriles et l'eau. Le ou les liquides ioniques peuvent être choisis parmi les sels d' imidazolium, tels que le l-éthyl-3- méthylimidazolium tétrafluoroborate (emim-BF4) , le 1-éthyl- 3-méthylimidazolium trifluorométhane sulfonate (emim- CF3SO3) , le l-éthyl-3-méthylimidazolium bis (trifluorométhylsulfonyl) imide (emim-N (CF3SO2) 2 ou emim- TSFI) et le l-butyl-3-méthylimidazolium bis (trifluorométhylsulfonyl) imide (bmim-N (CF3SO2) 2 ou bmim- TSFI) .The solvent (s) may be chosen from dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and N-methyl-2-pyrrolidone (1-methyl-2). pyrrolidinone), gamma-butyrolactone, ethylene glycols, alcohols, ketones, nitriles and water. The ionic liquid or liquids may be chosen from imidazolium salts, such as 1-ethyl-3-methylimidazolium tetrafluoroborate (emim-BF 4 ), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (emim-CF 3 SO 3 ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (emim-N (CF 3 SO 2 ) 2 or emim-TSFI) and 1-butyl-3-methylimidazolium bis (trifluoromethylsulphonyl) imide (bmim-N ( CF 3 SO 2 ) 2 or bmim-TSFI).
La matrice polymère autosupportée peut être constituée par au moins une couche polymère dans laquelle ledit liquide a pénétré à cœur.
Le ou les polymères de matrice et le liquide peuvent être choisis pour que le milieu actif autosupporté résiste à une température correspondant à la température nécessaire à une étape de feuilletage ou de calandrage ultérieure, à savoir à une température d'au moins 800C, en particulier d'au moins 1000C.The autosupported polymer matrix may consist of at least one polymer layer in which said liquid has penetrated to the core. The matrix polymer (s) and the liquid may be chosen so that the self-supporting active medium withstands a temperature corresponding to the temperature necessary for a subsequent lamination or calendering step, namely at a temperature of at least 80 ° C. in particular of at least 100 ° C.
Le polymère constituant au moins une couche peut être un homo- ou copolymère se présentant sous la forme d'un film non poreux mais capable de gonfler dans ledit liquide.The polymer constituting at least one layer may be a homo- or copolymer in the form of a non-porous film capable of swelling in said liquid.
Le film a notamment une épaisseur inférieure à 1 mm, de préférence de 10 à 500 μm, de façon davantage préférée de 50 à 120 μm.The film has in particular a thickness of less than 1 mm, preferably of 10 to 500 μm, more preferably of 50 to 120 μm.
Le polymère constituant au moins une couche peut aussi être un homo- ou copolymère se présentant sous la forme d'un film poreux, ledit film poreux étant éventuellement capable de gonfler dans le liquide comportant des charges ioniques et dont la porosité après gonflement est choisie pour permettre la percolation des charges ioniques dans l'épaisseur du film imprégné de liquide .The polymer constituting at least one layer may also be a homo- or copolymer in the form of a porous film, said porous film optionally being capable of swelling in the liquid comprising ionic charges and whose porosity after swelling is chosen for allow the percolation of the ionic charges in the thickness of the film impregnated with liquid.
Ledit film a alors notamment une épaisseur inférieure à 1 mm, de préférence inférieure à 800 μm, de façon davantage préférée de 10 à 500 μm, et de façon encore plus préférée de 50 à 120 μm.Said film then has a thickness of less than 1 mm, preferably less than 800 μm, more preferably 10 to 500 μm, and even more preferably 50 to 120 μm.
Par ailleurs, le polymère ou les polymères de la matrice polymère sont avantageusement choisis pour pouvoir résister à des conditions de feuilletage et de calandrage éventuellement sous chauffage. Le matériau polymère constituant au moins une couche peut être choisi parmi :Moreover, the polymer or the polymers of the polymer matrix are advantageously chosen so as to be able to withstand laminating and calendering conditions, possibly under heating. The polymeric material constituting at least one layer may be chosen from:
- les homo- ou copolymères ne comportant pas de charges ioniques, auquel cas celles-ci sont portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu ;
- les homo- ou copolymères comportant des charges ioniques, auquel cas des charges supplémentaires permettant de renforcer la vitesse de percolation peuvent être portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu ; etthe homo- or copolymers having no ionic charges, in which case they are borne by the electroactive organic compound (s) and / or by at least one solubilized ionic or acidic salt and / or by at least one ionic liquid or salt; melted; homo or copolymers comprising ionic charges, in which case additional charges making it possible to increase the percolation rate may be carried by the electroactive organic compound (s) and / or by at least one solubilized ionic or acidic salt and / or by minus an ionic liquid or molten salt; and
— les mélanges d' au moins un homo- ou copolymère ne portant pas de charges ioniques et d'au moins un homo- ou copolymère comportant des charges ioniques, auquel cas des charges supplémentaires permettant de renforcer la vitesse de percolation peuvent être portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu.Mixtures of at least one homo- or copolymer not bearing ionic charges and at least one homo- or copolymer containing ionic charges, in which case additional charges making it possible to increase the percolation rate may be carried by the or the electroactive organic compounds and / or by at least one ionic salt or solubilized acid and / or by at least one ionic liquid or molten salt.
La matrice polymère peut être constituée par un film à base d'un homo- ou copolymère comportant des charges ioniques, apte à donner par lui-même un film essentiellement capable d'assurer la vitesse de percolation recherchée pour le système électroactif ou une vitesse de percolation supérieure à celle-ci et d'un homo- ou copolymère comportant ou non des charges ioniques, apte à donner par lui-même un film ne permettant pas nécessairement d'assurer la vitesse de percolation recherchée mais essentiellement capable d'assurer la tenue mécanique, les teneurs de chacun de ces deux homo- ou copolymères étant réglées pour que soient assurées à la fois la vitesse de percolation recherchée et la tenue mécanique du milieu actif organique autosupporté résultant. Le ou les polymères de la matrice polymère ne comportant pas de charges ioniques peuvent être choisis parmi les copolymères d'éthylène, d'acétate de vinyle et éventuellement d'au moins un autre comonomère, tels que les
copolymères éthylène-acétate de vinyle (EVA) ; le polyuréthane (PU) ; le polyvinyl butyral (PVB) ; les polyimides (PI) ; les polyamides (PA) ; le polystyrèneThe polymer matrix may consist of a film based on a homo- or copolymer comprising ionic charges, capable of giving itself a film essentially capable of ensuring the desired percolation rate for the electroactive system or a speed of percolation greater than this and a homo- or copolymer with or without ionic charges, able to give by itself a film that does not necessarily ensure the desired percolation rate but essentially able to ensure the holding mechanically, the contents of each of these two homo- or copolymers being adjusted so that both the desired percolation rate and the mechanical strength of the resulting self-supporting organic active medium are ensured. The polymer or polymers of the polymer matrix not comprising ionic charges may be chosen from copolymers of ethylene, vinyl acetate and optionally at least one other comonomer, such as the ethylene-vinyl acetate copolymers (EVA); polyurethane (PU); polyvinyl butyral (PVB); polyimides (PI); polyamides (PA); polystyrene
(PS) ; le poly (fluorure de vinylidène) (PVDF) ; les polyéther-éther-cétones (PEEK) ; le poly (oxyde d'éthylène)(PS); polyvinylidene fluoride (PVDF); polyether ether ketones (PEEK); poly (ethylene oxide)
(POE) ; les copolymères d' épichlorhydrine et le poly (méthacrylate de méthyle) (PMMA).(POE); copolymers of epichlorohydrin and poly (methyl methacrylate) (PMMA).
Les polymères sont choisis dans la même famille qu' ils soient préparés sous la forme de films poreux ou non poreux, la porosité étant apportée par l'agent porogène utilisé lors de la fabrication du film.The polymers are chosen from the same family as they are prepared in the form of porous or non-porous films, the porosity being provided by the blowing agent used during the manufacture of the film.
Comme polymères préférés dans le cas du film non poreux, on peut citer le polyuréthanne (PU) ou les copolymères de l' éthylène-acétate de vinyle (EVA). Comme polymères préférés dans le cas du film poreux, on peut citer le poly (fluorure de vinylidène).Preferred polymers in the case of the non-porous film include polyurethane (PU) or copolymers of ethylene-vinyl acetate (EVA). Preferred polymers in the case of the porous film include polyvinylidene fluoride.
Le ou les polymères de la matrice polymère portant des charges ioniques ou polyélectrolytes peuvent être choisis parmi les polymères sulfonés qui ont subi un échange des ions H+ des groupements SO3H par les ions des charges ioniques souhaitées, cet échange d'ions ayant eu lieu avant et/ou simultanément avec le gonflement du polyélectrolyte dans le liquide comportant des charges ioniques . Le polymère sulfoné peut être choisi parmi les copolymères sulfonés de tétrafluoroéthylène, les polystyrènes sulfonés (PSS) , les copolymères de polystyrène sulfoné, le poly (2-acrylamido-2-méthyl-l-propanesulfonique acide) (PAMPS), les polyétheréthercétones (PEEK) sulfonées et les polyimides sulfonés.The polymer or polymers of the polymer matrix bearing ionic or polyelectrolyte charges may be chosen from sulphonated polymers which have been exchanged for H + ions of SO 3 H groups by the ions of the desired ionic charges, this ion exchange having taken place before and / or simultaneously with the swelling of the polyelectrolyte in the liquid having ionic charges. The sulphonated polymer may be chosen from sulphonated tetrafluoroethylene copolymers, sulphonated polystyrenes (PSS), sulphonated polystyrene copolymers, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), polyetheretherketones (PEEK ) sulphonated and sulphonated polyimides.
