CN116178410B - Boron-based electrochromic material and preparation method and application thereof - Google Patents
Boron-based electrochromic material and preparation method and application thereof Download PDFInfo
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- CN116178410B CN116178410B CN202310144201.8A CN202310144201A CN116178410B CN 116178410 B CN116178410 B CN 116178410B CN 202310144201 A CN202310144201 A CN 202310144201A CN 116178410 B CN116178410 B CN 116178410B
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- 239000000463 material Substances 0.000 title claims abstract description 95
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000006617 triphenylamine group Chemical group 0.000 claims abstract description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 claims description 26
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- XXFGKGMZLZIPCN-UHFFFAOYSA-N 2,5-dibromo-1,3-dimethylbenzene Chemical group CC1=CC(Br)=CC(C)=C1Br XXFGKGMZLZIPCN-UHFFFAOYSA-N 0.000 claims description 12
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 12
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 4
- 229910015900 BF3 Inorganic materials 0.000 claims 2
- 239000011521 glass Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000004040 coloring Methods 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 230000002238 attenuated effect Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 6
- 238000005562 fading Methods 0.000 abstract description 5
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- 150000001651 triphenylamine derivatives Chemical class 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 64
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 230000005526 G1 to G0 transition Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052754 neon Inorganic materials 0.000 description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012490 blank solution Substances 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000314 transition metal 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
- 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
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention belongs to the technical field of electrochromic materials, and provides a boron-based electrochromic material, and a preparation method and application thereof. The boron-based electrochromic material provided by the invention takes boron as a center, and triphenylamine derivatives as peripheral polymeric groups. The triphenylamine derivative has a strong conjugated structure, and the formed electrochromic material can realize color change from transparent to blue under the drive of voltage. The optical contrast of the boron-based electrochromic material provided by the invention is up to 60% at 740nm, and the response time of coloring and fading is 4.8s and 1.8s respectively. In addition, the optical contrast of the boron-based electrochromic material was hardly attenuated after 150 cycles. The boron-based electrochromic material provided by the invention is an electrochromic material with excellent properties, and has wide application prospects in the field of display devices (such as anti-counterfeiting, color-changing glass, mobile phone backshells, electronic tags and electronic paper).
Description
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to a boron-based electrochromic material and a preparation method and application thereof.
Background
Electrochromic materials are functional building blocks in electrochromic devices. Existing electrochromic materials are largely classified into inorganic electrochromic materials and organic electrochromic materials. The electrochromic materials mainly comprise transition metal oxides (such as oxides of tungsten, nickel, titanium, molybdenum, iridium, vanadium, cobalt and other inorganic materials), but have low response speed, single color display and low coloring efficiency, so that the application range of the electrochromic materials is severely limited, and the electrochromic materials are hardly realized, especially in electrochromic display devices. Compared with inorganic electrochromic materials, the organic electrochromic material has the advantages of rich structure types, good processing performance, high response speed, multiple color changes and the like, and is considered as the next generation electrochromic material with the most development prospect. Organic electrochromic materials are largely divided into two categories: conjugated polymer electrochromic materials and organic small molecule electrochromic materials (viologen). Conjugated polymer electrochromic materials are widely concerned and researched nowadays, and become an important development direction of a new generation of electrochromic display materials.
In the conjugated polymer electrochromic material, on one hand, the cathode coloring material needs to always apply voltage to keep a transparent state, so that the energy consumption is obviously improved; on the other hand, the application of a long-time voltage also damages the structure of the polymer, ultimately affecting the service life of the device. For some displays, we need to present a transparent state without voltage application, but a transient colored state with voltage application, which accords with the energy-saving concept, can achieve good confidentiality, and the transient driving voltage does not damage the polymer structure so as to achieve the purpose of prolonging the service life. Therefore, it is very important to provide an energy-saving electrochromic material capable of achieving the above color change.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a boron-based electrochromic material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a boron-based electrochromic material, which has a structural formula as follows:
The invention also provides a preparation method of the boron-based electrochromic material, which comprises the following steps:
(1) Mixing diphenylamine, cuprous iodide, 2-dipyridine, potassium tert-butoxide, 2, 5-dibromo-m-xylene and toluene in a protective atmosphere, and reacting to obtain a triphenylamine derivative;
(2) Under the protective atmosphere, mixing triphenylamine derivative and diethyl ether, and reacting to obtain a mixture;
(3) Mixing the mixture with tert-butyl lithium, and heating to obtain a mixed solution;
(4) Mixing the mixed solution with boron trifluoride diethyl etherate, and reacting to obtain a monomer of the boron-based electrochromic material;
(5) Mixing a monomer of the boron-based electrochromic material, chloroform, acetonitrile and tetrabutylammonium hexafluorophosphate, and performing electrochemical polymerization to obtain the boron-based electrochromic material.
