CN107267136A - Novel electrochromic material and preparation method thereof - Google Patents
Novel electrochromic material and preparation method thereof Download PDFInfo
- Publication number
- CN107267136A CN107267136A CN201710506028.6A CN201710506028A CN107267136A CN 107267136 A CN107267136 A CN 107267136A CN 201710506028 A CN201710506028 A CN 201710506028A CN 107267136 A CN107267136 A CN 107267136A
- Authority
- CN
- China
- Prior art keywords
- edt
- edot
- electrochromic material
- electrode
- preparation
- 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.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/145—Side-chains containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a kind of novel electrochromic material and preparation method thereof, belong to electrochromic material field.The structural formula of the novel electrochromic material P (EDT E5 EDT co EDOT) is as follows:The present invention is by adjusting the ratio of monomer ether chain bridged class thiophene and EDOT, the characteristics of making it have that color change is reversible, sensitivity is high, optical transmittance is high etc..
Description
Technical field
The present invention relates to electrochromic material field, a kind of novel electrochromic material and preparation method thereof is particularly related to.
Background technology
Electrochromism refers to the optical properties (being primarily referred to as reflectivity, transmitance, absorptivity etc.) of material in extra electric field
In the presence of occur the phenomenon of reversible color change, the reversible change of color and transparency is shown as in appearance.It is electroluminescent to become
Color material can be applied to light-duty and portable display device such as Electronic Paper and the device such as smart window using light transmittance.
The automatic anti-glare rearview mirror prepared with electrochromic material, can be adjusted by electronic induction system according to the intensity of ambient light
The intensity of reflected light is saved, reaches that abblendbar is acted on, makes driving safer.
Compared to inorganic material, organic electrochromic material has many advantages, mainly has:1) preparation technology is simple, can adopt
With drop coating, spin coating etc.;2) in device preparation, handling ease, low manufacture cost.It is some mistakes that inorganic electrochromic material is conventional
Metal oxide is crossed, this metalloid is due to resource scarcity, and often cost of manufacture is very high;3) (conduction is poly- for organic electrochromic material
Compound material) higher optical contrast is shown, the fast response time, service life is longer;4) various colors, species is numerous
It is many, and the control to color can be realized by the change of structure.
In numerous organic electrochromic materials, polythiophene-based derivatives are that most study is most in current conducting polymer
Important conjugated polymer, good redox active, high electrochemistry and optical stability, good electrochromism property
And processability, become a class conducting polymer materials of most application prospect.The research work of early stage shows, takes
Dai Ji not only influences polymer molecular structure and band structure, and has an effect on the aggregated forms of polymer, structure and microcosmic point
The sub- energy level regularity of distribution.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind with color change is reversible, sensitivity is high, optical transmittance
High novel electrochromic material and preparation method thereof.
In order to solve the above technical problems, present invention offer technical scheme is as follows:
On the one hand there is provided a kind of novel electrochromic material P (EDT-E5-EDT-co-EDOT), the P (EDT-E5-
EDT-co-EDOT structural formula) has as follows:
Further, the P (EDT-E5-EDT-co-EDOT) is gathered by monomer EDT-E5-EDT and EDOT by electrochemistry
Legal to be prepared from, the concentration ratio of the EDT-E5-EDT and EDOT are 1:1-5, in EDT-E5-EDT and EDOT monomer copolymerizations
During, because the α positions of thiphene ring are more active than β, EDT-E5-EDT and EDOT monomers is easier the electricity for occurring α-α
Chemical polymerization, so as to form effective conjugated polymer chain.
Further, the structural formula of the EDT-E5-EDT is as follows:
Further, the preparation method of the EDT-E5-EDT, including:
(1) 3- bromomethyl thiophenes are first synthesized into precursor T-E5-T by Williamson reaction;
(2) NBS bromo-reactions obtain intermediate product TBr-E5-TBr;
(3) TBr-E5-TBr and EDOT-SnBu are passed through3Stille coupling reactions synthesis target product EDT-E5-EDT.
Further, the electrochemical polymerization using three-electrode system react, the three-electrode system include working electrode,
To electrode and reference electrode;Working electrode is ITO electro-conductive glass, is platinized platinum to electrode, and reference electrode is Ag/AgCl electrodes.
Further, the preparation method of the reference electrode Ag/AgCl electrodes is in 6molL by Ag-1It is permanent in HCl solution
Current potential 1.5V, electrolysis 100s, electrode surface generation AgCl coating.