Le support peut comporter de une à trois couches. Lorsque le support comporte au moins deux couches, un empilement d'au moins deux couches peut avoir été constitué à partir de couches polymères électrolytes
et/ou non électrolytes avant pénétration à cœur du liquide, puis a été gonflé par ledit liquide.The support may comprise from one to three layers. When the support comprises at least two layers, a stack of at least two layers may have been formed from electrolyte polymer layers and / or non-electrolytes before penetration to the heart of the liquid, then was inflated by said liquid.
Lorsque le support comporte trois couches, les deux couches externes de l'empilement peuvent être des couches à faible gonflement pour favoriser la tenue mécanique dudit matériau et la couche centrale est une couche à fort gonflement pour favoriser la vitesse de percolation des charges ioniques.When the support comprises three layers, the two outer layers of the stack may be low-swelling layers to promote the mechanical strength of said material and the core layer is a high-swelling layer to promote the percolation rate of the ionic charges.
La matrice polymère autosupportée peut être nanostructurée par l'incorporation de nanoparticules de charges ou nanoparticules inorganiques, en particulier de nanoparticules de Siθ2, à raison notamment de quelques pourcents par rapport à la masse de polymère dans le support. Ceci permet d'améliorer certaines propriété dudit support telle que la tenue mécanique.The self-supporting polymer matrix may be nanostructured by the incorporation of nanoparticles of inorganic fillers or nanoparticles, in particular of SiO 2 nanoparticles, in particular by a few percent with respect to the mass of polymer in the support. This makes it possible to improve certain properties of said support such as the mechanical strength.
La présente invention a également pour objet un procédé de fabrication d'un matériau semi-électroactif tel que défini ci-dessus, caractérisé par le fait que l'on mélange des granulés de polymère avec un solvant et, si l'on souhaite fabriquer une matrice polymère poreuse, un agent porogène, on coule la formulation résultante sur un support et après évaporation du solvant, on élimine l'agent porogène par lavage dans un solvant adéquat par exemple si celui-ci n'a pas été éliminé lors de l' évaporation du solvant précité, on retire le film auto-supporté résultant, puis on réalise l'imprégnation dudit film par le liquide de solubilisation du système semi-électroactif, et l'on procède ensuite le cas échéant à un égouttage.The present invention also relates to a method for manufacturing a semi-electroactive material as defined above, characterized in that polymer granules are mixed with a solvent and, if it is desired to manufacture a porous polymer matrix, a pore-forming agent, pouring the resulting formulation on a support and after evaporation of the solvent, removing the pore-forming agent by washing in a suitable solvent for example if it was not removed during the evaporation of the above-mentioned solvent, the resulting self-supported film is removed, then the impregnation of said film is carried out by the solubilization liquid of the semi-electroactive system, and then, if necessary, draining is carried out.
On peut ensuite réaliser l'immersion pendant un laps de temps de 2 minutes à 3 heures. On peut réaliser l'immersion sous chauffage, par exemple à une température de 40 à 800C.
On peut aussi réaliser l'immersion avec application d'ultrasons pour aider à la pénétration du liquide de solubilisation dans la matrice.The immersion can then be carried out for a period of 2 minutes to 3 hours. Immersion can be carried out under heating, for example at a temperature of 40 to 80 ° C. Immersion can also be performed with the application of ultrasound to aid in the penetration of the solubilizing liquid into the matrix.
Egalement, la présente invention a également pour objet un kit de fabrication du matériau électroactif tel que défini ci-dessus, caractérisé par le fait qu'il consiste en :Also, the present invention also relates to a kit for manufacturing the electroactive material as defined above, characterized in that it consists of:
- une matrice polymère autosupportée telle que définie ci- dessus ; et — un liquide de solubilisation du système semi- électroactif tel que défini ci-dessus, dans lequel ledit système semi-électroactif a été solubilisé.a self-supporting polymer matrix as defined above; and a solubilization liquid of the semi-electroactive system as defined above, in which said semi-electroactive system has been solubilized.
La présente invention a aussi pour objet un dispositif électrocommandable comportant l'empilement suivant de couches :The present invention also relates to an electrically controllable device comprising the following stack of layers:
- un premier substrat à fonction verrière ;a first substrate with a glass function;
- une première couche électroniquement conductrice avec une amenée de courant associée ;a first electrically conductive layer with an associated current supply;
- un système électroactif ; — une deuxième couche électroniquement conductrice avec une amenée de courant associée ; etan electroactive system; A second electronically conducting layer with an associated current supply; and
- un second substrat à fonction verrière, caractérisé par le fait que le système électroactif est constitué par l'empilement suivant de couches : - un matériau semi-électroactif tel que défini ci-dessus ; eta second substrate with a glass function, characterized in that the electroactive system consists of the following stack of layers: a semi-electroactive material as defined above; and
- une couche autosupportée d' au moins un polymère électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation si le matériau semi-électroactif renferme au moins un composé organique électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations
jouant le rôle de charges de compensation, ou inversement d'au moins un polymère électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation si le matériau semi-électroactif renferme au moins un composé organique électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation, au moins l'un des composés électroactifs du milieu semiélectroactif et des polymères électroactifs de la couche autosupportée étant électrochrome pour obtenir un contraste de couleur, les charges ioniques dudit matériau semi-électroactif, sous l'action d'un courant électrique, permettant de réduire et/ou d' insérer des électrons et des cations ou bien d'oxyder et/ou de désinsérer des électrons et des cations dans la couche de polymère électroactif précitée et le composé organique électroactif du milieu semi-électroactif s' oxydant ou se réduisant pour obtenir un contraste de couleur.a self-supporting layer of at least one electroactive polymer capable of being reduced and / or of accepting electrons and cations acting as compensation charges if the semi-electroactive material contains at least one electroactive organic compound capable of oxidize and / or eject electrons and cations acting as compensation charges, or conversely at least one electroactive polymer capable of oxidizing and / or ejecting electrons and cations acting as compensation charges if the semi-electroactive material contains at least one an electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges, at least one of the electroactive compounds of the semi-electroactive medium and the electroactive polymers of the self-supporting layer being electrochromic to obtain a color contrast, the ionic charges of said semi-electroactive material, under the action of an electric current, for reducing and / or inserting electrons and cations or for oxidizing and / or disinsulating electrons and cations in the aforementioned electroactive polymer layer and the electroactive organic compound of the semi-electroactive medium oxidizing or reducing to obtain a color contrast.
Les cations jouant le rôle de charges de compensation peuvent aussi s'insérer ou se désinsérer dans les polymères électroactifs de la couche autosupportée.Cations acting as compensation charges can also be inserted or disinserted in the electroactive polymers of the self-supporting layer.
Les substrats à fonction verrière sont notamment choisis parmi le verre (verre float, ...) et les polymères transparents, tels que le poly (méthacrylate de méthyle) (PMMA) , le polycarbonate (PC) , le polyéthylène téréphtalate (PET) , le polyéthylène naphtoate (PEN) et les copolymères de cyclooléfines (COC) . Les couches électroniquement conductrices sont notamment des couches de type métallique, telles que des couches d'argent, d'or, de platine et de cuivre ; ou des couches de type oxyde conducteur transparent (TCO) , telles
que des couches d'oxyde d' indium dopé à l'étain (In2Os: Sn ou ITO), d'oxyde d' indium dopé à l'antimoine (In2Os: Sb), d'oxyde d' étain dopé au fluor (SnO2: F) et d'oxyde de zinc dopé à l'aluminium (ZnO:Al) ; ou des multicouches de type TCO/métal/TCO, le TCO et le métal étant notamment choisis parmi ceux énumérés ci-dessus ; ou des multicouches de type NiCr/métal/NiCr, le métal étant notamment choisi parmi ceux énumérés ci-dessus.The substrates with a glass function are chosen in particular from glass (float glass, etc.) and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthoate (PEN) and cycloolefin copolymers (COC). The electronically conductive layers are in particular metal-type layers, such as layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) type layers, such as tin doped indium oxide (In 2 Os: Sn or ITO), antimony doped indium oxide (In 2 Os: S b ), tin oxide fluorine-doped (SnO 2 : F) and zinc oxide doped with aluminum (ZnO: Al); or TCO / metal / TCO multilayers, the TCO and the metal being in particular chosen from those enumerated above; or NiC r / metal / NiC r multilayers, the metal being in particular chosen from those enumerated above.