Preferably, the molar ratio of the diphenylamine, the cuprous iodide, the 2, 2-bipyridine, the potassium tert-butoxide and the 2, 5-dibromo-m-xylene in the step (1) is 0.8-1.2: 0.04 to 0.06:0.04 to 0.06:1.8 to 2.2:1.0 to 1.4; the mass sum of the diphenylamine, the cuprous iodide, the 2, 2-bipyridine, the potassium tert-butoxide and the 2, 5-dibromo-m-xylene and the volume ratio of toluene are 1g: 10-15 mL.
Preferably, the temperature of the reaction in the step (1) is 115-135 ℃, and the time of the reaction is 22-26 hours.
Preferably, the molar ratio of the triphenylamine derivative in the step (2) to the tert-butyllithium in the step (3) and the boron trifluoride diethyl ether in the step (4) is 0.8-1.2: 1.3 to 1.7:0.23 to 0.43; the mass sum of the triphenylamine derivative, the tertiary butyl lithium and the boron trifluoride diethyl etherate and the volume ratio of the diethyl etherate in the step (2) are 1g: 10-15 mL.
Preferably, the temperature of the reaction in the step (2) is-68 to-88 ℃ and the time is 25 to 35min;
The temperature of the mixing in the step (3) is minus 68 to minus 88 ℃, the time is 25 to 35min, the temperature of the heating is minus 2 to 2 ℃ and the time is 25 to 35min.
Preferably, the temperature of the mixing in the step (4) is-2 ℃, the time is 25-35 min, the temperature of the reaction is 20-30 ℃, and the time is 14-18 h.
Preferably, the monomer concentration of the boron-based electrochromic material in the mixed solution in the step (5) is 0.1-2 mmol/L, the concentration of tetrabutylammonium hexafluorophosphate is 0.05-0.5 mol/L, and the volume ratio of chloroform to acetonitrile is 0.8-1.2: 2.8 to 3.2.
Preferably, the scanning speed of the electrochemical polymerization in the step (5) is 90-110 mV/s, the voltage is 0-1.3V, and the cycle number is 4-12.
The invention also provides application of the boron-based electrochromic material in electrochromic devices.
The beneficial effects of the invention are as follows:
The invention provides a boron-based electrochromic material, which takes boron as a center and triphenylamine derivatives as peripheral polymeric groups. The triphenylamine derivative has a strong conjugated structure, and the formed electrochromic material can realize color change from transparent to blue under the drive of voltage. The optical contrast of the boron-based electrochromic material provided by the invention is up to 60% at 740nm, and the response time of coloring and fading is 4.8s and 1.8s respectively. In addition, the optical contrast of the boron-based electrochromic material was hardly attenuated after 150 cycles. The boron-based electrochromic material provided by the invention is an electrochromic material with excellent properties, and has wide application prospects in the field of display devices (such as anti-counterfeiting, color-changing glass, mobile phone backshells, electronic tags and electronic paper).
