CN114920732A - Thiophene-bridged viologen ionic liquid and preparation and application of electrochromic elastomer thereof - Google Patents
Thiophene-bridged viologen ionic liquid and preparation and application of electrochromic elastomer thereof Download PDFInfo
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Abstract
The invention discloses a thiophene bridged viologen ionic liquid and preparation and application of an electrochromic elastomer thereof, wherein the thiophene bridged viologen ionic liquid with electrochromic and electrochromism performances and a polyacrylate elastomer with tensile performance are combined to prepare an ultrastable and stretchable electrochromic elastomer, and the material has the following advantages: the electrochromic elastomer has the characteristics of adhesion, stretchability and flexibility, so that the process of preparing the electrochromic device is extremely simple and convenient, and the electrochromic device can be obtained only by placing the electrochromic elastomer between two electrodes without packaging; the electrochromic elastomer based on the ionic liquid has extremely high stability, and still shows good color-changing performance after being placed for months or even one year; the conductivity of the elastomer changes along with the stretching condition, so that the electrochromic performance of the electrochromic device changes along with the stretching condition, and the electrochromic device has a huge application prospect in the field of developing visual sensors.
Description
Technical Field
The invention belongs to the field of multifunctional high polymer materials, and relates to thiophene bridged viologen ionic liquid and preparation and application of an electrochromic elastomer thereof, in particular to preparation of an electrochromic elastomer based on thiophene bridged viologen ionic liquid and double-network polyacrylate and application of an electrochromic device and visual sensing of the electrochromic elastomer.
Background
In recent years, chronic diseases have gradually become the leading factor threatening the health of residents, and wearable health monitoring sensors have been widely regarded by researchers for the purpose of strengthening personal health management and preventing chronic diseases, and also play an increasingly important role in physiological signal monitoring. However, the current sensing devices still have the defects of sensitivity, reliability and visualization. The viologen compound is widely applied to the actual fields of anti-dizziness rearview mirrors, intelligent windows, information display, biological sensing and the like due to the electrochromic property, and is expected to realize the visualization of the sensor.
However, the application of viologen derivatives in the field of photoelectricity is greatly limited by the defects of viologen compounds, such as single color change condition and weak absorption of visible light. Meanwhile, the solution-state electrochromic layer makes the manufacturing and packaging of the electrochromic device more complicated, and meanwhile, the risk of liquid leakage and the like exists, so that the large-scale production and use are difficult to realize.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide thiophene bridged viologen ionic liquids and preparation and application of electrochromic elastomers thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses thiophene bridged viologen ionic liquid which is viologen ionic liquid containing sulfur family elements in a symmetrical structure or viologen ionic liquid containing sulfur family elements in an asymmetrical structure;
the viologen ionic liquid containing the sulfur group elements with the symmetrical structure has the following structure:
wherein E is sulfur,Selenium or tellurium; n is 1, 2, 3; x — Is Cl — 、Br — 、I — 、CF 3 SO 2 O — 、PF 6 — 、CH 3 COO — Or OTf — ；
The structure of the viologen ionic liquid containing the sulfur group elements with the asymmetric structure is as follows:
wherein R is an amine, alkyl or aryl group; e is sulfur, selenium or tellurium; n is 1, 2, 3; x — Is Cl — 、Br — 、I — 、CF 3 SO 2 O — 、PF 6 — 、CH 3 COO — Or OTf — 。
The invention also discloses application of the thiophene-bridged viologen ionic liquid in preparation of an electrochromic elastomer.
The invention also discloses a preparation method of the electrochromic elastomer, which comprises the following steps: preparing a polyethylacrylate-based polymer matrix by photo-initiated free radical polymerization, and then soaking the polyethylacrylate-based polymer matrix in an ethanol solution containing 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonimide salt and the thiophene-bridged viologen ionic liquid of claim 1 to prepare the electrochromic elastomer through a swelling process.