Lorsque le système électrochrome est destiné à travailler en transmission, les matériaux électroconducteurs sont généralement des oxydes transparents dont la conduction électronique a été amplifiée par dopage tels que In2Os: Sn, In2Os: Sb , ZnO:Al ou SnO2:F. L'oxyde d' indium dopé à l'étain (In2O3:Sn ou ITO) est fréquemment retenu pour ses propriétés de conductivité électronique élevée et son absorption lumineuse faible. Lorsque le système est destiné à travailler en réflexion, l'un des matériaux électroconducteurs peut être de nature métallique . Le polymère capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation est choisi parmi les polyviologènes est notamment choisi parmi les polyviologènes, les polymères contenant des unités ou des groupements bispyridinium, pyrylium, pyrazinium, ou quinoxalium, les polyarylènes et les polyhétéroarylènes tels que les polythiophènes comme par exemple le poly (3, 4- éthylènedioxythiophène) (PEDOT), la poly [3, 3-diméthyl-3, 4- dihydro-2H-thiéno- (3, 4-b) dioxepine] (ProD0T-Me2) , le poly (isothianophtène, les polyisothianaphtène (PITN), les polyimides, les polyquinones et les polydisulfures .When the electrochromic system is intended to work in transmission, the electroconductive materials are generally transparent oxides whose electronic conduction has been amplified by doping such as In 2 Os: Sn, In 2 Os: Sb, ZnO: Al or SnO 2 : F . Tin doped indium oxide (In 2 O 3 : Sn or ITO) is frequently selected for its high electronic conductivity and low light absorption properties. When the system is intended to work in reflection, one of the electroconductive materials may be metallic in nature. The polymer capable of being reduced and / or of accepting electrons and cations acting as compensation charges is chosen from among the polyviologenes is chosen in particular from polyviologenes, polymers containing units or groups bispyridinium, pyrylium, pyrazinium, or quinoxalium, polyarylenes and polyheteroarylenes such as polythiophenes such as for example poly (3,4-ethylenedioxythiophene) (PEDOT), poly [3,3-dimethyl-3,4-dihydro-2H-thieno-3, 4-b) dioxepine] (ProD0T-Me 2 ), polyisothianophtene, polyisothianaphthene (PITN), polyimides, polyquinones and polydisulfides.
Le polymère capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de
compensation est notamment choisi parmi les polyarylamines, telles que les polyanilines, les polyarylènes, tels que les polyphénylènes ou les polyfluorènes, les polyhétéroarylènes tels que les polypyrroles comme par exemple le poly (N- suifonatopropoxy-3, 4-propylènedioxypyrrole) (PProDOP-NPrS) , les polylindoles, les copolymères du thiophène tels que le poly (acide octanoïque 2-thiophène-3-yl éthyl ester) (POTE), le poly [acide décanedioïque bis- (2-thiophén-3-yl- éthyl) ester] (PDATE), le poly{2-[3- thiénylcarbonyl) oxy] éthyl 3-thiophène carboxylate} (PTOET), le poly{ 2, 3-bis [3-thiénylcarbonyl) oxy] propyl 3-thiophène carboxylate} (PTOPT), le poly{ 3- [ (3-thiénylcarbonyl) oxy] - 2, 2-bis[3-thiénylcarbonyl) oxy] propyl 3-thiophène carboxylate} (PTOTPT), le poly [3, 6-bis (2- éthylènedioxythiényl) -N-méthyl-carbazole] (PBEDOT-NMeCz), les polyaylènevinylènes tels que les poly (para-phénylène vinylènes) (PPV) , les polyhétéroarylènevinylènes et les polymères contenant des unités ou des groupements ferrocène . Le dispositif électrocommandable de la présente invention est notamment configuré pour former :The polymer capable of oxidizing and / or ejecting electrons and cations acting as charges of compensation is chosen in particular from polyarylamines, such as polyanilines, polyarylenes, such as polyphenylenes or polyfluorenes, polyheteroarylenes such as polypyrroles, for instance poly (N-sulfonatopropoxy-3,4-propylenedioxypyrrole) (PProDOP-NPrS) ), polylindoles, thiophene copolymers such as poly [octanoic acid 2-thiophen-3-yl ethyl ester] (POTE), poly [decanedioic acid bis- (2-thiophen-3-yl-ethyl) ester] (PDATE), poly {2- [3-thienylcarbonyl) oxy] ethyl-3-thiophene carboxylate} (PTOET), poly {2,3-bis [3-thienylcarbonyl) oxy] propyl-3-thiophene carboxylate} (PTOPT) poly {3 - [(3-thienylcarbonyl) oxy] -2,2-bis [3-thienylcarbonyl) oxy] propyl-3-thiophene carboxylate} (PTOTPT), poly [3,6-bis (2-ethylenedioxythienyl) N-methyl-carbazole] (PBEDOT-NMeCz), polyaylenevinylenes such as poly (para-phenylene vinylenes) (PPV), polyheteroarylenevinylenes and polymers containing ferrocene units or groups. The electrically controllable device of the present invention is in particular configured to form:
- un toit pour véhicule automobile, activable de façon autonome, ou une vitre latérale ou une lunette arrière pour véhicule automobile ou un rétroviseur ; — un pare-brise ou une portion de pare-brise d'un véhicule automobile, d'un avion ou d'un navire, un toit d'automobile ;- a motor vehicle roof, which can be activated autonomously, or a side window or a rear window for a motor vehicle or a rear-view mirror; - a windshield or a portion of the windshield of a motor vehicle, an airplane or a ship, an automobile roof;
- un hublot d' avion ;- an airplane window;
- un panneau d'affichage d'informations graphiques et/ou alphanumériques ;a display panel of graphical and / or alphanumeric information;
- un vitrage intérieur ou extérieur pour le bâtiment ;- an interior or exterior glazing for the building;
- une fenêtre de toit ;
- un présentoir, comptoir de magasin ;- a roof window; - a display stand, store counter;
- un vitrage de protection d'un objet du type tableau ;- a protective glazing of an object of the table type;
- un écran anti-éblouissement d'ordinateur ;- anti-glare computer screen;
- un mobilier verrier ; - une paroi de séparation de deux pièces à l'intérieur d'un bâtiment.- glass furniture; - a separating wall of two rooms inside a building.
Le dispositif électrocommandable peut fonctionner en transmission ou en réflexion.The electrically controllable device can operate in transmission or in reflection.
Les substrats peuvent être transparents, plans ou bombés, clairs ou teintés dans la masse, opaques ou opacifiés, de forme polygonale ou au moins partiellement courbe. Au moins l'un des substrats peut incorporer une autre fonctionnalité, telle qu'une fonctionnalité contrôle solaire, anti-reflet ou auto-nettoyante . La présente invention porte également sur un procédé de fabrication du dispositif électrocommandable tel que défini ci-dessus, caractérisé par le fait que l'on assemble les différentes couches qui le composent par calandrage ou feuilletage éventuellement sous chauffage. Dans le cas où le dispositif électrocommandable est destiné à constituer un vitrage, le procédé ci-dessus comprend également le montage des différentes couches en vitrage simple ou multiple.The substrates may be transparent, flat or curved, clear or tinted in the mass, opaque or opacified, polygonal in shape or at least partially curved. At least one of the substrates may incorporate another feature, such as solar control, anti-reflective, or self-cleaning functionality. The present invention also relates to a method of manufacturing the electrically controllable device as defined above, characterized in that it assembles the various layers that compose it by calendering or laminating possibly under heating. In the case where the electrically controllable device is intended to constitute a glazing unit, the above method also comprises the mounting of the different layers in single or multiple glazing.
Les Exemples suivants illustrent la présente invention sans toutefois en limiter la portée. Dans ces exemples, on a utilisé les abréviations suivantes :The following Examples illustrate the present invention without however limiting its scope. In these examples, the following abbreviations have been used:
PEDOT/PSS : poly (3, 4-éthylènedioxythiophène) /polystyrène sulfonate commercialisé sous la dénomination Baytron® P par la Société « HC Stark ».PEDOT / PSS: poly (3, 4-ethylenedioxythiophene) / polystyrene sulfonate sold under the name Baytron ® P by the Company "HC Stark".
PVDF : poly (fluorure de vinylidène)
Dans ces exemples, on a effectué le dépôt des formulations humides de PEDOT/PSS (Baytron® P) en suivant la recette CPP 105D de la Société « HC Stark ».PVDF: Poly (vinylidene fluoride) In these examples, was carried out the deposition of wet formulations of PEDOT / PSS (Baytron ® P) following the CPC 105D recipe for "HC Stark" Company.
Le verre utilisé dans ces exemples est un verre muni d'une couche électroconductrice de SnC>2:F, commercialisé sous la dénomination « K-glass™ » par la Société « Pilkington ».The glass used in these examples is a glass provided with an electroconductive layer of SnC> 2: F, sold under the name "K-glass ™" by the company "Pilkington".
Pour préparer les films de PVDF, on a utilisé les poudres de poly (fluorure de vinylidène) fabriquées par ma Société « Arkema » sous la dénomination de « Kynar® » 2501 ou 2821.To prepare the PVDF films used was poly powder (polyvinylidene fluoride) manufactured by my company "Arkema" under the name "Kynar ®" in 2501 or 2821.