Drawings
FIG. 1 is a synthetic route diagram of a boron-based electrochromic material of the present invention;
FIG. 2 is a cyclic voltammogram (Potential-voltage, current-Current, ordinate) of the boron-based electrochromic material of example 1;
FIG. 3 is a graph of electrochemical polymerization of the boron-based electrochromic material of example 1 (abscissa Potential-voltage, ordinate Current-Current);
FIG. 4 is a graph of the ultraviolet-visible absorption spectrum (Wavelength on the abscissa, UVAbsorption intensity on the ordinate, absorption intensity) of the boron-based electrochromic material of example 1 at various voltages;
FIG. 5 is an electrochromic property graph (abscissa Time-Time, ordinate T-contrast) of the boron-based electrochromic material of example 1;
Fig. 6 is a graph of optical contrast and response Time (abscissa Time-Time, ordinate T-contrast) for a boron-based electrochromic material.
Detailed Description
The invention provides a boron-based electrochromic material, which has a structural formula as follows:
The invention also provides a preparation method of the boron-based electrochromic material, which comprises the following steps:
(1) Mixing diphenylamine, cuprous iodide, 2-dipyridine, potassium tert-butoxide, 2, 5-dibromo-m-xylene and toluene in a protective atmosphere, and reacting to obtain a triphenylamine derivative;
(2) Under the protective atmosphere, mixing triphenylamine derivative and diethyl ether, and reacting to obtain a mixture;
(3) Mixing the mixture with tert-butyl lithium, and heating to obtain a mixed solution;
(4) Mixing the mixed solution with boron trifluoride diethyl etherate, and reacting to obtain a monomer of the boron-based electrochromic material;
(5) Mixing a monomer of the boron-based electrochromic material, chloroform, acetonitrile and tetrabutylammonium hexafluorophosphate, and performing electrochemical polymerization to obtain the boron-based electrochromic material.
In the present invention, the molar ratio of the diphenylamine, cuprous iodide, 2-bipyridine, potassium t-butoxide and 2, 5-dibromometaxylene in step (1) is preferably 0.8 to 1.2:0.04 to 0.06:0.04 to 0.06:1.8 to 2.2:1.0 to 1.4, more preferably 0.85 to 1.15:0.045 to 0.055:0.045 to 0.055:1.85 to 2.15:1.05 to 1.35, more preferably 0.9 to 1.1: 0.047-0.053: 0.047-0.053: 1.9 to 2.1:1.1 to 1.3; the mass sum of the diphenylamine, the cuprous iodide, the 2, 2-bipyridine, the potassium tert-butoxide and the 2, 5-dibromo-m-xylene and the volume ratio of toluene are preferably 1g:10 to 15mL, more preferably 1g:11 to 14mL, more preferably 1g: 12-13 mL.
In the present invention, the protective atmosphere in the step (1) is nitrogen, argon, helium or neon.
In the present invention, the temperature of the reaction in the step (1) is preferably 115 to 135 ℃, more preferably 120 to 130 ℃, still more preferably 122 to 128 ℃; the reaction time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and still more preferably 23.5 to 24.5 hours.
In the present invention, it is preferable to carry out a post-treatment after the reaction of step (1) is completed, the post-treatment comprising the steps of: and extracting a sample obtained by the reaction, concentrating an extract after the reaction is finished, removing water by using anhydrous sodium sulfate, performing column chromatography purification, and finally collecting the obtained sample for rotary evaporation and drying to obtain the triphenylamine derivative.
In the invention, the extracted reagent is saturated sodium chloride solution and dichloromethane, and the volume ratio of the saturated sodium chloride solution to the dichloromethane is preferably 0.8-1.2: 0.8 to 1.2, more preferably 0.85 to 1.15:0.85 to 1.15, more preferably 0.9 to 1.1:0.9 to 1.1, the number of times of the extraction is preferably 2 to 4 times, more preferably 3 times; the stationary phase of the column chromatography purification is silica gel, the mobile phase comprises dichloromethane and n-hexane, and the volume ratio of the dichloromethane to the n-hexane is preferably 0.8-1.2: 2.8 to 3.2, more preferably 0.85 to 1.15:2.85 to 3.15, more preferably 0.9 to 1.1:2.9 to 3.1; the temperature of the rotary steaming is preferably 60-70 ℃, more preferably 62-68 ℃, and even more preferably 64-66 ℃; the spin-steaming time is preferably 35 to 45 minutes, more preferably 37 to 43 minutes, and even more preferably 39 to 41 minutes; the drying temperature is preferably 50 to 60 ℃, more preferably 52 to 58 ℃, and even more preferably 54 to 56 ℃; the drying time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and even more preferably 23.5 to 24.5 hours.