Preferably, the polyethylacrylate-based polymer matrix is prepared by photoinitiated free radical polymerization, as follows:
dissolving ethyl acrylate, ethylene glycol dimethacrylate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide in toluene to obtain a mixed solution, adding the mixed solution into a PVDF (polyvinylidene fluoride) mould, placing the PVDF mould under an ultraviolet lamp for reacting for 1 hour, taking out a polyethylacrylate film from the mould, soaking the polyethylacrylate film in a toluene/n-hexane mixed solvent to remove residual reactants, and drying to obtain mono-network polyethylacrylate;
soaking the mono-network polyethyl acrylate in a mixed system of ethyl acrylate, ethylene glycol dimethacrylate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, standing for 24 hours, taking out, placing under an ultraviolet lamp for reacting for 1 hour, and drying to obtain a bi-network polyethyl acrylate matrix, namely the polyethyl acrylate-based polymer matrix.
Further preferably, ethyl acrylate, ethylene glycol dimethacrylate (0.68 mol%), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (1.16 mol%) were dissolved in an equal volume of toluene, and the solution was added to a 1mm thick PVDF mold and placed under an ultraviolet lamp for 1 hour. And taking the polyethylacrylate film out of the grinding tool, soaking the polyethylacrylate film in a toluene/n-hexane mixed solvent to remove residual reactants, and then placing the polyethylacrylate film in a vacuum drying oven to be dried at 80 ℃ to obtain the single-network polyethylacrylate. Soaking mono-network polyethyl acrylate in a mixture of ethyl acrylate, ethylene glycol dimethacrylate (0.01 mol%) and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (0.01 mol%) for 24 hours, taking out, and placing under an ultraviolet lamp for reacting for one hour. Placing the mixture in a vacuum drying oven at 80 ℃ for 12 hours to obtain the double-network polyethylacrylate matrix.
Preferably, the polymer matrix based on the polyethylacrylate is immersed in an ethanol solution containing 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and the above thiophene-bridged viologen ionic liquid for 24 hours, and dried to obtain the electrochromic elastomer.
Further preferably, the electrochromic elastomer is obtained by immersing the polymer matrix based on the polyethylacrylate in an ethanol solution containing 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt and the above-mentioned thiophene-bridged viologen ionic liquid for 24 hours and then placing the solution in a vacuum drying oven at 80 ℃ for 12 hours.
The invention also discloses the electrochromic elastomer prepared by the preparation method of the electrochromic elastomer.
The invention also discloses an application of the electrochromic elastomer in preparing a packaging-free electrochromic device.
Preferably, when the packaging-free electrochromic device is prepared, the electrochromic elastomer is placed between two pieces of conductive substrates, and the electrochromic device is obtained without packaging.
Further preferably, the conductive substrate is made of ITO conductive glass or a flexible ITO-PET conductive film.
Compared with the prior art, the invention has the following beneficial effects:
the invention successfully synthesizes the thiophene-bridged viologen ionic liquid and applies the thiophene-bridged viologen ionic liquid to the preparation of flexible electrochromic devices. The invention utilizes thiophene-bridged viologen ionic liquid and a polymer of polyethylacrylate to prepare the electrochromic elastomer, the electrochromic elastomer has excellent tensile and adhesive properties and ultrahigh stability, and can be used for preparing packaging-free electrochromic devices and flexible devices with the color-changing property changing along with the tensile property.
The invention combines the thiophene bridged viologen ionic liquid with electrochromic and electrochromism performances and the polyacrylate elastomer with tensile performance to prepare the ultrastable and stretchable electrochromic elastomer, and the material has the following advantages: the electrochromic elastomer has the characteristics of adhesiveness, stretchability and flexibility, so that the process for preparing the electrochromic device is extremely simple and convenient, and the electrochromic device can be obtained only by placing the electrochromic elastomer between two electrodes without packaging; 2, the electrochromic elastomer based on the ionic liquid has extremely high stability, and still shows good color-changing performance after being placed for months or even one year; and 3, the conductivity of the elastomer changes along with the stretching condition, so that the electrochromic performance of the electrochromic device changes along with the stretching condition, and the electrochromic device has a huge application prospect in the field of developing visual sensors.