When hydrogen atom is replaced by electron donating groups such as chain alkyl, alkoxies on thiphene ring β positions after, it is to avoid monomer polymerization
During alpha-beta position coupling, electrochemical polymerization can realize preferably longer conjugated polymer chain, can not only improve polymer
Environmental stability, moreover it is possible to improve polymeric material stability in use and the transmission performance of electronics.Moreover, by
In the space behavior of long chain substituents, interchain tack and main chain rigidity are reduced, thiophene interannular twist angle and main chain is improved
Conformation randomness, easily realizes the crosslinking coupling between monomer, so as to prepare the thin polymer film of high-quality self-supporting.In addition,
Relative to alkyl chain, the introducing of polyether chain can further improve the water solubility of polymer so that the processing characteristics of material is greatly
Improve.The polymer of the present invention is introduced into oxygen atom in ether chain, can increase the pliability of main polymer chain, and the orphan on oxygen atom
It can also make main polymer chain that there is certain electronic transmission performance electronics, be conducive to the raising of its electric property.
On the other hand, present invention also offers the preparation method of novel electrochromic material, including:
Step 1, under protective gas atmosphere, by solvent, EDT-E5-EDT, EDOT and supporting electrolyte add three electrodes electricity
Xie Chizhong constitutes electrolyte;
Step 2, using potentiostatic method, galvanostatic method or cyclic voltammetry, electro-deposition obtains polymer thin on the working electrode (s
Film.
Further, in addition to step 3, the thin polymer film acetonitrile that electro-deposition is obtained is soaked, is rinsed, it is poly- to remove
The oligomer of electrolyte solution and generation in compound.
Wherein, in the step 1, the solvent is acetonitrile, and the supporting electrolyte is lithium perchlorate, the protective gas
For nitrogen.
Wherein, the concentration of the supporting electrolyte is 0.2molL-1。
The invention has the advantages that:
1st, Inventive polymers have the two advantageous feature, ether chain based on ether chain bridge bithiophene EDT-E5-EDT and EDOT
Bridging thiophene makes the polymer of synthesis have good electrochromic property, and synthesized electrochemistry oxidation of precursor current potential is lower
(electrochemical polymerization for being more beneficial for monomer), can make that the polymer inherent band gap of synthesis is relatively low, and EDOT has important hole transport
Layer ability, helps to prepare electroluminescent device.
2nd, the present invention is adjusted Polymer absorption spectrum, entered by two monomers EDT-E5-EDT and EDOT of regulation ratio
And change the color of polymer.
3rd, Inventive polymers have good electrochromic property (good color change invertibity, color change spirit
Sensitivity is high, optical transmittance is high and has certain storing memory function).
Brief description of the drawings
Fig. 1 is the synthesis path of the EDT-E5-EDT monomers of the present invention.
Fig. 2 is EDT-E5-EDT monomers in the present invention, and the mixed liquor of EDOT monomers and different proportion monomer is in acetonitrile/height
Lithium chlorate (ACN/LiClO4) in anodic polarization curves, sweep speed:(A) EDT-E5-EDT (B) EDT- in 10mV/s, figure
E5-EDT/EDOT=1:1 (C) EDT-E5-EDT/EDOT=1:2 (D) EDT-E5-EDT/EDOT=1:3(E)EDT-E5-EDT/
EDOT=1:5(F)EDOT.
Fig. 3 is EDT-E5-EDT monomers in the present invention, and the mixed liquor of EDOT monomers and different proportion monomer is in ACN/
LiClO4In cyclic voltammetry curve, sweep speed:50mV/s;In figure:(A)EDT-E5-EDT,(B)EDT-E5-EDT/EDOT
=1:1, (C) EDT-E5-EDT/EDOT=1:2, (D) EDT-E5-EDT/EDOT=1:3, (E) EDT-E5-EDT/EDOT=1:
5,(F)EDOT。
Fig. 4 is (A) P (EDT-E5-EDT) and EDT-E5-EDT/EDOT=(B) 1 in the present invention:1,(C)1:2,(D)1:3,
(E)1:The P (EDT-E5-EDT-co-EDOT) and (F) PEDOT prepared in 5 mixed solution is in the ACN/ without monomer
LiClO4In cyclic voltammetry curve.