In the present invention, the purpose of the rotary evaporation is to remove the solvent toluene.
In the present invention, the molar ratio of the triphenylamine derivative in the step (2) to the t-butyllithium in the step (3) and the boron trifluoride diethyl etherate in the step (4) is preferably 0.8 to 1.2:1.3 to 1.7:0.23 to 0.43, more preferably 0.9 to 1.1:1.4 to 1.6:0.25 to 0.41, more preferably 0.95 to 1.05:1.45 to 1.55:0.27 to 0.39; the mass sum of the triphenylamine derivative, the tert-butyllithium and the boron trifluoride diethyl etherate and the volume ratio of the diethyl etherate in the step (2) are preferably 1g:10 to 15mL, more preferably 1g:11 to 14mL, more preferably 1g: 12-13 mL.
In the present invention, the protective atmosphere in the step (2) is nitrogen, argon, helium or neon.
In the present invention, the temperature of the reaction in the step (2) is preferably-68 to-88 ℃, more preferably-70 to-86 ℃, and even more preferably-75 to-81 ℃; the time is preferably 25 to 35 minutes, more preferably 27 to 33 minutes, and still more preferably 29 to 31 minutes;
The mixing in the step (3) is to drop tert-butyl lithium into the mixture; the rate of the dropping is preferably 37 to 43 drops/min, more preferably 38 to 42 drops/min, still more preferably 39 to 41 drops/min; the temperature of the mixing is preferably-68 to-88 ℃, more preferably-70 to-86 ℃, and even more preferably-75 to-81 ℃; the time is preferably 25 to 35 minutes, more preferably 27 to 33 minutes, and still more preferably 29 to 31 minutes; the heating temperature is preferably-2 to 2 ℃, more preferably-1 to 1 ℃, and even more preferably-0.5 to 0.5 ℃; the time is preferably 25 to 35 minutes, more preferably 27 to 33 minutes, and still more preferably 29 to 31 minutes.
In the present invention, the temperature of the mixing in the step (4) is preferably-2 to 2 ℃, more preferably-1 to 1 ℃, and still more preferably-0.5 to 0.5 ℃; the time is preferably 25 to 35 minutes, more preferably 27 to 33 minutes, and still more preferably 29 to 31 minutes; the temperature of the reaction is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 24 to 26 ℃; the time is preferably 14 to 18 hours, more preferably 15 to 17 hours, and still more preferably 15.5 to 16.5 hours.
In the present invention, it is preferable to carry out a post-treatment after the reaction of step (4) is completed, the post-treatment comprising the steps of: and extracting a sample obtained by the reaction, concentrating an extract after the reaction is finished, removing water by using anhydrous sodium sulfate, performing column chromatography purification, and finally collecting the obtained sample for rotary evaporation and drying to obtain the triphenylamine derivative.
In the invention, the extracted reagent is saturated sodium chloride solution and dichloromethane, and the volume ratio of the saturated sodium chloride solution to the dichloromethane is preferably 0.8-1.2: 0.8 to 1.2, more preferably 0.85 to 1.15:0.85 to 1.15, more preferably 0.9 to 1.1:0.9 to 1.1, the number of times of the extraction is preferably 2 to 4 times, more preferably 3 times; the stationary phase of the column chromatography purification is silica gel, the mobile phase comprises dichloromethane and n-hexane, and the volume ratio of the dichloromethane to the n-hexane is preferably 0.8-1.2: 2.8 to 3.2, more preferably 0.85 to 1.15:2.85 to 3.15, more preferably 0.9 to 1.1:2.9 to 3.1; the temperature of the rotary steaming is preferably 60-70 ℃, more preferably 62-68 ℃, and even more preferably 64-66 ℃; the spin-steaming time is preferably 35 to 45 minutes, more preferably 37 to 43 minutes, and even more preferably 39 to 41 minutes; the drying temperature is preferably 50 to 60 ℃, more preferably 52 to 58 ℃, and even more preferably 54 to 56 ℃; the drying time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and even more preferably 23.5 to 24.5 hours.