Drawings
FIG. 1a shows compound 5 thiophene bridged viologen ionic liquid (c ═ 10) -3 M) UV absorption in DMF solution;
FIG. 1b shows the UV absorption of compound 5 after reduction with Zn powder in DMF solution;
FIG. 1c is an excitation, emission spectrum of Compound 5;
FIG. 1d is the electron paramagnetic spectrum of the radical cation of Compound 5;
FIG. 2a is a photograph of polyethylacrylate, an electrochromic elastomer, and an electrochromic elastomer under UV light irradiation;
FIG. 2b is a drawing of a center-knotted electrochromic elastomer;
FIG. 2c is adhesion of electrochromic elastomer;
FIG. 2d is a stress-strain curve for polyacrylates and elastomers with varying proportions of ionic liquids;
FIG. 2e is a graph of the energy to break and Young's modulus of polyacrylates and elastomers with varying proportions of ionic liquids;
FIG. 2f is a graph showing the relationship between the ionic liquid content in the elastomer and the soaking time of polyethylacrylate in a solution containing ionic liquid;
FIG. 2g shows elastomer at 6X 10 -4 A weight retention curve in a Pa environment;
FIG. 3a is a schematic view of an encapsulation-free electrochromic device;
FIG. 3b is a photograph of an electrochromic device containing an electrochromic elastomer;
FIG. 3c is a color change of an electrochromic device containing an electrochromic elastomer;
FIG. 3d is a color change of a flexible electrochromic device containing an electrochromic elastomer;
FIG. 3e is a cyclic voltammogram of viologen ion;
FIG. 3f is an electrochemical spectrum of an electrochromic device;
FIG. 3g is a color change-recovery time for an electrochromic device;
figure 3h is the coloring efficiency of the electrochromic elastomer.
FIG. 4a is a color change of an elastomer after standing for different periods of time;
FIG. 4b is an electrochromic cycle stability test of a freshly prepared elastomer;
figure 4c is an electrochromic cycle stability test of the elastomer after one year of standing.
FIG. 5(a is the electrochromic condition of elastomers in different tensile states after a voltage of 3.5V is applied for 150 seconds;
FIG. 5b is a graph of transmittance, current, and voltage during electrochromic process for elastomers in different tensile states;
fig. 5c shows different electrochromic conditions in the stretched (e 300%), relaxed (e 0%) state with continuous application of a voltage of 3.5V;
fig. 5d shows the transmittance, current and voltage curves during electrochromic in stretched (e 300%) and relaxed (e 0%) states, wherein the electrochromic elastomer exhibits substantially unchanged transmittance in stretched (e 300%) state, undergoes electrochromic after relaxation (e 0%) and changes transmittance, and fades after changing voltage to 0V in relaxed (e 0%) state, under the condition of continuous application of 3.5V voltage.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the thiophene-bridged viologen ionic liquid prepared by the invention can be prepared by the following steps of the reaction equation:
1) preparation of imidazolium salts 2
1.3-dibromopropane (752mmol) was dissolved in acetonitrile (40mL), and Compound 1(37.6mmol) was dissolved in acetonitrile (10mL) and added dropwise to a solution of 1, 3-dibromopropane in acetonitrile and heated under reflux for 24 hours. The product was isolated by vacuum filtration. The reaction equation is as follows:
