CN104910892A - Electrochromic material and electrochromic device - Google Patents
Electrochromic material and electrochromic device Download PDFInfo
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- CN104910892A CN104910892A CN201510292210.7A CN201510292210A CN104910892A CN 104910892 A CN104910892 A CN 104910892A CN 201510292210 A CN201510292210 A CN 201510292210A CN 104910892 A CN104910892 A CN 104910892A
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- electrochromic material
- glass
- electrochromic
- conducting
- sodium
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- 239000000463 material Substances 0.000 title claims abstract description 58
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000010975 amethyst Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- -1 Sodium tetrafluoroborate Chemical compound 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QVLNJJLJVMLHFO-UHFFFAOYSA-N [F].[O-2].[Zn+2] Chemical compound [F].[O-2].[Zn+2] QVLNJJLJVMLHFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000005562 fading Methods 0.000 abstract description 4
- 239000004984 smart glass Substances 0.000 abstract description 4
- 238000002845 discoloration Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000004313 glare Effects 0.000 abstract 1
- 229910052757 nitrogen Chemical group 0.000 description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 235000019476 oil-water mixture Nutrition 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 4
- HJKGBRPNSJADMB-UHFFFAOYSA-N 3-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1 HJKGBRPNSJADMB-UHFFFAOYSA-N 0.000 description 4
- PUACTIIESPYWSI-UHFFFAOYSA-N 3-propan-2-ylpyridine Chemical compound CC(C)C1=CC=CN=C1 PUACTIIESPYWSI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- YQDGQEKUTLYWJU-UHFFFAOYSA-N 5,6,7,8-tetrahydroquinoline Chemical compound C1=CC=C2CCCCC2=N1 YQDGQEKUTLYWJU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 1
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- KVQUJOXTTHAVJE-UHFFFAOYSA-N 4-(5,6,7,8-tetrahydroquinolin-4-yl)-5,6,7,8-tetrahydroquinoline Chemical compound N1=CC=C(C=2CCCCC1=2)C1=CC=NC=2CCCCC1=2 KVQUJOXTTHAVJE-UHFFFAOYSA-N 0.000 description 1
- MVWFINKRIQNHGG-UHFFFAOYSA-N 4-quinolin-4-ylquinoline Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4N=CC=3)=CC=NC2=C1 MVWFINKRIQNHGG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- RZEQQEXIZXEASF-UHFFFAOYSA-N lithium trifluoro(sulfinato)methane Chemical compound [Li+].C(F)(F)(F)[S-](=O)=O RZEQQEXIZXEASF-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention relates to an electrochromic material and an electrochromic device thereof. The invention is characterized in that the electrochromic material is a mixture composed of a cathode electrochromic material and an anode electrochromic material, wherein the structural general formula of the cathode electrochromic material is disclosed in the specification, and the cathode electrochromic material has various substituent groups on the pyridine ring and aims to enhance the structure stability from orthogonal state to plane state and the charge dispersity in the pyridine ring in the reinforced discoloration process, thereby enhancing the potential difference DeltaE value between the two states. The electrochromic device comprises transparent conducting glass and conducting reflecting glass, wherein a transparent conducting layer (2) of the transparent conducting glass and a conducting reflecting layer (4) of the conducting reflecting glass are arranged in opposite; the peripheries of the transparent conducting glass and conducting reflecting glass are bonded with an adhesive to form a cavity; and the cavity is filled with the electrochromic material. The electrochromic device has the characteristics of long service life and high discoloration and fading rate, and is applicable to the field of automobile non-glare rearview mirrors or building switchable glass intelligent windows.
Description
This case is divisional application, and the applying date of original application is: on November 14th, 2012, clear number of Shen is: 201210482670.2, and the name of original application is called " electrochromic material and electrochromic device ".
Technical field
The present invention relates to a kind of electrochromic material, specifically refer to a kind of electrochromic material being applied to the fields such as automatically dimmed anti-dazzle driving mirror and relevant dimming glass and the electrochromic device adopting this electrochromic material to prepare thereof.