Fig. 5 is (A) P (EDT-E5-EDT) and EDT-E5-EDT/EDOT=(B) 1:1,(C)1:2,(D)1:3,(E)1:5
The P (EDT-E5-EDT-co-EDOT) and (F) PEDOT spectroelectrochemistry prepared in mixed solution.
Fig. 6 is (A) P (EDT-E5-EDT) and EDT-E5-EDT/EDOT=(B) 1:1,(C)1:2,(D) 1:3,(E)1:5
Mixed solution in the electrochromism switching of the P (EDT-E5-EDT-co-EDOT) and (F) PEDOT that prepare at different wave length
Curve, conversion time is 5s.
Fig. 7 is (a) P (EDT-E5-EDT) and EDT-E5-EDT/EDOT=(b) 1:1,(c)1:2,(d)1:3,(e)1:5
The P (EDT-E5-EDT-co-EDOT) and (f) PEDOT infrared absorption spectroscopy prepared in mixed solution.
Fig. 8 (d) is P (EDT-E5-EDT) monomer, and a and b represent EDT-E5- in P (EDT-E5-EDT-co-EDOT) respectively
EDT and EDOT ratios are 1:3、1:5 and (c) PEDOT thermal gravimetric analysis curve.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
The present invention is for there is provided one kind the problem of electrochromic property is poor in the prior art, color change interval is more single
Novel electrochromic material and preparation method thereof.
Embodiment 1
The electrochemical polymerization step of novel electrochromic material P (EDT-E5-EDT-co-EDOT) polymer:
(1) the chemical synthesis process (as shown in Figure 1) of subject monomers
1. precursor T-E5-T preparation:The thiophene presoma T-E5-T of ether chain bridged is synthesized by the inferior prestige reaction of William;
2. intermediate product TBr-E5-TBr preparation:Intermediate product TBr-E5-TBr is synthesized by bromo-reaction;
③EDOT-SnBu3Preparation:EDOT is dissolved in dry tetrahydrofuran (100mL), in inert nitrogen protection
Under, n-BuLi is added dropwise, stirring heating adds tributyltin chloride, and stirring is warmed to room temperature again, lasting stirring.After end, filtering
And filtrate is collected, revolving removes organic solvent, obtains crude product EDOT-SnBu3;
4. the preparation of subject monomers (EDT-E5-EDT):TBr-E5-TBr and EDOT-SnBu3Stille coupling reactions close
Into target product EDT-E5-EDT.
(2) preparation of novel electrochromic material P (EDT-E5-EDT-co-EDOT) polymer
Electrochemical polymerization is carried out in a Room three-electrode system, and working electrode is ITO electro-conductive glass, is platinized platinum to electrode,
Reference electrode is that (Ag in 6molL for Ag/AgCl electrodes-1HCl solution constant potential 1.5V, 100s electrolytic surface generation AgCl cover
Layer);
Using 4mL acetonitrile as electrolyte, lithium perchlorate (0.08512g, 0.8mmol) is supporting electrolyte, EDT-E5-EDT
It is polymerized monomer with EDOT, EDT-E5-EDT and EDOT polymerization ratio are 1:0,1:1,1:2,1:3,1:5,0:1;Using permanent electricity
Position method is polymerize, and polymerization current potential is respectively 0.95V, 1.05V, 1.05V, 1.05V, 1.05V, 1.2V, and polymerization time is 500s,
The thin polymer film acetonitrile that electro-deposition is obtained soaks, rinsed, to remove the oligomeric of electrolyte solution in polymer and generation
Thing.
Embodiment 2
The infrared spectrogram of P (EDT-E5-EDT-co-EDOT), P (EDT-E5-EDT) and PEDOT in the present invention, such as scheme
Shown in 7, P (EDT-E5-EDT) infrared spectrum curve (a) is in 2920 and 2870cm-1Occur in that C-H stretching vibration characteristic peak.
In 1630 and 1370cm-1Absorption band result from the stretch mode of C=C and C-C in thiphene ring, and in 1240 and 1080cm-1
C-O-C and C-S-C stretching vibration are attributed to respectively.1630,1430 and 1020cm in the curve of spectrum (b-e) of copolymer-1's
Characteristic peak is more closely similar to P (EDT-E5-EDT).In 2960 and 2860cm-1The weak absworption peak in place and ether chain in EDT-E5-EDT structures
Upper CH2Stretching vibration it is relevant, this shows in P (EDT-E5-EDT-co-EDOT) chain with the presence of EDT-E5-EDT units.With this
Meanwhile, 1080cm-1Absworption peak it is relevant with C-O-C stretching vibration.Infrared absorption spectroscopy confirms that thiphene ring does not have in polymer
There is the successful synthesis of destroyed and conjugated polymer.