2) preparation of thiophene-bridged viologen 4
Compound 2(12.6mmol) and thiophene-bridged pyridine 3(4.2mmol) were dissolved in nitromethane (50mL) and reacted at 60 ℃ for 4 hours. The product was centrifuged and washed with dichloromethane to give thiophene-bridged viologen 4. The reaction equation is as follows:
3) preparation of thiophene-bridged viologen Ionic liquids 5
Thiophene-bridged viologen 4(2.5mmol) dissolved in H 2 O (50mL), LiTFSI (12mmol) was added. The product was obtained by centrifugation, and the reaction equation was as follows:
the physical properties and the structure of the thiophene bridged viologen prepared by the invention are analyzed as follows:
1. nuclear magnetic data for thiophene-bridged viologen 4
1 H NMR(400MHz,D 2 O)δ8.77(s,2H,ImH),8.75(m,4H,PyH),8.27(m,4H,PyH),8.08(m,2H,ThH),7.48(dd,J＝2.0 1.9Hz,2H,ImH),7.41(dd,J＝1.9,1.8Hz,2H,ImH),4.62(t,J＝7.6Hz,4H,CH 2 ),4.34(t,J＝7.3Hz,4H,CH 2 ),3.83(s,6H,CH 3 ),2.60(q,J＝7.4Hz,4H,CH 2 )ppm. 13 C NMR(100MHz,DMSO-d 6 )δ147.26,145.90,143.10,137.31,134.33,124.23,123.75,122.73,99.99,57.39,46.15,36.35,31.00ppm.
2. Nuclear magnetic, ultraviolet absorption, mass spectrum and fluorescence data of thiophene bridged viologen 5
1 H NMR(400MHz,DMSO-d 6 )δ9.11(s,2H,ImH),9.08(m,4H,PyH),8.53(m,4H,PyH),8.50(m,2H,ThH),7.75(m,4H,ImH),4.61(t,J＝7.6Hz,4H,CH 2 ),4.28(t,J＝7.3Hz,4H,CH 2 ),3.87(s,6H,CH 3 ),2.53(m,4H,CH 2 )ppm. 19 F NMR(282MHz,DMSO-d 6 )δ-78.73ppm. 13 C NMR(100MHz,DMSO-d 6 )δ147.31,145.86,143.07,137.25,134.28,124.28,123.70,122.72,121.52,118.32,57.51,46.15,36.31,31.96ppm.HRMS(ESI)m/z:calcd for C 28 H 34 N 6 S 4+ 121.56359；found 121.56360.UV/vis(in DMF):λ max (ε)＝475nm(4.175×10 4 M -1 cm -1 ).Fluorescence emission(in DMF)(λ ex ＝495nm):λ emis ＝580nm.Mp(℃):-16
2. Preparing polyethylacrylate ionic gel based on thiophene bridged viologen ionic liquid:
preparation of single-network polyethylacrylate: ethyl acrylate, ethylene glycol dimethacrylate (0.68 mol%), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (1.16 mol%) were dissolved in toluene of equal volume, the solution was added to a PVDF mold of 1mm thickness, and placed under an ultraviolet lamp for reaction for 1 hour. And taking the polyethylacrylate film out of the grinding tool, and soaking the polyethylacrylate film in a toluene/n-hexane mixed solvent to remove residual reactants. And (3) placing the mono-network polyethyl acrylate in a vacuum drying oven for drying at 80 ℃, and storing at room temperature for later use.
Preparation of double-network polyethylacrylate: soaking mono-network polyethyl acrylate in a mixture of ethyl acrylate, ethylene glycol dimethacrylate (0.01 mol%) and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (0.01 mol%) for 24 hours, taking out, and placing under an ultraviolet lamp for reacting for one hour. The double-network polyethylacrylate is obtained after being placed in a vacuum drying oven at the temperature of 80 ℃ for 12 hours.
Preparation of electrochromic ionic gel: soaking polyethylacrylate in an ethanol solution containing thiophene bridged viologen ionic liquid (100mg/mL) and 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (1/5V/V), taking out, and drying in a vacuum drying oven at 80 ℃ to obtain the electrochromic elastomer.