EXEMPLE 1 : Fabrication d'un dispositif électrochrome :EXAMPLE 1 Manufacture of an Electrochromic Device
- verre à couche de SnC>2:F revêtu d'une couche de PEDOT/PSS ;- SnC-coated glass> 2: F coated with a layer of PEDOT / PSS;
- système semi-électroactif : ferrocène + perchlorate de lithium + carbonate de propylène- semi-electroactive system: ferrocene + lithium perchlorate + propylene carbonate
- verre à couche de SnC>2:F. On a fabriqué un dispositif électrochrome en utilisant une plaque de K-glass nu et une plaque de K-glass sur laquelle une couche de PEDOT/PSS avait été déposée- SnC layer glass> 2: F. An electrochromic device was made using a bare K-glass plate and a K-glass plate on which a layer of PEDOT / PSS had been deposited.
(dépôt de 360 microns humide) . Avant assemblage, la couche de PEDOT/PSS a été réduite dans une solution d' acétonitrile et de perchlorate de lithium à IM.(wet 360 micron deposit). Before assembly, the PEDOT / PSS layer was reduced in a solution of acetonitrile and lithium perchlorate at 1M.
On a fabriqué un film autosupporté de PVDF en mélangeant 3,5 g de PVDF (Kynar® 2501), 6,5 g de phtalate de dibutyle et 12 g d'acétone. On a agité la formulation pendant deux heures, et on l'a coulée sur une plaque de verre. Après évaporation du solvant, on a retiré le film de PVDF de la plaque de verre sous un filet d'eau.Was fabricated PVDF self-supporting film by mixing 3.5 g of PVDF (Kynar ® 2501), 6.5 g of dibutyl phthalate and 12 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water.
On a préparé une solution semi-électroactive en mélangeant 0,23 g de ferrocène et 0,27 g de perchlorate de
lithium dans 40 ml de carbonate de propylène. On a agité la solution pendant 1 heure.A semi-electroactive solution was prepared by mixing 0.23 g of ferrocene and 0.27 g of sodium perchlorate. lithium in 40 ml of propylene carbonate. The solution was stirred for 1 hour.
On a obtenu le milieu semi-électroactif auto- supporté en plongeant pendant 5 minutes le film de PVDF d'environ 80 microns d'épaisseur dans de l'éther diéthylique puis 5 minutes dans la solution semi- électroactive . On a ensuite essuyé le film de PVDF imprégné de solution semi-électroactive entre deux papiers absorbants avant de le déposer sur une plaque de verre K- glass nu. Un cadre en adhésif double face a été utilisé comme joint et la plaque de K-glass recouverte de PEDOT/PSS a été déposée sur le film semi-électroactif pour terminer le dispositif électrochrome.The self-supported semi-electroactive medium was obtained by immersing the PVDF film about 80 microns thick in diethyl ether for 5 minutes and then in the semi- electroactive solution for 5 minutes. The PVDF film impregnated with semi-electroactive solution was then wiped between two absorbent papers before being deposited on a bare K-glass glass plate. A double-sided adhesive frame was used as a seal and the K-glass plate coated with PEDOT / PSS was deposited on the semi-electroactive film to terminate the electrochromic device.
Le dispositif électrochrome ainsi fabriqué a une transmission lumineuse de 42% à l'état décoloré, sous une tension de 1,5V et de 13,5% à l'état coloré sous une tension de -1,5V. Après 1000 cycles de décoloration et de coloration les performances du dispositif électrochrome sont demeurées inchangées.The electrochromic device thus manufactured has a light transmission of 42% in the decolorized state, at a voltage of 1.5V and 13.5% in the colored state at a voltage of -1.5V. After 1000 cycles of discoloration and coloration the performance of the electrochromic device remained unchanged.
Exemple 2 : Fabrication d'un dispositif électrochrome :Example 2 Manufacture of an Electrochromic Device
- verre à couche de SnÛ2:F revêtu d'une couche de PEDOT/PSS ; — système semi-électroactif : ferrocène + trifluorométhanesulfonate de lithium + carbonate de propylène- SnO2 layer glass: F coated with a layer of PEDOT / PSS; - semi-electroactive system: ferrocene + lithium trifluoromethanesulfonate + propylene carbonate
- verre à couche de SnÛ2:F.- SnÛ2 layered glass: F.
On a fabriqué un dispositif électrochrome en utilisant une plaque de K-glass nu et une plaque de K-glass sur laquelle une couche de PEDOT/PSS avait été déposéeAn electrochromic device was made using a bare K-glass plate and a K-glass plate on which a layer of PEDOT / PSS had been deposited.
(dépôt de 360 microns humide) . Avant assemblage, la couche
de PEDOT/PSS a été réduite dans une solution d' acétonitrile et de perchlorate de lithium à IM.(wet 360 micron deposit). Before assembly, the layer of PEDOT / PSS was reduced in a solution of acetonitrile and lithium perchlorate at 1M.
On a fabriqué un film autosupporté de PVDF en mélangeant 3,5 g de PVDF (Kynar® 2821), 6,5 g de phtalate de dibutyle et 12 g d'acétone. On a agité la formulation pendant deux heures, et on l'a coulée sur une plaque de verre. Après évaporation du solvant, on a retiré le film de PVDF de la plaque de verre sous un filet d'eau.Was fabricated PVDF self-supporting film by mixing 3.5 g of PVDF (Kynar ® 2821), 6.5 g of dibutyl phthalate and 12 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water.
On a préparé une solution semi-électroactive en mélangeant 0,23 g de ferrocène et 0,39 g de trifluorométhanesulfonate de lithium dans 40 ml de carbonate de propylène. On a agité la solution pendant 1 heure .A semi-electroactive solution was prepared by mixing 0.23 g of ferrocene and 0.39 g of lithium trifluoromethanesulfonate in 40 ml of propylene carbonate. The solution was stirred for 1 hour.
On a obtenu le milieu semi-électroactif auto- supporté en plongeant pendant 5 minutes le film de PVDF d'environ 80 microns d'épaisseur dans de l'éther diéthylique puis 5 minutes dans la solution semi- électroactive. On a ensuite essuyé le film de PVDF imprégné de solution semi-électroactive entre deux papiers absorbants avant de le déposer sur une plaque de verre K- glass nu. Un cadre en adhésif double face a été utilisé comme joint et la plaque de K-glass recouverte de PEDOT/PSS a été déposée sur le film semi-électroactif pour terminer le dispositif électrochrome. Le dispositif électrochrome ainsi fabriqué a une transmission lumineuse de 45% à l'état décoloré sous une tension de 1,5V et de 15% à l'état coloré sous une tension de -1,5V. Après 100 cycles de décoloration et de coloration les performances du dispositif électrochrome sont demeurées inchangées.The self-supported semi-electroactive medium was obtained by immersing the PVDF film about 80 microns thick in diethyl ether for 5 minutes and then in the semi- electroactive solution for 5 minutes. The PVDF film impregnated with semi-electroactive solution was then wiped between two absorbent papers before being deposited on a bare K-glass glass plate. A double-sided adhesive frame was used as a seal and the K-glass plate coated with PEDOT / PSS was deposited on the semi-electroactive film to terminate the electrochromic device. The electrochromic device thus manufactured has a light transmission of 45% in the decolorized state at a voltage of 1.5V and 15% in the colored state at a voltage of -1.5V. After 100 cycles of discoloration and coloration the performance of the electrochromic device remained unchanged.
Exemple comparatif 3 : Préparation d' un dispositif électrochrome :
- verre à couche de Snθ2:F revêtu d'une couche de PEDOT/PSS ;Comparative Example 3 Preparation of an Electrochromic Device - SnO2: F coated glass coated with a layer of PEDOT / PSS;
- électrolyte : perchlorate de lithium + carbonate de propylène- electrolyte: lithium perchlorate + propylene carbonate
- verre à couche de Snθ2:F revêtu d'une couche de PEDOT/PSS.- SnO2: F coated glass coated with a layer of PEDOT / PSS.
On a fabriqué un dispositif électrochrome en utilisant deux plaques de K-glass sur chacune desquelles une couche de PEDOT/PSS avait été déposée (dépôt de 180 microns humide) . Avant assemblage, les couches de PEDOT/PSS ont été réduites dans une solution d' acétonitrile et de perchlorate de lithium à IM. On a fabriqué un film autosupporté de PVDF en mélangeant 3,5 g de PVDF (Kynar® 2821), 6,5 g de phtalate de dibutyle et 12 g d'acétone. On a agité la formulation pendant deux heures et on l'a coulée sur une plaque de verre. Après évaporation du solvant, on a retiré le film de PVDF de la plaque de verre sous un filet d'eau.An electrochromic device was manufactured using two K-glass plates on each of which a PEDOT / PSS layer had been deposited (wet 180 micron deposit). Before assembly, the PEDOT / PSS layers were reduced in a solution of acetonitrile and lithium perchlorate at 1M. Was fabricated PVDF self-supporting film by mixing 3.5 g of PVDF (Kynar ® 2821), 6.5 g of dibutyl phthalate and 12 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water.