Background technology
Electrochromic material is under the effect of volts DS, and materials from oxidizing or reduction causes it to produce reversible change to visible transmission or reflection.Current electrochromic material is mainly divided into inorganic electrochromic material and organic electrochromic material, inorganic electrochromic material is mainly the metal oxides such as tungstic oxide, nickel oxide, iridium oxide or titanium oxide, and organic electrochromic material mainly comprises polyaniline, Polythiophene, amethyst or phenothiazine compound and derivative thereof.Although electrochromic material is applied in anti-dazzle driving mirror field, but the variable color caused due to compound own characteristic/fade slow, less stable, the shortcomings such as off-color material is residual.Therefore certain limitation is subject in actual applications.In patent of invention 200480031402.2, propose amethyst compound, in variable color with process of fading, there is following structure:
When amethyst compound is in reduction-state, two orthogonal thereto states of pyridine quaternary ammonium salt ring, reduce steric hindrance, highly stable, show water white transparency state.When amethyst compound obtains an electronics, be provided with double bond between two pyridine quaternary ammonium salts and appear in a plane, producing resonance, thus produce dark color.When two dimensional structure appears in amethyst molecular structure, be easy between molecule form conjugated structure, occur the overlap between aromatic ring, have sequence between molecular structure, therefore the color of amethyst is also become light yellow from dark color.Now amethyst compounds is easy to suffer irreversible destruction, and therefore the life-span of electrochromic device shortens.
In addition, due to the electron donating property of R1 and R2 group, make amethyst analog derivative after variable color, easily produce variable color and accumulate on pyridine ring, fading time is longer.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of electrochromic material, cathode electrochromic material in this electrochromic material is with various substituting group on pyridine ring, the potential difference Δ E of two states when contributing to improving amethyst compounds structure is transformed into flat state by quadrature in colourshifting process, the feature that there is high life, quick color-changing and fade.
Second technical problem to be solved by this invention is to provide a kind of electrochromic device, and it is long that this device has the life-span, and variable color and the fast feature of fade rates, be applicable to the smart window of anti-glare rear-view mirror for automobile field or dimming glass for building.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of electrochromic material, it is characterized in that: the mixture that this electrochromic material is made up of cathode electrochromic material and anode electrochromic material, the chemical structure of general formula of described cathode electrochromic material is: following general structure one, general structure two or general structure three:
In above-mentioned: R
1, R
2for normal paraffin or isoparaffin that carbonatoms is 1 ~ 20;
R
3, R
4for normal paraffin or isoparaffin or methoxy or ethoxy or carboxyl that carbonatoms is 1 ~ 4;
R
5, R
6for F or Cl or Br or NO
2or SO
3h;
R
7, R
8for alkane or O or N or S heteroatoms that carbonatoms is 1 ~ 3;
R
9, R
10for R
3, R
4for alkane or Alkane isomer or methoxy or ethoxy or carboxyl that carbonatoms is 1 ~ 4;
X is
cl
-, Br
-, BF4
-or PF6
-;
Described anode electrochromic material is Polyvinyl carbazole, and its chemical structure of general formula is:
N wherein represents the polymerization degree, is natural number.
As improvement, the preparation method of described cathode electrochromic material, comprises the following steps:
1), 4 are synthesized, 4 '-dipyridyl derivatives: will join in reaction flask containing substituent pyridine and sodium Metal 99.5, described pyridine and sodium Metal 99.5 mol ratio are: 35 ~ 45: 1, then be heated to 100 ~ 120 DEG C of backflows 20 ~ 28 hours, after having reacted, be cooled to room temperature, and mixture is poured in ice cube, make sodium Metal 99.5 react complete, obtain oily aqueous mixture
Carry out oily water separation: add anhydrous sodium sulphate by the oily matter of gained, leave standstill 16 ~ 24 hours, what then vacuum rotary steam removing was excessive contains substituent pyridine, after vacuum rotary steam, the product of gained carries out recrystallization in ethanolic soln, obtain white or light yellow product, be 4,4'-Bipyridine derivative;
2), synthesis amethyst compounds: get step 1) synthesized by 4, the halogenated alkane of 4 '-dipyridyl derivatives, 0.015 ~ 0.025mol and 0.045 ~ 0.055mol or halo derivatives are dissolved in the acetonitrile solution of 15 ~ 25ml, reflux was cooled to room temperature after 8 ~ 12 hours, solution precipitation is separated out complete, cross and filter solvent and unreacted by product completely, filter cake is soluble in water, add Sodium tetrafluoroborate, sodium hexafluoro phosphate, the aqueous solution of paratoluenesulfonic acid sodium salt or sodium laurylsulfonate, solution precipitation is separated out complete, throw out is filtered and filter cake is carried out recrystallization, namely cathode electrochromic material is obtained.