In the present invention, the purpose of the rotary evaporation is to remove the solvent diethyl ether.
In the present invention, the mixing in the step (5) is preferably carried out by adding the monomer of the boron-based electrochromic material and tetrabutylammonium hexafluorophosphate to a mixed solution of chloroform and acetonitrile, and the frequency of the ultrasonic is preferably 35-45 kHz, more preferably 37-43 kHz, and even more preferably 39-41 kHz; the time of the ultrasonic wave is preferably 2 to 4 minutes, more preferably 2.5 to 3.5 minutes, and still more preferably 2.6 to 3.4 minutes.
In the invention, the electrochemical polymerization method in the step (5) is preferably cyclic voltammetry, tetrabutylammonium hexafluorophosphate is used as an electrolyte, ITO glass is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode; the size of the ITO glass is preferably 0.8 to 1.0 cm. Times.3.5 to 4.5cm, more preferably 0.85 to 0.95 cm. Times.3.6 to 4.4cm, and still more preferably 0.87 to 0.93 cm. Times.3.7 to 4.3cm.
In the present invention, the concentration of the monomer of the boron-based electrochromic material in the mixed solution of step (5) is preferably 0.1 to 2mmol/L, more preferably 0.5 to 1.6mmol/L, still more preferably 0.7 to 1.4mmol/L; the concentration of tetrabutylammonium hexafluorophosphate is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.45mol/L, still more preferably 0.2 to 0.35mol/L; the volume ratio of chloroform to acetonitrile is preferably 0.8-1.2: 2.8 to 3.2, more preferably 0.85 to 1.15:2.85 to 3.15, more preferably 0.9 to 1.1:2.9 to 3.1.
In the present invention, the scanning rate of the electrochemical polymerization in the step (5) is preferably 90 to 110mV/s, more preferably 95 to 105mV/s, still more preferably 98 to 103mV/s; the voltage is preferably 0 to 1.3V, more preferably 0.5 to 0.8V, and still more preferably 0.6 to 0.7V; the number of cycles is preferably 4 to 12, more preferably 5 to 11, and still more preferably 6 to 10.
In the invention, after the polymerization in the step (5) is finished, the obtained sample is dedoped in a blank solution, and after the completion, the sample is alternately cleaned and dried by nitrogen, so that the electrolyte and the oligomer on the surface of the membrane are removed.
In the invention, the blank solution is acetonitrile solution of tetrabutylammonium hexafluorophosphate, and the mass volume ratio of the tetrabutylammonium hexafluorophosphate to the acetonitrile is preferably 0.37-0.40 g:8 to 12mL, more preferably 0.38 to 0.39g:9 to 11mL, more preferably 0.382 to 0.388g: 9.5-10.5 mL; the time for the dedoping is preferably 0.5 to 1.5min, more preferably 0.7 to 1.3min, and still more preferably 0.9 to 1.1min.
In the invention, the cleaning solution is a mixed solution of chloroform and acetonitrile, and the volume ratio of the chloroform to the acetonitrile is preferably 0.8-1.2: 0.8 to 1.2, more preferably 0.85 to 1.15:0.85 to 1.15, more preferably 0.9 to 1.1:0.9 to 1.1; the number of alternations is preferably 2 to 4, more preferably 3.