On a préparé une solution d' électrolyte en solubilisant 0,27 g de perchlorate de lithium dans 40 ml de carbonate de propylène. On a agité la solution pendant 1 heure. On a obtenu l' électrolyte auto-supporté en plongeant pendant 5 minutes le film de PVDF d'environ 80 microns d'épaisseur 5 minutes dans de l'éther diéthylique puis 5 minutes dans la solution d' électrolyte . On a ensuite essuyé le film de PVDF imprégné de solution d' électrolyte entre deux papiers absorbants avant de le déposer sur l'une des deux plaques de K-glass recouverte de PEDOT/PSS. Un cadre en adhésif double face a été utilisé comme joint et la seconde plaque de K-glass recouverte de
PEDOT/PSS a été déposée sur le film électrolyte auto- supporté pour terminer le dispositif électrochrome.An electrolyte solution was prepared by solubilizing 0.27 g of lithium perchlorate in 40 ml of propylene carbonate. The solution was stirred for 1 hour. The self-supporting electrolyte was obtained by dipping for 5 minutes the PVDF film about 80 microns thick 5 minutes in diethyl ether and then 5 minutes in the electrolyte solution. The PVDF film impregnated with electrolyte solution was then wiped between two absorbent papers before being deposited on one of the two K-glass plates covered with PEDOT / PSS. A double-sided adhesive frame was used as a seal and the second K-glass plate covered with PEDOT / PSS was deposited on the self-supported electrolyte film to terminate the electrochromic device.
Le dispositif électrochrome ainsi fabriqué a une transmission lumineuse de 18% à l'état décoloré sous une tension de OV et de 10,5% à l'état coloré sous une tension de -2V.
The electrochromic device thus manufactured has a light transmission of 18% in the decolorized state under a voltage of OV and 10.5% in the colored state under a voltage of -2V.
Claims
REVENDICATIONS
1 - Matériau semi-électroactif de dispositif électrocommandable à propriétés optiques/énergétiques variables, caractérisé par le fait qu'il comprend une matrice polymère autosupportée dans laquelle est inséré un système électroactif comprenant ou constitué par:1 - Semi-electroactive material for an electrocontrollable device with variable optical/energetic properties, characterized in that it comprises a self-supported polymer matrix in which an electroactive system is inserted comprising or constituted by:
- au moins un composé organique électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation; ou- at least one electroactive organic compound capable of oxidizing and/or ejecting electrons and cations acting as compensation charges; Or
- au moins un composé organique électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; et- at least one electroactive organic compound capable of reducing and/or accepting electrons and cations acting as compensation charges; And
- des charges ioniques ; ainsi qu'un liquide de solubilisation dudit système semi- électroactif, ledit liquide ne solubilisant pas ladite matrice polymère autosupportée, cette dernière étant choisie pour assurer un chemin de percolation des charges ioniques, ceci permettant, sous l'action d'un courant diélectrique, des réactions d'oxydation et de réduction desdits composés organiques électroactifs, lesquelles sont nécessaires pour obtenir un contraste de couleur.- ionic charges; as well as a liquid for solubilizing said semi-electroactive system, said liquid not solubilizing said self-supported polymer matrix, the latter being chosen to ensure a percolation path for the ionic charges, this allowing, under the action of a dielectric current, oxidation and reduction reactions of said electroactive organic compounds, which are necessary to obtain color contrast.
2 - Matériau semi-électroactif selon la revendication 1, caractérisé par le fait que le ou les composés organiques électroactifs capables de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation est ou sont choisis parmi les bipyridiniums ou viologènes tels que le diperchlorate de 1 , l ' -diéthyl-4 , 4 ' -bipyridinium, les pyraziniums, les pyrimidiniums, les quinoxaliniums, les pyryliums, les pyridiniums, les tétrazoliums, les verdazyls, les quinones, les quinodiméthanes, les tricyanovinylbenzènes, le tétracyanoéthylène, les polysulfures et les disulfures,
ainsi que tous les dérivés polymériques électroactifs des composés électroactifs qui viennent d'être mentionnés, et le ou les composés organiques électroactifs capables de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation est ou sont choisis parmi les métallocènes, tels que les cobaltocènes, les ferrocènes, la N, N, N' , N' -tétraméthylphénylènediamine2 - Semi-electroactive material according to claim 1, characterized in that the electroactive organic compound(s) capable of reducing and/or accepting electrons and cations playing the role of compensation charges is or are chosen from among the bipyridiniums or viologens such as 1, l'-diethyl-4, 4'-bipyridinium diperchlorate, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulphides and disulphides, as well as all the electroactive polymeric derivatives of the electroactive compounds which have just been mentioned, and the electroactive organic compound(s) capable of oxidizing and/or ejecting electrons and cations acting as compensation charges is or are chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N', N' -tetramethylphenylenediamine
(TMPD) , les phénothiazines telles que la phénothiazine, les dihydrophénazines telles que la 5, 10-dihydro-5, 10- diméthylphénazine, la méthylphénothiazone réduite (MPT) , le violet de méthylène bernthsen (MVB) , les verdazyls, ainsi que tous les dérivés polymériques électroactifs des composés électroactifs qui viennent d'être mentionnés.(TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene berthsen violet (MVB), verdazyls, as well as all the electroactive polymeric derivatives of the electroactive compounds which have just been mentioned.
3 - Matériau semi-électroactif selon l'une des revendications 1 et 2, caractérisé par le fait que les charges ioniques sont portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique et/ou au moins un acide solubilisé dans ledit liquide et/ou par ladite matrice polymère autosupportée, le ou les sels ioniques étant choisis notamment parmi le perchlorate de lithium, les sels trifluorométhanesulfonates ou triflates, les sels de trifluorométhanesulfonylimide et les sels d'ammonium, et le ou les acides étant notamment choisis parmi l'acide sulfurique (H2SO4), l'acide triflique (CF3SO3H), l'acide phosphorique (H3PO4) et l'acide polyphosphorique (Hn+2 Pn O3n+i) .3 - Semi-electroactive material according to one of claims 1 and 2, characterized in that the ionic charges are carried by the electroactive organic compound(s) and/or by at least one ionic salt and/or at least one solubilized acid in said liquid and/or by said self-supported polymer matrix, the ionic salt(s) being chosen in particular from lithium perchlorate, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts, and the acid(s) being in particular chosen from sulfuric acid (H 2 SO 4 ), triflic acid (CF 3 SO 3 H), phosphoric acid (H 3 PO 4 ) and polyphosphoric acid (H n+2 P n O 3n+ i ) .
4 - Matériau semi-électroactif selon l'une des revendications 1 à 3, caractérisé par le fait que le liquide de solubilisation est constitué par un solvant ou un mélange de solvants et/ou par au moins un liquide ionique ou sel fondu à température ambiante, ledit liquide ionique ou sel fondu ou lesdits liquides ioniques ou sels fondus constituant alors un liquide de solubilisation portant des charges ioniques, lesquelles représentent tout ou partie des charges ioniques dudit système semi-
électroactif, le ou les solvants étant notamment choisis parmi le diméthylsulfoxyde, le N, N-diméthylformamide, le N, N-diméthylacétamide, le carbonate de propylène, le carbonate d'éthylène, la N-méthyl-2-pyrrolidone (1- méthyl-2-pyrrolidinone) , la gamma-butyrolactone, les éthylène glycols, les alcools, les cétones, les nitriles et l'eau, et le ou les liquides ioniques étant notamment choisis parmi les sels d' imidazolium, tels que le 1-éthyl- 3-méthylimidazolium tétrafluoroborate (emim-BF4) , le 1- éthyl-3-méthylimidazolium trifluorométhane sulfonate (emim- CF3SO3) , le l-éthyl-3-méthylimidazolium bis (trifluorométhylsulfonyl) imide (emim-N (CF3SO2) 2 ou emim- TSFI) et le l-butyl-3-méthylimidazolium bis (trifluorométhylsulfonyl) imide (bmim-N (CF3SO2) 2 ou bmim- TSFI) .4 - Semi-electroactive material according to one of claims 1 to 3, characterized in that the solubilization liquid is constituted by a solvent or a mixture of solvents and/or by at least one ionic liquid or salt molten at room temperature , said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said semi-system. electroactive, the solvent(s) being chosen in particular from dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate, N-methyl-2-pyrrolidone (1-methyl -2-pyrrolidinone), gamma-butyrolactone, ethylene glycols, alcohols, ketones, nitriles and water, and the ionic liquid(s) being chosen in particular from imidazolium salts, such as 1-ethyl - 3-methylimidazolium tetrafluoroborate (emim-BF 4 ), 1-ethyl-3-methylimidazolium trifluoromethane sulfonate (emim-CF 3 SO 3 ), l-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (emim-N (CF3SO2) ) 2 or emim-TSFI) and l-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (bmim-N (CF3SO2) 2 or bmim-TSFI).