As preferably, described step 1) in substituting group containing substituent pyridine to be carbonatoms be 1 ~ 4 alkane or Alkane isomer or methoxy or ethoxy or carboxyl.
Preferred again, the described mol ratio containing substituent pyridine and sodium Metal 99.5 is 40: 1.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of electrochromic device, it is characterized in that: described electrochromic device includes transparent conducting glass, conducting reflective glass, the transparency conducting layer of described transparent conducting glass and the conductive reflective of conducting reflective glass are oppositely arranged, form cavity in the surrounding of described transparent conducting glass and conducting reflective glass by colloid bonding, inside described cavity, be filled with electrochromic material described above.
As preferably, described transparency conducting layer is stannic oxide, indium tin oxide target, the stannic oxide mixing fluorine, zinc oxide or mix fluorine zinc oxide, and the resistance of described transparency conducting layer is less than 20 ohm, and at visible ray 550nm place, transmittance is more than 80%.
Finally, described conductive reflective is preferably silver, rhodium, aluminium, nickel or platinum.
Compared with prior art, the invention has the advantages that: the cathode electrochromic material in electrochromic material of the present invention on pyridine ring with various substituting group, in stability when being intended to strengthen amethyst compounds structure is transformed into flat state by quadrature in colourshifting process and pyridine ring, electric charge is dispersed, also improve the potential difference Δ E value between two states simultaneously, solve amethyst compounds and be easy to suffer irreversible destruction, after variable color, easily produce the defect that variable color accumulates on pyridine ring, fading time is longer.Equally, the electrochromic device adopting electrochromic material of the present invention to prepare has the long lifetime, and variable color and the fast feature of fade rates, be applicable to the smart window of anti-glare rear-view mirror for automobile field or dimming glass for building.
Accompanying drawing explanation
Fig. 1 is the structural representation of electrochromic device of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
A kind of electrochromic material, the mixture be made up of cathode electrochromic material and anode electrochromic material, wherein the building-up process of cathode electrochromic material is divided into two steps:
The first step is synthesis 4,4'-Bipyridine derivative, and pyridine derivate is obtained required target product under the katalysis of suitable sodium Metal 99.5; Reaction equation is as follows:
Second step is synthesis amethyst compounds, and the dipyridyl derivatives synthesized by the first step and halogenated compound are obtained by reacting corresponding amethyst compounds, and reaction equation is as follows:
Preparation process below by specific embodiment anticathode electrochromic material is described in detail.
Embodiment 1
The 3-picoline of 0.1mol and 0.025mol sodium Metal 99.5 are joined in reaction flask, is heated to 110 DEG C of backflows 24 hours, after having reacted, is cooled to room temperature, and mixture is poured in ice cube, make excessive sodium Metal 99.5 reaction complete.Obtain oil-water mixture, carry out oily water separation.In the oily matter of gained, add anhydrous sodium sulphate, hold over night, what then vacuum rotary steam removing was excessive contains 3-picoline.After revolving steaming, the product of gained carries out recrystallization in ethanolic soln, obtains white or light yellow product, i.e. 3,3-dimethyl-4,4-dipyridyls.3,3-dimethyl-4, the 4-dipyridyls getting 0.02mol are dissolved in 20mL acetonitrile solution, then add the monobromethane of 0.05mol, back flow reaction 8h.After having reacted, the mixing solutions of gained is filtered, and filter cake is dissolved in deionized water, add Sodium tetrafluoroborate, occur a large amount of white precipitates.White precipitate is filtered and obtains product (there is the compound that chemical structural formula is Fig. 1).