The invention also provides application of the boron-based electrochromic material in electrochromic devices.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under the protection of nitrogen, 6.8mmol of diphenylamine, 0.34mmol of cuprous iodide, 0.35mmol of 2, 2-bipyridine, 13mmol of potassium tert-butoxide and 8mmol of 2, 5-dibromo-m-xylene are mixed with 60mL of toluene, the mixture is reacted for 24 hours at 125 ℃, the obtained sample is extracted for 3 times by using saturated sodium chloride solution and methylene chloride (volume ratio is 1:1), the obtained extract is concentrated, anhydrous sodium sulfate is used for removing water, then silica gel is used as a stationary phase, methylene chloride and normal hexane are used as mobile phases (volume ratio of methylene chloride and normal hexane is 1:3), column chromatography purification is carried out, the obtained sample is collected, distilled for 40 minutes at 65 ℃ in a rotary mode, and then dried for 24 hours at 55 ℃ to obtain white solid, namely the triphenylamine derivative, wherein the yield of the triphenylamine derivative is 32%, and the characterization structure of the triphenylamine derivative is as follows: 1HNMR(500MHzCDCl3 ) δ=7.27 to 7.21 (4 h, m), 7.05 to 7.01 (6 h, m), 6.81 (2 h, s);
Mixing triphenylamine derivative and diethyl ether under the protection of nitrogen, reacting for 30min at-78 ℃, then dropwise adding tert-butyllithium into the mixture at 40 drops/min, mixing for 30min at-78 ℃, then heating the mixture to 0 ℃, stirring for 30min, adding boron trifluoride diethyl ether (the molar ratio of triphenylamine derivative, tert-butyllithium and boron trifluoride diethyl ether is 1:1.5:0.33), stirring for 30min at 0 ℃, heating to 25 ℃, reacting for 16h, extracting the obtained sample for 3 times by using saturated sodium chloride solution and dichloromethane (the volume ratio is 1:1), concentrating the obtained extract, dehydrating by using anhydrous sodium sulfate, purifying by column chromatography by using silica gel as a stationary phase, collecting the obtained sample, performing rotary evaporation for 40min at 65 ℃, and drying for 24h at 55 ℃ to obtain yellow solid, namely, the monomer structure of the boron electrochromic material, wherein the yield of the monomer is 16 percent: 1HNMR(CDCl3 ) δ=7.31 to 7.21 (12 h, m), 7.09 (12 h, td), 7.02 (6 h, tt), 6.63 (6 h, s);
Adding monomers of a boron-based electrochromic material and tetrabutylammonium hexafluorophosphate into a mixed solution of 2.5mL of chloroform and 7.5mL of acetonitrile (the concentration of the monomers in the mixed solution is 0.5mmol/L, the concentration of the tetrabutylammonium hexafluorophosphate is 0.1 mol/L), performing ultrasonic treatment at 40kHz for 3min, then performing electrochemical polymerization by using ITO glass (0.9 x 4 cm) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode by adopting a cyclic voltammetry, setting the scanning speed to be 100mV/s, setting the voltage to be 0.6V and the cycle number to be 10, and after the polymerization is finished, removing the obtained sample in an acetonitrile solution of tetrabutylammonium hexafluorophosphate (the mass volume ratio of the tetrabutylammonium hexafluorophosphate to the acetonitrile is 0.387g:10 mL), cleaning by using the mixed solution of chloroform and acetonitrile (the volume ratio of 1:1), and performing repeated cleaning and drying by nitrogen for 3 times to obtain the boron-based electrochromic material (p 3 TPA-B), wherein the boron-based electrochromic material is shown in a graph of a figure 1.
Adding 0.387g of tetrabutylammonium hexafluorophosphate into a 10mL volumetric flask, using acetonitrile to fix the volume, taking the mixture as a blank solution, taking ITO glass covered with the boron-based electrochromic material prepared in the embodiment as a working electrode and Ag/AgCl as a reference electrode, and performing electrochemical, optical and electrochromic performance tests to obtain a cyclic voltammogram of the boron-based electrochromic material, as shown in figure 2; electrochemical polymerization profile of a boron-based electrochromic material, as shown in fig. 3; ultraviolet-visible absorption spectra of the boron-based electrochromic material at different voltages are shown in fig. 4; electrochromic properties of the boron-based electrochromic material are shown in fig. 5; an optical contrast and response time plot of the boron-based electrochromic material is shown in fig. 6.