Embodiment 3
P (EDT-E5-EDT-co-EDOT), P (EDT-E5-EDT) and PEDOT films thermal degradation row are tested by TGA
For.As shown in figure 8, the main decomposition of polymer is since 130K, the weight loss from the temperature to 800K polymer is fast
Speed increase.Polymer undergo two steps it is diversified decompose, the first step (130-454K) correspond to ether chain backbone, ethylene two oxy and
The decomposition of conjugated chain, and second step (454-800K) is relevant with the disconnection of polythiophene chain.Homopolymer P (EDT-E5-EDT) and
PEDOT is respectively 46.2% and 72.0% in the weight loss of the first step.Copolymer p (EDT-E5-EDT-co-EDOT) is first
The weight loss of step is 32.3%-39.3%.This result shows that copolymer film is more preferable than the heat endurance of homopolymer.
Embodiment 4
Determine P (EDT-E5-EDT), PEDOT and P (EDT-E5-EDT-co-EDOT) chemical property
Electrochemical property test is carried out in a Room three-electrode system, and working electrode used is ITO electro-conductive glass, to electrode
For diameter 1mm platinum filament, reference electrode reference electrode is Ag/AgCl electrodes.During electrochemistry experiment, between three electrodes
Distance keeps 0.5cm.
(1) chemical property of monomer
Using 4mL acetonitrile as electrolyte, lithium perchlorate (0.08512g, 0.8mmol) is supporting electrolyte, EDT-E5-EDT
It is polymerized monomer with EDOT, EDT-E5-EDT and EDOT polymerization ratio are 1:0,1:1,1:2,1:3,1:5,0:1;Utilize anode
Polarization curve, cyclic voltammetry curve, with the time current curve and current potential-current curve of electrochemical workstation record body, sentence
The initial oxidation current potential and record oxidation-reduction process of disconnected monomer.
The anodic polarization curves of the gained mix monomer of testing example 1 are as shown in Figure 2, cyclic voltammetry curve is as shown in Figure 3.
In principle, the oxidizing potential difference of two materials, which is less than 0.5V, to be copolymerized, and understood with reference to Fig. 2, EDT-E5-
EDT (a) and EDOT (f) initial oxidation current potential is respectively 0.82V and 1.06V, and both differ 0.24V oxidizing potential, meaning
The electrochemistry copolymerization for EDT-E5-EDT and EDOT is feasible.As seen from the figure, the initial oxidation current potential of mix monomer exists
Between 0.70V and 0.78V, electrochemical polymerization current potential has declined.
With reference to Fig. 3, all cyclic voltammetry curves show the electropolymerization feature similar to other conducting polymers.Polymerization
Current density gradually increases with the continuous scanning of cyclic voltammetry curve, shows the life of corresponding conducting polymer on working electrode
It is long, while meaning that the conducting polymer prepared has good electro-chemical activity.Cyclic voltammetry curve shows wide oxidation
Reduction potential scope and different redox spike potentials.In figure there is obvious difference in the cyclic voltammetry curve of mix monomer,
Show that EDT-E5-EDT and EDOT realize electrochemical polymerization.Also, with the increase of EDOT content of monomer, corresponding oxidation and
Reduction potential scope is wider.
(2) chemical property of polymer
Using 4mL acetonitrile as electrolyte, lithium perchlorate (0.08512g, 0.8mmol) is supporting electrolyte, EDT-E5-EDT
It is polymerized monomer with EDOT, EDT-E5-EDT and EDOT polymerization ratio are 1:0,1:1,1:2,1:3,1:5,0:1;Using permanent electricity
Position method is polymerize, and polymerization current potential is respectively 0.95V, 1.05V, 1.05V, 1.05V, 1.05V, 1.2V, and polymerization time is 30s,
The thin polymer film acetonitrile that electro-deposition is obtained on platinum filament soaks, rinsed.By electrode transposition, using 4mL acetonitrile as electrolyte,
Lithium perchlorate (0.08512g, 0.8mmol) is supporting electrolyte, no polymerized monomer.Using cyclic voltammetry curve, swept in different
Retouch under speed, current potential-current curve of polymer is recorded with electrochemical workstation, the electroactive of thin polymer film is judged.