The sign of its chemical structure is as follows: H1 NMR (CDCl3-d1): 0.9t (6H ,-CH3), 1.4q (4H,-CH2-), 2.3d (6H ,-CH3), 8.6d (2H, CH), 9.3dd (4H, CH). ultimate analysis: actual measurement C 78.7wt%, H 9.3wt%, N 11.4%; Calculated value C 79.3wt%, H 9.1wt%, N 11.6wt%. mass spectrum: mass-to-charge ratio m/z value is 241.3.
Embodiment 2
The 3-phenylpyridine of 0.1mol and 0.025mol sodium Metal 99.5 are joined in reaction flask, is heated to 110 DEG C of backflows 24 hours, after having reacted, is cooled to room temperature, and mixture is poured in ice cube, make excessive sodium Metal 99.5 reaction complete.Obtain oil-water mixture, carry out oily water separation.In the oily matter of gained, add anhydrous sodium sulphate, hold over night, what then vacuum rotary steam removing was excessive contains 3-phenylpyridine.After revolving steaming, the product of gained carries out recrystallization in ethanolic soln, obtains white or light yellow product, i.e. 3,3-phenylbenzene-4,4-dipyridyls.3,3-phenylbenzene-4, the 4-dipyridyls getting 0.02mol are dissolved in 20mL acetonitrile solution, then add the heptyl bromide of 0.05mol, back flow reaction 8h.After having reacted, the mixing solutions of gained is filtered, and filter cake is dissolved in deionized water, add paratoluenesulfonic acid sodium salt, occur a large amount of white precipitates.By white precipitate filter and in dehydrated alcohol recrystallization obtain product (there is the compound that chemical structural formula is Fig. 1).
The sign of its chemical structure is as follows: H1 NMR (CDCl3-d1): 0.92t (6H ,-CH3), 1.1 ~ 1.6m (24H,-CH2-), 7.2 ~ 7.5m (12H, CH), 9.3d (2H, CH), 9.5d (2H, CH). ultimate analysis: actual measurement C 85.1wt%, H 9.0wt%, N 5.3%; Calculated value C 85.4wt%, H 9.1wt%, N 5.5wt%. mass spectrum: mass-to-charge ratio m/z value is 505.1.
Embodiment 3
The quinoline of 0.1mol and 0.025mol sodium Metal 99.5 are joined in reaction flask, is heated to 120 DEG C of backflows 24 hours, after having reacted, is cooled to room temperature, and mixture is poured in ice cube, make excessive sodium Metal 99.5 reaction complete.Obtain oil-water mixture, carry out oily water separation.In the oily matter of gained, add anhydrous sodium sulphate, hold over night, what then vacuum rotary steam removing was excessive contains quinoline.After revolving steaming, the product of gained carries out recrystallization in ethanolic soln, obtains white or light yellow product, i.e. 4-(quinolin-4-yl) quinoline.4-(quinolin-4-yl) quinoline getting 0.02mol is dissolved in 20mL acetonitrile solution, then adds the N-dodeeyl bromide of 0.05mol, back flow reaction 8h.After having reacted, the mixing solutions of gained is filtered, and filter cake is dissolved in deionized water, add Sodium dodecylbenzene sulfonate, occur a large amount of white precipitates.White precipitate is filtered and obtains product (there is the compound that chemical structural formula is Fig. 1).
The sign of its chemical structure is as follows: H1 NMR (CDCl3-d1): 0.9t (6H ,-CH3), 1.05 ~ 1.5m (44H,-CH2-), 7.2 ~ 7.8m (8H, CH), 8.6d (2H, CH), 9.3d (2H, CH). ultimate analysis: actual measurement C 78.7wt%, H 9.3wt%, N 11.4%; Calculated value C 84.8wt%, H 10.4wt%, N 4.7wt%. mass spectrum: mass-to-charge ratio m/z value is 593.4.