As can be seen from fig. 2, the boron-based electrochromic material has a pair of oxidation-reduction peaks at 0 to 1.3V, i.e., the oxidation peak is 1.1V and the reduction peak is 0.6V; as can be seen from FIG. 3, the polymerization voltage of the boron-based electrochromic material monomer is 0-1.2V, the sweeping speed is 100mV/s, and the polymerization circle number is 10; as can be seen from fig. 4, the boron-based electrochromic material is capable of achieving a reversible color change from clear to blue at a voltage of 0 to 1.2V; as can be seen from fig. 6, the color time of the boron-based electrochromic material at 740nm is 4.8s, the color fading time is 1.8s, and the contrast ratio at 740nm is as high as 60%; and as can also be seen from fig. 5, the contrast of the boron-based electrochromic material is hardly attenuated after 150 cycles, showing good electrochemical stability.
Example 2
Under the protection of neon, 7mmol of diphenylamine, 0.35mmol of cuprous iodide, 0.36mmol of 2, 2-bipyridine, 13.2mmol of potassium tert-butoxide and 8.4mmol of 2, 5-dibromo-m-xylene are mixed with 56mL of toluene, the mixture is reacted for 25 hours at 118 ℃, the obtained sample is extracted for 4 times by using saturated sodium chloride solution and methylene dichloride (volume ratio is 1:1.1), the obtained extract is concentrated, anhydrous sodium sulfate is used for removing water, then silica gel is used as a stationary phase, methylene dichloride and normal hexane are used as mobile phases (volume ratio of methylene dichloride and normal hexane is 1:3.2) for column chromatography purification, the obtained sample is collected, distilled for 38 minutes at 66 ℃ in a rotating way, and then dried for 23 hours at 57 ℃ to obtain white solid, namely the triphenylamine derivative;
mixing triphenylamine derivative and diethyl ether under the protection of neon, reacting for 27min at the temperature of minus 75 ℃, dripping tert-butyllithium into the mixture at the temperature of minus 75 ℃ for 27min, heating the mixture to the temperature of minus 75 ℃ for 28min, adding boron trifluoride diethyl ether (the molar ratio of triphenylamine derivative, tert-butyllithium and boron trifluoride diethyl ether is 1.1:1.55:0.35, the mass ratio of triphenylamine derivative, tert-butyllithium and boron trifluoride diethyl ether to diethyl ether is 1g:13 mL), stirring for 28min at the temperature of 1 ℃, heating to the temperature of 27 ℃ for 16.5h, extracting the obtained sample for 4 times by using saturated sodium chloride solution and dichloromethane (the volume ratio is 1:1.1), concentrating the obtained extract, dehydrating by using anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase, and using dichloromethane and n-hexane as mobile phases (the volume ratio of dichloromethane to n-hexane is 1:2.8), collecting the obtained sample, performing rotary evaporation for 38min at the temperature of 66 ℃, and drying at the temperature of 57 ℃ for 23h to obtain a boron-based electrochromic material;
Adding a monomer of a boron-based electrochromic material and tetrabutylammonium hexafluorophosphate into a mixed solution of 2.4mL of chloroform and 7.6mL of acetonitrile (the concentration of the monomer in the mixed solution is 0.7mmol/L, the concentration of tetrabutylammonium hexafluorophosphate is 0.3 mol/L), performing ultrasonic treatment at 37kHz for 2.5min, then performing electrochemical polymerization by using ITO glass (0.95 x 4.2 cm) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode and adopting a cyclic voltammetry, setting the scanning speed to be 105mV/s, setting the voltage to be 0.65V, setting the cycle number to be 8, and after polymerization, removing doping the obtained sample into an acetonitrile solution of tetrabutylammonium hexafluorophosphate (the mass volume ratio of tetrabutylammonium hexafluorophosphate to acetonitrile is 0.375g:10 mL), performing cleaning by using a mixed solution of chloroform and acetonitrile (the volume ratio is 1:1.1), and performing repeated cleaning and 2 times by using nitrogen gas to obtain the boron-based electrochromic material.
The boron-based electrochromic material obtained in the embodiment is tested by adopting the method consistent with the embodiment 1, so that the boron-based electrochromic material obtained in the embodiment can realize transparent to blue reversible color change under the step voltage of 0-1.2V, the coloring time at 740nm is 4.6s, the fading time is 2.0s, the contrast at 740nm is up to 58%, the contrast is hardly attenuated after 150 cycles, and the good electrochemical stability is shown.