5 - Matériau semi-électroactif selon l'une des revendications 1 à 4, caractérisé par le fait que la matrice polymère autosupportée est constituée par au moins une couche polymère dans laquelle ledit liquide a pénétré à cœur, en particulier comportant de une à trois couches, le polymère constituant au moins une couche étant un homo- ou copolymère se présentant sous la forme d'un film non poreux mais capable de gonfler dans ledit liquide, ou se présentant sous la forme d'un film poreux, ledit film poreux étant éventuellement capable de gonfler dans le liquide comportant des charges ioniques et dont la porosité après gonflement est choisie pour permettre la percolation des charges ioniques dans l'épaisseur du film imprégné de liquide . 6 - Matériau semi-électroactif selon la revendication 5, caractérisé par le fait que le matériau polymère constituant au moins une couche est choisi parmi :5 - Semi-electroactive material according to one of claims 1 to 4, characterized in that the self-supported polymer matrix is constituted by at least one polymer layer into which said liquid has penetrated, in particular comprising from one to three layers , the polymer constituting at least one layer being a homo- or copolymer in the form of a non-porous film but capable of swelling in said liquid, or in the form of a porous film, said porous film optionally being capable of swelling in the liquid containing ionic charges and whose porosity after swelling is chosen to allow the percolation of the ionic charges in the thickness of the film impregnated with liquid. 6 - Semi-electroactive material according to claim 5, characterized in that the polymer material constituting at least one layer is chosen from:
- les homo- ou copolymères ne comportant pas de charges ioniques, auquel cas celles-ci sont portées par le ou les composés organiques électroactifs et/ou par au moins
un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu ;- homo- or copolymers not containing ionic charges, in which case these are carried by the electroactive organic compound(s) and/or by at least an ionic salt or acid solubilized and/or by at least one ionic liquid or molten salt;
- les homo- ou copolymères comportant des charges ioniques, auquel cas des charges supplémentaires permettant de renforcer la vitesse de percolation peuvent être portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu ; et - les mélanges d' au moins un homo- ou copolymère ne portant pas de charges ioniques et d'au moins un homo- ou copolymère comportant des charges ioniques, auquel cas des charges supplémentaires permettant de renforcer la vitesse de percolation peuvent être portées par le ou les composés organiques électroactifs et/ou par au moins un sel ionique ou acide solubilisé et/ou par au moins un liquide ionique ou sel fondu.- homo- or copolymers comprising ionic charges, in which case additional charges making it possible to reinforce the percolation speed can be carried by the electroactive organic compound(s) and/or by at least one ionic salt or solubilized acid and/or by at minus one ionic liquid or molten salt; and - mixtures of at least one homo- or copolymer not carrying ionic charges and at least one homo- or copolymer comprising ionic charges, in which case additional charges making it possible to reinforce the percolation speed can be carried by the electroactive organic compound(s) and/or by at least one ionic salt or solubilized acid and/or by at least one ionic liquid or molten salt.
7 - Matériau semi-électroactif selon l'une des revendications 1 à 6, caractérisé par le fait que la matrice polymère est constituée par un film à base d'un homo- ou copolymère comportant des charges ioniques, apte à donner par lui-même un film essentiellement capable d'assurer la vitesse de percolation recherchée pour le système électroactif ou une vitesse de percolation supérieure à celle-ci et d'un homo- ou copolymère comportant ou non des charges ioniques, apte à donner par lui-même un film ne permettant pas nécessairement d'assurer la vitesse de percolation recherchée mais essentiellement capable d'assurer la tenue mécanique, les teneurs de chacun de ces deux homo- ou copolymères étant réglées pour que soient assurées à la fois la vitesse de percolation recherchée et la tenue mécanique du milieu actif organique autosupporté résultant.
8 - Matériau semi-électroactif selon l'une des revendications 6 et 7, caractérisé par le fait que le ou les polymères de la matrice polymère ne comportant pas de charges ioniques sont choisis parmi les copolymères d'éthylène, d'acétate de vinyle et éventuellement d'au moins un autre comonomère, tels que les copolymères éthylène-acétate de vinyle (EVA) ; le polyuréthane (PU) ; le polyvinyl butyral (PVB) ; les polyimides (PI) ; les polyamides (PA) ; le polystyrène (PS) ; le poly (fluorure de vinylidène) (PVDF) ; les polyéther-éther-cétones (PEEK) ; le poly (oxyde d'éthylène) (POE) ; les copolymères d' épichlorhydrine et le poly (méthacrylate de méthyle)7 - Semi-electroactive material according to one of claims 1 to 6, characterized in that the polymer matrix is constituted by a film based on a homo- or copolymer comprising ionic charges, capable of giving by itself a film essentially capable of ensuring the desired percolation speed for the electroactive system or a percolation speed greater than this and a homo- or copolymer comprising or not ionic charges, capable of giving by itself a film not necessarily ensuring the desired percolation speed but essentially capable of ensuring the mechanical strength, the contents of each of these two homo- or copolymers being adjusted so that both the desired percolation speed and the strength are ensured mechanics of the resulting self-supported organic active medium. 8 - Semi-electroactive material according to one of claims 6 and 7, characterized in that the polymer(s) of the polymer matrix not comprising ionic charges are chosen from copolymers of ethylene, vinyl acetate and optionally at least one other comonomer, such as ethylene-vinyl acetate (EVA) copolymers; polyurethane (PU); polyvinyl butyral (PVB); polyimides (PI); polyamides (PA); polystyrene (PS); poly(vinylidene fluoride) (PVDF); polyether-ether-ketones (PEEK); poly(ethylene oxide) (POE); epichlorohydrin copolymers and poly(methyl methacrylate)
(PMMA) , et que le ou les polymères de la matrice polymère portant des charges ioniques ou polyélectrolytes sont choisis parmi les polymères sulfonés qui ont subi un échange des ions H+ des groupements SO3H par les ions des charges ioniques souhaitées, cet échange d'ions ayant eu lieu avant et/ou simultanément avec le gonflement du polyélectrolyte dans le liquide comportant des charges ioniques, le polymère sulfoné étant notamment choisi parmi les copolymères sulfonés de tétrafluoroéthylène, les polystyrènes sulfonés (PSS) , les copolymères de polystyrène sulfoné, le poly (2-acrylamido-2-méthyl-l-propanesulfonique acide) (PAMPS), les polyétheréthercétones (PEEK) sulfonées et les polyimides sulfonés.(PMMA), and that the polymer(s) of the polymer matrix carrying ionic charges or polyelectrolytes are chosen from sulfonated polymers which have undergone an exchange of H + ions of SO3H groups by ions of the desired ionic charges, this exchange of ions having taken place before and/or simultaneously with the swelling of the polyelectrolyte in the liquid comprising ionic charges, the sulfonated polymer being chosen in particular from sulfonated copolymers of tetrafluoroethylene, sulfonated polystyrenes (PSS), copolymers of sulfonated polystyrene, poly (2-acrylamido-2-methyl-l-propanesulfonic acid) (PAMPS), sulfonated polyetheretherketones (PEEK) and sulfonated polyimides.
9 - Matériau semi-électroactif selon l'une des revendications 1 à 8, dans lequel le support comporte au moins deux couches, caractérisé par le fait qu'un empilement d'au moins deux couches a été constitué à partir de couches polymères électrolytes et/ou non électrolytes avant pénétration à cœur du liquide, puis a été gonflé par ledit liquide.9 - Semi-electroactive material according to one of claims 1 to 8, in which the support comprises at least two layers, characterized in that a stack of at least two layers was formed from electrolyte polymer layers and /or no electrolytes before penetration into the heart of the liquid, then was inflated by said liquid.
10 - Matériau semi-électroactif selon l'une des revendications 1 à 9, dans lequel le support comporte trois couches, caractérisé par le fait que les deux couches externes de l'empilement sont des couches à faible gonflement pour favoriser la tenue mécanique dudit matériau
et la couche centrale est une couche à fort gonflement pour favoriser la vitesse de percolation des charges ioniques.10 - Semi-electroactive material according to one of claims 1 to 9, in which the support comprises three layers, characterized in that the two external layers of the stack are layers with low swelling to promote the mechanical strength of said material and the central layer is a highly swelling layer to promote the percolation speed of the ionic charges.
11 - Matériau semi-électroactif selon l'une des revendications 1 à 10, caractérisé par le fait que la matrice polymère auto-supportée est nanostructurée par l'incorporation de nanoparticules de charges ou nanoparticules inorganiques, en particulier de nanoparticules de Siθ2.11 - Semi-electroactive material according to one of claims 1 to 10, characterized in that the self-supported polymer matrix is nanostructured by the incorporation of charged nanoparticles or inorganic nanoparticles, in particular Siθ2 nanoparticles.