The volt of the circulation in the acetonitrile without monomer of the thin polymer film being deposited on platinum filament of the gained of testing example 1
Pacify curve as shown in Figure 4.
With reference to represented by Fig. 4, P (EDT-E5-EDT), P (EDT-E5-EDT-co-EDOT) and PEDOT cyclic voltammetric are bent
Line is significantly different, further confirms the generation of EDT-E5-EDT and EDOT copolymerization.In addition, P (EDT-E5-EDT-co-EDOT) is thin
Film shows larger peak current density compared with PEDOT, has broader potential range compared with P (EDT-E5-EDT).
Embodiment 5
Determine P (EDT-E5-EDT-co-EDOT) electrochromic property
(1) electrochemical optical spectra
By the thin polymer film being deposited on ITO electro-conductive glass of preparation, it is placed in three-electrode cell, is in electrolytic cell
0.2mol·L-1Lithium perchlorate acetonitrile solution, wherein working electrode is ITO electro-conductive glass with thin polymer film, to electrode
For platinized platinum, reference electrode is Ag/AgCl electrodes, and using constant potential method, work electricity is applied to by electrochemical workstation regulation
Voltage on extremely, while recording the variation tendency of polymer absorption spectrum under different voltages with ultraviolet-visual spectrometer, is produced
The spectroelectrochemistry collection of illustrative plates of polymer is arrived.
The electrochemistry spectrum spectrogram difference of the thin polymer film being deposited on ITO electro-conductive glass of the gained of testing example 1
As shown in Figure 5.
With reference to Fig. 5, occurs strong absworption peak at 474nm during condition in P (EDT-E5-EDT).With current potential from-
The absworption peak reduction that 0.2V increases at 1.2V, 474nm, new peak appears in 690nm or so, while in IR regions about
Along with a wide absworption peak at 900nm.Also may be used in P (EDT-E5-EDT-co-EDOT) and PEDOT electrochemistry spectrogram
To observe similar trend.
For the thin polymer film of preparation, the Change of absorption of electronics is completely reversibility under different application current potentials, by
Limited in length, only with EDT-E5-EDT and EDOT 1:Polymerizeing obtained P (EDT-E5-EDT-co-EDOT) under the conditions of 5 is
Example, the change of absorption spectrum is along with from orange red to the color change (being shown in Table 1) of blueness.
Table 1
(2) the dynamic performance research of polymer film
Determined using ultraviolet-uisible spectrophotometer under square wave current potential, polymer film at a particular wavelength, it is doped and
The transmitance of middle condition, so that optical contrast is calculated, response time etc.;Ultraviolet-uisible spectrophotometer record for when
M- transmittance curve, electrochemical workstation record for time current curve, can also calculate coloring according to this two curves
Efficiency.
The when m- transmittance curve of the thin polymer film being deposited on ITO electro-conductive glass of the gained of embodiment 1 is such as schemed respectively
Shown in 6.By two when response time for calculating of m- transmittance curve, coloration efficiency be shown in Table 2 respectively.
Timing absorption process research has been carried out to P (EDT-E5-EDT) under 474nm wavelength, 460nm, 469nm, 481nm,
To different monomers ratio (1 under 469nm wavelength:1,1:2,1:3,1:5) P (EDT-E5-EDT-co-EDOT) has carried out timing suction
Receipts method research;PEDOT has been carried out in timing absorption process research, experimentation under 600nm wavelength, potential Spline smoothing when
Between at intervals of 5s, as shown in Figure 6.Under a wavelength, polymer all shows certain optical contrast and good light
Learn stability;In addition, optical transmittance has a great impact to the color change of polymer, the polymer can be from orange red
Middle condition is to the doped transformation of blueness.
Table 2
Note:Coloration efficiency:Refer to electrochromic material under given wavelength, the change of absorbance is with causing whole electronics to be noted
Ratio when entering or extracting out.