Example 3
Mixing 6.5mmol of diphenylamine, 0.34mmol of cuprous iodide, 0.32mmol of 2, 2-bipyridine, 13mmol of potassium tert-butoxide and 6.5mmol of 2, 5-dibromo-m-xylene with 52mL of toluene under the protection of nitrogen, reacting at 127 ℃ for 23h, extracting the obtained sample with saturated sodium chloride solution and methylene dichloride (volume ratio of 0.9:1) for 3 times, concentrating the obtained extract, dewatering with anhydrous sodium sulfate, then taking silica gel as a stationary phase, taking methylene dichloride and n-hexane as mobile phases (volume ratio of 1:2.9) for column chromatography purification, collecting the obtained sample, performing rotary evaporation at 63 ℃ for 42min, and drying at 57 ℃ for 22h to obtain white solid, namely the triphenylamine derivative;
Mixing triphenylamine derivative and diethyl ether under the protection of nitrogen, reacting for 31min at the temperature of minus 82 ℃, then dripping tertiary butyl lithium into the mixture at 39 drops per minute, mixing for 28min at the temperature of minus 82 ℃, then heating the mixture to the temperature of minus 1 ℃ and stirring for 31min, then adding boron trifluoride diethyl ether (the molar ratio of triphenylamine derivative, tertiary butyl lithium and boron trifluoride diethyl ether is 0.8:1.4:0.27, the mass ratio of triphenylamine derivative, tertiary butyl lithium and boron trifluoride diethyl ether to diethyl ether is 1g:11.5 ml), stirring for 30min at the temperature of 1 ℃, then heating to the temperature of 24 ℃ and reacting for 15h, extracting the obtained sample for 3 times by using saturated sodium chloride solution and dichloromethane (the volume ratio is 0.9:1), concentrating the obtained extract, dehydrating by using anhydrous sodium sulfate, then carrying out column chromatography purification by using silica gel as a stationary phase, and using dichloromethane and n-hexane as mobile phases (the volume ratio of dichloromethane to be 1:2.9), collecting the obtained sample, steaming for 42min at the temperature of 63 ℃ in a rotating way, and drying at the temperature of 57 ℃ for 22h to obtain the electrochromic monomer material of boron base;
Adding monomers of a boron-based electrochromic material and tetrabutylammonium hexafluorophosphate into a mixed solution of 2.6mL of chloroform and 7.4mL of acetonitrile (the concentration of the monomers in the mixed solution is 1mmol/L, the concentration of the tetrabutylammonium hexafluorophosphate is 0.25 mol/L), performing ultrasonic treatment at 42kHz for 3min, performing electrochemical polymerization by using ITO glass (0.8 x 3.5 cm) as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode through a cyclic voltammetry, setting the scanning speed to be 95mV/s, setting the voltage to be 0.5V, setting the number of cycles to be 11, and after the polymerization is finished, dedoping the obtained sample into an acetonitrile solution of tetrabutylammonium hexafluorophosphate (the mass-volume ratio of the tetrabutylammonium hexafluorophosphate to the acetonitrile is 0.39g:10 mL), and cleaning the obtained sample by using the mixed solution of chloroform and acetonitrile.
The boron-based electrochromic material obtained in the embodiment is tested by adopting the method consistent with the embodiment 1, so that the boron-based electrochromic material obtained in the embodiment can realize transparent to blue reversible color change under the step voltage of 0-1.2V, the coloring time at 740nm is 4.7s, the fading time is 1.9s, the contrast at 740nm is up to 57%, the contrast is hardly attenuated after 150 cycles, and the good electrochemical stability is shown.
From the above examples, the present invention provides a boron-based electrochromic material with an optical contrast of up to 60% at 740nm, and response times of 4.8s and 1.8s for coloring and bleaching, respectively. In addition, the optical contrast of the boron-based electrochromic material was hardly attenuated after 150 cycles. The boron-based electrochromic material provided by the invention is an electrochromic material with excellent properties, and has wide application prospects in the field of display devices (such as anti-counterfeiting, color-changing glass, mobile phone backshells, electronic tags and electronic paper).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
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