12 - Procédé de fabrication d'un matériau semi- électroactif tel que défini à l'une des revendications 1 à12 - Process for manufacturing a semi-electroactive material as defined in one of claims 1 to
11, caractérisé par le fait que l'on mélange des granulés de polymère avec un solvant et, si l'on souhaite fabriquer une matrice polymère poreuse, un agent porogène, on coule la formulation résultante sur un support et après évaporation du solvant, on élimine l'agent porogène par lavage dans un solvant adéquat par exemple si celui-ci n'a pas été éliminé lors de l' évaporation du solvant précité, on retire le film autosupporté résultant, puis on réalise l'imprégnation dudit film par le liquide de solubilisation du système semi-électroactif, et l'on procède ensuite le cas échéant à un égouttage.11, characterized in that polymer granules are mixed with a solvent and, if it is desired to manufacture a porous polymer matrix, a pore-forming agent, the resulting formulation is poured onto a support and after evaporation of the solvent, we eliminates the pore-forming agent by washing in a suitable solvent, for example if it has not been eliminated during the evaporation of the aforementioned solvent, the resulting self-supported film is removed, then said film is impregnated with the liquid solubilization of the semi-electroactive system, and then, if necessary, draining is carried out.
13 - Kit de fabrication du matériau semi- électroactif tel que défini à l'une des revendications 1 à 11, caractérisé par le fait qu'il consiste en : - une matrice polymère autosupportée telle que définie à l'une des revendications 5 à 11 ; et13 - Kit for manufacturing the semi-electroactive material as defined in one of claims 1 to 11, characterized in that it consists of: - a self-supported polymer matrix as defined in one of claims 5 to 11 ; And
- un liquide de solubilisation du système semi- électroactif tel que défini à la revendication 4, dans lequel ledit système semi-électroactif a été solubilisé. 14 - Dispositif électrocommandable à propriétés optiques/énergétiques variables, fonctionnant notamment en transmission ou en réflexion, comportant l'empilement suivant de couches :
— un premier substrat à fonction verrière ;- a liquid for solubilizing the semi-electroactive system as defined in claim 4, in which said semi-electroactive system has been solubilized. 14 - Electrocontrollable device with variable optical/energetic properties, operating in particular in transmission or reflection, comprising the following stack of layers: — a first substrate with a glass function;
— une première couche électroniquement conductrice avec une amenée de courant associée ;— a first electronically conductive layer with an associated current supply;
- un système électroactif ; — une deuxième couche électroniquement conductrice avec une amenée de courant associée ; et- an electroactive system; — a second electronically conductive layer with an associated current supply; And
- un second substrat à fonction verrière, les substrats étant notamment transparents, plans ou bombés, clairs ou teintés dans la masse, opaques ou opacifiés, de forme polygonale ou au moins partiellement courbe, et au moins l'un des substrats pouvant incorporer une autre fonctionnalité telle qu'une fonctionnalité de contrôle solaire, anti-reflet ou auto-nettoyante, le système électroactif étant constitué par l'empilement suivant de couches :- a second substrate with a glass function, the substrates being in particular transparent, flat or curved, clear or mass-tinted, opaque or opacified, of polygonal shape or at least partially curved, and at least one of the substrates being able to incorporate another functionality such as solar control, anti-reflection or self-cleaning functionality, the electroactive system being constituted by the following stack of layers:
— un matériau semi-électroactif tel que défini à l'une des revendications 1 à 11 ; et— a semi-electroactive material as defined in one of claims 1 to 11; And
- une couche autosupportée d' au moins un polymère électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation si le matériau semi-électroactif renferme au moins un composé organique électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation, ou inversement d'au moins un polymère électroactif capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation si le matériau semi-électroactif renferme au moins un composé organique électroactif capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation,
au moins l'un des composés électroactifs du milieu semiélectroactif et des polymères électroactifs de la couche autosupportée étant électrochrome pour obtenir un contraste de couleur, les charges ioniques dudit matériau semi-électroactif, sous l'action d'un courant électrique, permettant de réduire et/ou d' insérer des électrons et des cations ou bien d'oxyder et/ou de désinsérer des électrons et des cations dans la couche de polymère électroactif précitée et le composé organique électroactif du milieu semi-électroactif s' oxydant ou se réduisant pour obtenir un contraste de couleur .- a self-supported layer of at least one electroactive polymer capable of reducing and/or accepting electrons and cations playing the role of compensation charges if the semi-electroactive material contains at least one electroactive organic compound capable of being reduced oxidize and/or eject electrons and cations acting as compensation charges, or conversely at least one electroactive polymer capable of oxidizing and/or ejecting electrons and cations acting as charges compensation if the semi-electroactive material contains at least one electroactive organic compound capable of reducing and/or accepting electrons and cations playing the role of compensation charges, at least one of the electroactive compounds of the semi-electroactive medium and of the electroactive polymers of the self-supported layer being electrochromic to obtain a color contrast, the ionic charges of said semi-electroactive material, under the action of an electric current, making it possible to reduce and/or to insert electrons and cations or to oxidize and/or to remove electrons and cations in the aforementioned electroactive polymer layer and the electroactive organic compound of the semi-electroactive medium oxidizing or reducing to achieve color contrast.
15 - Dispositif électrocommandable selon la revendication 14, caractérisé par le fait que le polymère capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation est choisi parmi les polyviologènes, les polymères contenant des unités ou des groupements bispyridinium, pyrylium, pyrazinium, ou quinoxalium, les polyarylènes et les polyhétéroarylènes tels que les polythiophènes, comme par exemple le poly (3, 4-éthylènedioxythiophène) (PEDOT), la poly [3, 3-diméthyl-3, 4-dihydro-2H-thiéno- (3, 4-b) dioxépine]15 - Electrocontrollable device according to claim 14, characterized in that the polymer capable of reducing and/or accepting electrons and cations playing the role of compensation charges is chosen from polyviologens, polymers containing units or bispyridinium, pyrylium, pyrazinium, or quinoxalium groups, polyarylenes and polyheteroarylenes such as polythiophenes, such as for example poly (3, 4-ethylenedioxythiophene) (PEDOT), poly [3, 3-dimethyl-3, 4- dihydro-2H-thieno-(3,4-b)dioxepin]
(ProDOT-Me2) , le poly (isothianophtène) , les polyisothianaphtène (PITN), les polyimides, les polyquinones et les polydisulfures et que le polymère capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation est choisi parmi les polyarylamines, telles que les polyanilines, les polyarylènes, tels que les polyphénylènes ou les polyfluorènes, les polyhétéroarylènes tels que les polypyrroles comme par exemple le poly (N-sulfonatopropoxy- 3, 4-propylènedioxypyrrole) (PProDOP-NPrS) , les poylindoles, les copolymères du thiophène tels que le poly (acide
octanoïque 2-thiophène-3-yl éthyl ester) (POTE) , le poly [acide décanedioïque bis- (2-thiophén-3-yl-éthyl) ester](ProDOT-Me2), poly (isothianophthene), polyisothianaphthene (PITN), polyimides, polyquinones and polydisulfides and that the polymer capable of oxidizing and/or ejecting electrons and cations playing the role of compensation fillers is chosen from polyarylamines, such as polyanilines, polyarylenes, such as polyphenylenes or polyfluorenes, polyheteroarylenes such as polypyrroles such as for example poly (N-sulfonatopropoxy- 3, 4-propylenedioxypyrrole) (PProDOP- NPrS), poylindoles, thiophene copolymers such as poly (acid octanoic 2-thiophene-3-yl ethyl ester) (POTE), poly [decanedioic acid bis-(2-thiophen-3-yl-ethyl) ester]
(PDATE), le poly{ 2- [ 3-thiénylcarbonyl) oxy] éthyl 3-thiophène carboxylate} (PTOET), le poly{ 2, 3-bis [3- thiénylcarbonyl) oxy] propyl 3-thiophène carboxylate}(PDATE), poly{2-[3-thienylcarbonyl)oxy]ethyl 3-thiophene carboxylate} (PTOET), poly{2,3-bis[3-thienylcarbonyl)oxy]propyl 3-thiophene carboxylate}
(PTOPT), le poly{3- [ (3-thiénylcarbonyl) oxy] -2,2-bis [3- thiénylcarbonyl) oxy] propyl 3-thiophène carboxylate}(PTOPT), poly{3-[(3-thienylcarbonyl)oxy]-2,2-bis[3-thienylcarbonyl)oxy]propyl 3-thiophene carboxylate}
(PTOTPT), le poly [3, 6-bis (2-éthylènedioxythiényl) -N-méthyl- carbazole] (PBEDOT-NMeCz) , les polyaylènevinylènes tels que les poly (para-phénylène vinylènes) (PPV), les polyhétéroarylènevinylènes et les polymères contenant des unités ou des groupements ferrocène.(PTOTPT), poly [3, 6-bis (2-ethylenedioxythienyl) -N-methyl- carbazole] (PBEDOT-NMeCz), polyaylene vinylenes such as poly (para-phenylene vinylenes) (PPV), polyheteroarylene vinylenes and polymers containing ferrocene units or groups.