Embodiment 4
5,6,7,8-tetrahydroquinoline of 0.1mol and 0.025mol sodium Metal 99.5 are joined in reaction flask, is heated to 110 DEG C of backflows 24 hours, after having reacted, is cooled to room temperature, and mixture is poured in ice cube, make excessive sodium Metal 99.5 reaction complete.Obtain oil-water mixture, carry out oily water separation.In the oily matter of gained, add anhydrous sodium sulphate, hold over night, what then vacuum rotary steam removing was excessive contains 5,6,7,8-tetrahydroquinoline.After revolving steaming, the product of gained carries out recrystallization in ethanolic soln, obtains white or light yellow product, i.e. 5,6,7,8-tetrahydro-4-(5,6,7,8-tetrahydroquinolin-4-yl) quinoline.5,6,7,8-tetrahydro-4-(5,6,7, the 8-tetrahydroquinolin-4-yl) quinoline getting 0.02mol is dissolved in 20mL acetonitrile solution, then adds the bromo Octadecane of 0.05mol, back flow reaction 8h.After having reacted, the mixing solutions of gained is filtered, and filter cake is dissolved in deionized water, add trifluoromethyl sulfonyl lithium, occur a large amount of white precipitates.White precipitate is filtered and in dehydrated alcohol, carries out recrystallization and obtains product (there is the compound that chemical structural formula is Fig. 1).
The sign of its chemical structure is as follows: H1 NMR (CDCl3-d1): 0.9t (6H ,-CH3), 1.0 ~ 1.5m (68H,-CH2-), 1.7m (8H ,-CH2-), 2.6t (8H ,-CH2-), 8.4d (2H, CH), 9.2d (2H, CH). ultimate analysis: actual measurement C 83.9wt%, H 12.1wt%, N3.4%; Calculated value C 84.1wt%, H 12.2wt%, N 3.6wt%. mass spectrum: mass-to-charge ratio m/z value is 769.1.
Embodiment 5
The 3-isopropyl pyridine of 0.1mol and 0.025mol sodium Metal 99.5 are joined in reaction flask, is heated to 110 DEG C of backflows 24 hours, after having reacted, is cooled to room temperature, and mixture is poured in ice cube, make excessive sodium Metal 99.5 reaction complete.Obtain oil-water mixture, carry out oily water separation.In the oily matter of gained, add anhydrous sodium sulphate, hold over night, what then vacuum rotary steam removing was excessive contains 3-isopropyl pyridine.After revolving steaming, the product of gained carries out recrystallization in ethanolic soln, obtains white or light yellow product, i.e. 3,3-di-isopropyl-4,4-dipyridyls.3,3-di-isopropyl-4, the 4-dipyridyls getting 0.02mol are dissolved in 20mL acetonitrile solution, then add the bromo-iso-octane of 0.05mol, back flow reaction 8h.Light yellow look sedimentation and filtration is carried out recrystallization and obtains product (having the compound that chemical structural formula is Fig. 1) in ethanolic soln.
The sign of its chemical structure is as follows: H1 NMR (CDCl3-d1): 0.97t (12H ,-CH3), 1.05 ~ 1.6m (34H,-CH2 &-CH3), 3.1m (2H, CH), 8.6d (2H, CH), 9.3dd (4H, CH). ultimate analysis: actual measurement C 78.7wt%, H 9.3wt%, N 11.4%; Calculated value C 82.4wt%, H 11.6wt%, N 6.0wt%. mass spectrum: mass-to-charge ratio m/z value is 465.5.
Above-mentioned composite cathode electrochromic material is applied to respectively electrochromic device (EC device).
Concrete making method is as follows: adopt sizing agent to be glued together in surrounding with the substrate glass 5 being coated with conductive reflective 4 glass substrate 1 being coated with transparency conducting layer 2, obtain a cavity, electrochromic material 3 is being injected this cavity (wherein the anode off-color material of electrochromic material 3 is Polyvinyl carbazole), and with UV rubber seal mouth.Test result is respectively as following table:
Can show that electrochromic device prepared by the present invention has the long lifetime from above-described embodiment data, variable color and the fast feature of fade rates, be applicable to the smart window of anti-glare rear-view mirror for automobile field or dimming glass for building.