3. Application of electrochromic elastomer in electrochromic device
The electrochromic elastomer is placed between two pieces of ITO conductive glass or flexible ITO-PET conductive films, and the electrochromic device can be obtained without packaging.
Example 1
The thiophene bridged viologen ionic liquid prepared by the invention can be prepared by the following steps:
1) preparation of imidazolium salts 2
1.3-dibromopropane (752mmol) was dissolved in acetonitrile (40mL), and Compound 1(37.6mmol) was dissolved in acetonitrile (10mL) and added dropwise to a solution of 1, 3-dibromopropane in acetonitrile and heated under reflux for 24 hours. The product was isolated by vacuum filtration. The reaction equation is as follows:
2) preparation of thiophene-bridged viologen 4
Compound 2(12.6mmol) and thiophene-bridged pyridine 3(4.2mmol) were dissolved in nitromethane (50mL) and reacted at 60 ℃ for 4 hours. The product was centrifuged and washed with dichloromethane to give thiophene-bridged viologen 4. The reaction equation is as follows:
3) preparation of thiophene-bridged viologen Ionic liquids 5
Thiophene-bridged viologen 4(2.5mmol) dissolved in H 2 O (50mL), LiTFSI (12mmol) was added. The product was obtained by centrifugation, and the reaction equation was as follows:
electrochromic ionic gels were prepared using the thiophene-bridged viologen ionic liquids prepared in example 1:
ethyl acrylate, ethylene glycol dimethacrylate (0.68 mol%), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (1.16 mol%) were dissolved in toluene of equal volume, the solution was added to a PVDF mold of 1mm thickness, and placed under an ultraviolet lamp for reaction for 1 hour. And taking the polyethylacrylate film out of the grinding tool, and soaking the polyethylacrylate film in a toluene/n-hexane mixed solvent to remove residual reactants. And (3) placing the mono-network polyethylacrylate in a vacuum drying oven for drying at 80 ℃, and storing at room temperature for later use. Soaking mono-network polyethyl acrylate in a mixture of ethyl acrylate, ethylene glycol dimethacrylate (0.01 mol%) and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (0.01 mol%) for 24 hours, taking out, and placing under an ultraviolet lamp for reacting for one hour. The double-network polyethylacrylate is obtained after being placed in a vacuum drying oven at the temperature of 80 ℃ for 12 hours. Soaking double-network polyethylacrylate in an ethanol solution containing thiophene bridged viologen ionic liquid (100mg/mL) and 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (1/5V/V), taking out, and drying in a vacuum drying oven at 80 ℃ to obtain the electrochromic elastomer.
Electrochromic devices were prepared using the electrochromic elastomers worthy of example 1:
the electrochromic elastomer is placed between two pieces of ITO conductive glass or flexible ITO-PET conductive films, and the electrochromic device can be obtained without packaging.
The test results are shown in fig. 1-5, and fig. 1a and 1b respectively show the ultraviolet absorption spectrum of the viologen ionic liquid and the ultraviolet absorption spectrum of the viologen ionic liquid after being reduced by the zinc powder, and the ultraviolet absorption of the viologen ionic liquid after being reduced by the zinc powder at 570nm, 905nm and 1050nm is obviously enhanced, which indicates that the viologen generates cation free radicals after being reduced by the zinc powder. FIG. 1c is the fluorescence absorption and emission spectra of viologen ionic liquids, illustrating that the presence of thiophene group is that viologen has fluorescent properties, and that the material has a quantum yield of 86.12% and a fluorescence lifetime of 2.65 ns. Figure 1d is the electron paramagnetic resonance spectrum (EPR) of the viologen ion solution reduced by zinc powder, illustrating the formation of radical species upon reduction of the viologen ion solution by zinc powder.