16 - Dispositif électrocommandable selon l'une des revendications 14 et 15, caractérisé par le fait qu'il est configuré pour former :16 - Electrocontrollable device according to one of claims 14 and 15, characterized in that it is configured to form:
- un toit pour véhicule automobile, activable de façon autonome, ou une vitre latérale ou une lunette arrière pour véhicule automobile ou un rétroviseur ;- a roof for a motor vehicle, which can be activated independently, or a side window or a rear window for a motor vehicle or a rear-view mirror;
- un pare-brise ou une portion de pare-brise d'un véhicule automobile, d'un avion, d'un navire, un toit d'automobile ;- a windshield or a portion of a windshield of a motor vehicle, an airplane, a ship, an automobile roof;
- un hublot d' avion ;- an airplane window;
- un vitrage pour grues, engins de chantiers, tracteurs ;- glazing for cranes, construction machinery, tractors;
- un panneau d'affichage d'informations graphiques et/ou alphanumériques ;- a display panel with graphic and/or alphanumeric information;
- un vitrage intérieur ou extérieur pour le bâtiment ;- interior or exterior glazing for the building;
- une fenêtre de toit ;- a roof window;
- un présentoir, comptoir de magasin ;- a display, store counter;
- un vitrage de protection d'un objet du type tableau ; - un écran anti-éblouissement d'ordinateur ;- protective glazing for a painting type object; - an anti-glare computer screen;
- un mobilier verrier ;
- une paroi de séparation de deux pièces à l'intérieur d'un bâtiment.- glass furniture; - a wall separating two rooms inside a building.
17 - Procédé de fabrication du dispositif électrocommandable tel que défini à l'une des revendications 14 à 16, caractérisé par le fait que l'on assemble les différentes couches qui le composent par calandrage ou feuilletage éventuellement sous chauffage, et lorsque le dispositif électrocommandable est destiné à constituer un vitrage, on assemble les différentes couches composant ledit système en vitrage simple ou multiple.17 - Method of manufacturing the electrocontrollable device as defined in one of claims 14 to 16, characterized in that the different layers which compose it are assembled by calendering or lamination optionally under heating, and when the electrocontrollable device is intended to constitute glazing, the different layers composing said system are assembled into single or multiple glazing.
18 - Vitrage simple ou multiple caractérisé par le fait qu' il comprend un dispositif électrocommandable tel que défini à l'une des revendications 14 à 16.
18 - Single or multiple glazing characterized in that it comprises an electrocontrollable device as defined in one of claims 14 to 16.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0755987A FR2917849B1 (en) | 2007-06-25 | 2007-06-25 | SEMI-ELECTROACTIVE MATERIAL COMPRISING ORGANIC COMPOUNDS WITH POSITIVE OR NEGATIVE REDOX ACTIVITY, METHOD AND KIT FOR PRODUCING SAID MATERIAL, ELECTRO-CONTROLLABLE DEVICE AND GLAZING USING SUCH MATERIAL |
| PCT/FR2008/051161 WO2009007602A1 (en) | 2007-06-25 | 2008-06-25 | Semi-electroactive material containing organic compounds with positive or negative redox activity, method and kit for making such material, electrically controlled device and glazing using such semi-electroactive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2162787A1 true EP2162787A1 (en) | 2010-03-17 |
Family
ID=38963091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08806090A Withdrawn EP2162787A1 (en) | 2007-06-25 | 2008-06-25 | Semi-electroactive material containing organic compounds with positive or negative redox activity, method and kit for making such material, electrically controlled device and glazing using such semi-electroactive material |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20100172011A1 (en) |
| EP (1) | EP2162787A1 (en) |
| JP (1) | JP2010531379A (en) |
| KR (1) | KR20100025534A (en) |
| CN (1) | CN101689002A (en) |
| BR (1) | BRPI0813399A2 (en) |
| CA (1) | CA2692035A1 (en) |
| FR (1) | FR2917849B1 (en) |
| WO (1) | WO2009007602A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| EP2239626A1 (en) * | 2008-01-31 | 2010-10-13 | Fundacion Cidetec | Electrochromic compositions containing viologens, which can be formulated and used at ambient temperature |
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| US8183390B1 (en) | 2006-07-24 | 2012-05-22 | The United States Of America As Represented By The Secretary Of The Navy | Bis(thienyl)isopyrazoles and process for preparing and method for using bis(thienyl)isopyrazoles |
| US7456295B1 (en) | 2006-11-25 | 2008-11-25 | The United States Of America As Represented By The Secretary Of The Navy | Bis(thienyl)isopyrazoles and process for preparing and method for using bis(thienyl)isopyrazoles |
| US8427812B1 (en) | 2008-07-24 | 2013-04-23 | The United States Of America As Represented By The Secretary Of The Navy | Electroactive polymer based supercapacitors including a cathode having BBL or Pry-BBL |
| US9782949B2 (en) | 2008-05-30 | 2017-10-10 | Corning Incorporated | Glass laminated articles and layered articles |
| WO2012023989A2 (en) | 2010-08-20 | 2012-02-23 | Rhodia Operations | Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels, and foams |
| EP2828901B1 (en) | 2012-03-21 | 2017-01-04 | Parker Hannifin Corporation | Roll-to-roll manufacturing processes for producing self-healing electroactive polymer devices |
| JP2015521366A (en) * | 2012-04-12 | 2015-07-27 | パーカー−ハネフィン コーポレーションＰａｒｋｅｒ−Ｈａｎｎｉｆｉｎ Ｃｏｒｐｏｒａｔｉｏｎ | EAP converter with improved performance |
| CN102690646B (en) * | 2012-06-04 | 2014-10-15 | 仝泽彬 | Electrochromism material and electrochromism device |
| EP2885867A4 (en) | 2012-08-16 | 2016-04-13 | Bayer Ip Gmbh | Electrical interconnect terminals for rolled dielectric elastomer transducers |
| TWI565737B (en) | 2015-12-16 | 2017-01-11 | 財團法人工業技術研究院 | Porous hydrophobic fluorine-containing polymer membrane and production methods thereof |
| CN105623642B (en) * | 2016-02-24 | 2017-12-26 | 青岛科技大学 | A kind of novel electrochromic material P (6NIIn co EDOT) and preparation method thereof |
| KR102596288B1 (en) * | 2016-11-29 | 2023-10-30 | 엘지디스플레이 주식회사 | Touch sensitive device and display device comprising the same |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
| US11624962B2 (en) * | 2019-10-02 | 2023-04-11 | Gentex Corporation | Electro-optic elements and method of forming |
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| US5910854A (en) * | 1993-02-26 | 1999-06-08 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
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| EP1004649A3 (en) * | 1993-02-26 | 2000-07-26 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
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| EP1041425A4 (en) * | 1997-12-19 | 2007-05-02 | Nippon Mitsubishi Oil Corp | Electrochromic element |
| ES2164029B1 (en) * | 2000-07-07 | 2003-05-16 | Fico Mirrors Sa | ELECTROCHROMICAL DEVICE AND CORRESPONDING APPLICATIONS. |
| US6620342B1 (en) * | 2000-10-23 | 2003-09-16 | Atofina Chemicals, Inc. | Narrow composition distribution polyvinylidene fluoride RECLT films, processes, articles of manufacture and compositions |
| US6747780B2 (en) * | 2001-06-25 | 2004-06-08 | University Of Washington | Electrochromic organic polymer synthesis and devices utilizing electrochromic organic polymers |
| JP2003015163A (en) * | 2001-06-27 | 2003-01-15 | Nippon Oil Corp | Electrochromic element |
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-
2007
- 2007-06-25 FR FR0755987A patent/FR2917849B1/en not_active Expired - Fee Related
-
2008
- 2008-06-25 CN CN200880022162A patent/CN101689002A/en active Pending
- 2008-06-25 JP JP2010514064A patent/JP2010531379A/en active Pending
- 2008-06-25 EP EP08806090A patent/EP2162787A1/en not_active Withdrawn
- 2008-06-25 CA CA002692035A patent/CA2692035A1/en not_active Abandoned
- 2008-06-25 BR BRPI0813399 patent/BRPI0813399A2/en not_active IP Right Cessation
- 2008-06-25 WO PCT/FR2008/051161 patent/WO2009007602A1/en active Application Filing
- 2008-06-25 KR KR20097026969A patent/KR20100025534A/en not_active Application Discontinuation
- 2008-06-25 US US12/666,334 patent/US20100172011A1/en not_active Abandoned
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| US5910854A (en) * | 1993-02-26 | 1999-06-08 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
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| EP2239626A1 (en) * | 2008-01-31 | 2010-10-13 | Fundacion Cidetec | Electrochromic compositions containing viologens, which can be formulated and used at ambient temperature |
| EP2239626A4 (en) * | 2008-01-31 | 2011-08-03 | Fundacion Cidetec | Electrochromic compositions containing viologens, which can be formulated and used at ambient temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100025534A (en) | 2010-03-09 |
| BRPI0813399A2 (en) | 2014-12-30 |
| FR2917849B1 (en) | 2009-09-25 |
| CA2692035A1 (en) | 2009-01-15 |
| US20100172011A1 (en) | 2010-07-08 |
| CN101689002A (en) | 2010-03-31 |
| JP2010531379A (en) | 2010-09-24 |
| FR2917849A1 (en) | 2008-12-26 |
| WO2009007602A1 (en) | 2009-01-15 |
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