Claims (7)
1. an electrochromic material, is characterized in that: the mixture that this electrochromic material is made up of cathode electrochromic material and anode electrochromic material, and the chemical structure of general formula of described cathode electrochromic material is:
In above-mentioned: R
1for normal paraffin or isoparaffin that carbonatoms is 1-20;
R
6for F or Cl or Br or NO
2or SO
3h;
R
9, R
10for alkane or Alkane isomer or methoxy or ethoxy or carboxyl that carbonatoms is 1 ~ 4;
X is:
cl
-, Br
-, BF4
-or PF6
-;
Described anode electrochromic material is Polyvinyl carbazole, and its chemical structure of general formula is:
N wherein represents the polymerization degree, is natural number.
2. electrochromic material according to claim 1, is characterized in that: the preparation method of described cathode electrochromic material, comprises the following steps:
1), synthesis 4, 4 '-dipyridyl derivatives: will join in reaction flask containing substituent pyridine and sodium Metal 99.5, described pyridine and sodium Metal 99.5 mol ratio are: 35 ~ 45: 1, then 100 ~ 120 DEG C of backflows 20 ~ 28 hours are heated to, after having reacted, be cooled to room temperature, and mixture is poured in ice cube, sodium Metal 99.5 is made to react complete, obtain oily aqueous mixture, carry out oily water separation: add anhydrous sodium sulphate by the oily matter of gained, leave standstill 16 ~ 24 hours, what then vacuum rotary steam removing was excessive contains substituent pyridine, after vacuum rotary steam, the product of gained carries out recrystallization in ethanolic soln, obtain white or light yellow product, be 4, 4 '-dipyridyl derivatives,
2), synthesis amethyst compounds: get step 1) synthesized by 4, the halogenated alkane of 4 '-dipyridyl derivatives, 0.015 ~ 0.025mol and 0.045 ~ 0.055mol or halo derivatives are dissolved in the acetonitrile solution of 15 ~ 25ml, reflux was cooled to room temperature after 8 ~ 12 hours, solution precipitation is separated out complete, cross and filter solvent and unreacted by product completely, filter cake is soluble in water, add Sodium tetrafluoroborate, sodium hexafluoro phosphate, the aqueous solution of paratoluenesulfonic acid sodium salt or sodium laurylsulfonate, solution precipitation is separated out complete, throw out is filtered and filter cake is carried out recrystallization, namely cathode electrochromic material is obtained.
3. electrochromic material according to claim 2, is characterized in that: described step 1) in containing the substituting group of substituent pyridine to be carbonatoms be 1 ~ 4 alkane or Alkane isomer or methoxy or ethoxy or carboxyl.
4. electrochromic material according to claim 2, is characterized in that: the described mol ratio containing substituent pyridine and sodium Metal 99.5 is 40: 1.
5. an electrochromic device, it is characterized in that: described electrochromic device includes transparent conducting glass, conducting reflective glass, the transparency conducting layer (2) of described transparent conducting glass and the conductive reflective (4) of conducting reflective glass are oppositely arranged, form cavity in the surrounding of described transparent conducting glass and conducting reflective glass by colloid bonding, inside described cavity, be filled with electrochromic material according to claim 1.
6. electrochromic device according to claim 5, it is characterized in that: described transparency conducting layer (2) is stannic oxide, indium tin oxide target, the stannic oxide mixing fluorine, zinc oxide or mix fluorine zinc oxide, the resistance of described transparency conducting layer (2) is less than 20 ohm, and at visible ray 550nm place, transmittance is more than 80%.
7. electrochromic device according to claim 5, is characterized in that: described conductive reflective is silver, rhodium, aluminium, nickel or platinum.
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| CN104804720A (en) | 2015-07-29 |
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