For a kind of electrochromic material, coloration efficiency is an important parameter for evaluating material property.Coloring effect
The coloration efficiency of rate research conducting polymer will combine the electrochemistry and spectrum change process of electrochromic film, and its calculation formula is such as
Under:
CE=Δs OD/Qd (1)
Wherein, the change (Δ OD) of optical contrast ratio refers in a specific wavelength λmaxUnder, electrochemical oxidation and reductive polymerization
During thing film, corresponding transmitance value (transmitance T when polymer film is dopedoxTransmitance T during with middle conditionred) ratio,
Calculated by below equation:
Δ OD=log (Tox/Tred) (2)
The color for absorbing position decision polymer of polymer, has weight for preparing a variety of colors electrochromic polymeric compounds
Meaning is wanted, the response time is equally the important parameter of electrochromic material, and it is disclosed during doping, Doped ions enter
The speed of main polymer chain;As can be seen from Table 2, homopolymer film P (EDT-E5-EDT) and PEDOT are in visibility region Δ
T% points are 35.38%, 48.86%, and the polymerized monomer ratio used has a significant effect to Δ T%.Ratio is 1:1,1:2,1:3,
1:Δ T% of 5 copolymer p (EDT-E5-EDT-co-EDOT) respectively at 460nm, 469nm, 481nm, 469nm reaches
26.88%th, 24.78%, 30.51%, 19.04%.Than homopolymer film PEDOT, therefrom condition switches copolymer to oxidation state
Speed is faster.The CE values of homopolymer film P (EDT-E5-EDT) and PEDOT at 474nm and 600nm are respectively
203.2cm2C-1、98.0cm2C-1.Compared with P (EDT-E5-EDT) CE values, P (EDT-E5-EDT) and PEDOT is 1:3 conditions
The CE values of the copolymer of lower formation improve 23.67%.
Copolymer p (EDT-E5-EDT-co-EDOT) film shows good electroluminescent change between middle condition and oxidation state
Color invertibity, its bandwidth is low, various colors, have certain storing memory function, contributes to the application of electrochromic material.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of novel electrochromic material P (EDT-E5-EDT-co-EDOT), it is characterised in that the P (EDT-E5-EDT-
Co-EDOT structural formula) has as follows:
2. novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 1, it is characterised in that institute
P (EDT-E5-EDT-co-EDOT) is stated to be prepared from by electrochemical polymerization method by monomer EDT-E5-EDT and EDOT, it is described
EDT-E5-EDT and EDOT concentration ratio is 1:1-5.
3. novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 2, it is characterised in that institute
The structural formula for stating EDT-E5-EDT is as follows:
4. novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 3, it is characterised in that institute
EDT-E5-EDT preparation method is stated, including:
(1) 3- bromomethyl thiophenes are first synthesized into precursor T-E5-T by Williamson reaction;
(2) NBS bromo-reactions obtain intermediate product TBr-E5-TBr;
(3) TBr-E5-TBr and EDOT-SnBu are passed through3Stille coupling reactions synthesis target product EDT-E5-EDT.
5. novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 2, it is characterised in that institute
State electrochemical polymerization to react using three-electrode system, the three-electrode system includes working electrode, to electrode and reference electrode;Work
Make electrode for ITO electro-conductive glass, be platinized platinum to electrode, reference electrode is Ag/AgCl electrodes.
6. novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 5, it is characterised in that institute
The preparation method for stating reference electrode Ag/AgCl electrodes is in 6molL by Ag-1Constant potential 1.5V, electrolysis in HCl solution
100s, electrode surface generation AgCl coating.
7. any described novel electrochromic material P (EDT-E5-EDT-co-EDOT) preparation method in claim 1-6,
It is characterised in that it includes:
Step 1, under protective gas atmosphere, by solvent, EDT-E5-EDT, EDOT and supporting electrolyte add three-electrode cell
Middle composition electrolyte;
Step 2, using potentiostatic method, galvanostatic method or cyclic voltammetry, electro-deposition obtains thin polymer film on the working electrode (s.
8. the preparation method of novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 7, it is special
Levy and be, in addition to step 3, the thin polymer film acetonitrile that electro-deposition is obtained soaked, is rinsed.
9. the preparation method of novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 8, it is special
Levy and be, in the step 1, the solvent is acetonitrile, and the supporting electrolyte is lithium perchlorate, and the protective gas is nitrogen
Gas.
10. the preparation method of novel electrochromic material P (EDT-E5-EDT-co-EDOT) according to claim 9, its
It is characterised by, the concentration of the supporting electrolyte is 0.2molL-1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710506028.6A CN107267136A (en) | 2017-06-28 | 2017-06-28 | Novel electrochromic material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710506028.6A CN107267136A (en) | 2017-06-28 | 2017-06-28 | Novel electrochromic material and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107267136A true CN107267136A (en) | 2017-10-20 |
Family
ID=60071090
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710506028.6A Pending CN107267136A (en) | 2017-06-28 | 2017-06-28 | Novel electrochromic material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107267136A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105199709A (en) * | 2015-09-09 | 2015-12-30 | 青岛科技大学 | Electrochromic material and preparation method thereof |
CN106243327A (en) * | 2016-07-08 | 2016-12-21 | 江西科技师范大学 | Di-indole dione class D A D type polymer electrochromic material and preparation method thereof |
-
2017
- 2017-06-28 CN CN201710506028.6A patent/CN107267136A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105199709A (en) * | 2015-09-09 | 2015-12-30 | 青岛科技大学 | Electrochromic material and preparation method thereof |
CN106243327A (en) * | 2016-07-08 | 2016-12-21 | 江西科技师范大学 | Di-indole dione class D A D type polymer electrochromic material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
YONGJING HU ET AL.: "Electrosynthesis and Electrochromic Properties of Free-Standing Copolymer Based on Oligo(Oxyethylene) Cross-Linked 2,2’-Bithiophene and 3,4-Ethylenedioxythiophene", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
YONGJING HU ET AL.: "Free-standing oligo(oxyethylene)-functionalized polythiophene with the 3,4-ethylenedioxythiophene building block: electrosynthesis, electrochromic and thermoelectric properties", 《ELECTROCHIMICA ACTA》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gaupp et al. | Poly (ProDOT‐Et2): a high‐contrast, high‐coloration efficiency electrochromic polymer | |
Xu et al. | Solution-processable electrochromic red-to-transmissive polymers with tunable neutral state colors, high contrast and enhanced stability | |
CN106543415B (en) | Thin polymer film and the preparation method and application thereof based on intersection construction conjugated molecule | |
Carbas et al. | Electrosynthesis of a new indole based donor-acceptor-donor type polymer and investigation of its electrochromic properties | |
Yao et al. | Flexible conjugated polyfurans for bifunctional electrochromic energy storage application | |
Sari et al. | Synthesis and characterization of polyurethane/polythiophene conducting copolymer by electrochemical method | |
Soganci et al. | Processable amide substituted 2, 5-bis (2-thienyl) pyrrole based conducting polymer and its fluorescent and electrochemical properties | |
CN114907551B (en) | Red electrochromic polymer, preparation method, film and device | |
Carbas et al. | A classified and comparative review of Poly (2, 5-dithienyl-N-substituted-pyrrole) derivatives for electrochromic applications | |
Hellström et al. | Influence of side chains on electrochromic properties of green donor–acceptor–donor polymers | |
Gumusay et al. | Electrochemistry of secondary amine substituted 2, 5-di (2-thienyl) pyrrole derivative and its copolymer | |
Turkoglu et al. | Electropolymerization, spectroelectrochemistry and electrochromic properties of cross-conjugated and conjugated selenophenothiophenes with thiophene bridge | |
CN110229312B (en) | Black polymer material and preparation method and application thereof | |
Balkhandia et al. | Tailoring the properties in conjugated copolymer P (EDOS-co-EDOT): Electrochemical polymerization and role of heteroatom | |
CN108503839B (en) | Multifunctional reticular polymer and film, preparation method and application of film in electrochromic or electric control fluorescence aspect | |
US6197921B1 (en) | Polymers of 1-(bithien-2-yl)-4-aminobenzene | |
Li et al. | Electrochemical copolymerization of 3, 4-ethylenedioxythiophene and 6-cyanoindole and its electrochromic property | |
CN101591425A (en) | Novel electrochromic copolymer and its production and application | |
Carbas | Novel electrochromic copolymers based on 3-3′-dibromo-2-2′-bithiophene and 3, 4 ethylene dioxythiophene | |
JPH075716B2 (en) | Process for producing N, N'-diphenylbenzidine polymer | |
CN107267136A (en) | Novel electrochromic material and preparation method thereof | |
CN111323980A (en) | Preparation method and application of titanium dioxide/poly [2- (4-thiophene) benzene ] amine composite film | |
Yildiz et al. | Conducting copolymers of 3-methylthienyl methacrylate and p-vinylbenzyloxy poly (ethyleneoxide) and their electrochromic properties | |
CN104387566B (en) | A kind of D A D type electrochromic polymeric compounds using pyrido heterocycle as acceptor | |
Chen et al. | Navy-to-transmissive electrochromic polymer based on 3, 4-propylenedioxythiophene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |
|
RJ01 | Rejection of invention patent application after publication |