Fig. 2a is a photograph of polyethylacrylate, electrochromic elastomer and electrochromic elastomer under uv light, and fig. 2b is a photograph of knotted electrochromic elastomer under tension, illustrating that the elastomer has very good tensile properties. Fig. 2c shows the adhesion of the elastomer to the skin and the plastic, which shows that the elastomer has very good adhesion to the skin and the plastic. FIGS. 2d and 2e are the mechanical properties of elastomers with different ionic liquid contents, illustrating that the elastomers have better tensile properties and mechanical strength, and the mechanical properties of the elastomers decrease with increasing ionic liquid content. FIG. 2f is a graph showing the change of the ionic liquid content in the elastomer with the soaking time of polyethylacrylate in the ionic liquid-containing solution, which shows that the ionic liquid content in the elastomer is saturated after soaking for 24 hours. FIG. 2e is a graph showing the change of the mass of an elastomer in a vacuum oven at 80 ℃ with time, which shows that the elastomer has very high stability and the quality of the elastomer does not change under vacuum and heating conditions.
Fig. 3a and 3b are schematic and physical diagrams of an encapsulation-free electrochromic device. Fig. 3c and 3d are color changes of rigid and flexible electrochromic devices before and after power-on. Fig. 3e is a cyclic voltammogram of a viologen ionic liquid, in which there are two sets of viologen-based redox peaks. FIG. 3f is the electrochemical spectrum of electrochromic device, new UV absorption peaks appear at 570nm, 910nm and 1055nm after-3.5V voltage is applied, indicating that viologen is reduced to cationic radical. Fig. 3g and 3h are the discoloration/fading time curves and coloring efficiencies of electrochromic devices, illustrating that the elastomers have shorter discoloration/fading times and better coloring efficiencies.
FIG. 4a shows the electrochromic condition of the elastomer after being placed in the air for different times, and the appearance and the discoloration condition of the elastomer are not obviously changed after the elastomer is placed for one year, which shows that the material has extremely high stability. FIGS. 4b and 4c are electrochromic cycling curves for a freshly prepared elastomer and an elastomer after one year of standing, illustrating the high cycling stability of the material.
Fig. 5a is the electrochromic condition of the stretchable electrochromic device in different stretching states, which illustrates that the electrochromic efficiency of the material is reduced as the stretching degree is increased, and this characteristic can be applied to manufacturing a visual sensing device. Fig. 5b is a graph of transmittance, current, voltage of elastomers in different tensile states during electrochromism, illustrating that the current through the material decreases with increasing degree of tension when the voltage is the same, and thus the efficiency of discoloration decreases. Fig. 5c is a schematic diagram of a simple visual sensor, in which a stretchable electrochromic device is fixed on a model finger, when a hand makes a fist, the elastic body is in a stretched state, the current is small, the electrochromic phenomenon is basically not observed, when the finger is straightened, the elastic body is in a relaxed state, the current is increased, and the color is changed. Fig. 5d shows the transmittance, current and voltage curves during electrochromic in stretched (e 300%) and relaxed (e 0%) states, wherein the electrochromic elastomer exhibits substantially unchanged transmittance in stretched (e 300%) state, undergoes electrochromic after relaxation (e 0%) and changes transmittance, and fades after changing voltage to 0V in relaxed (e 0%) state, under the condition of continuous application of 3.5V voltage. The result proves the application prospect of the material in the visual sensing field.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. The thiophene-bridged viologen ionic liquid is characterized by being a viologen ionic liquid containing a sulfur group element with a symmetrical structure or a viologen ionic liquid containing a sulfur group element with an asymmetrical structure;
the viologen ionic liquid containing the sulfur group elements with the symmetrical structure has the following structure:
wherein E is sulfur, selenium or tellurium; n is 1, 2, 3; x — Is Cl — 、Br — 、I — 、CF 3 SO 2 O — 、PF 6 — 、CH 3 COO — Or OTf — ；
The structure of the viologen ionic liquid containing the sulfur group elements with the asymmetric structure is as follows:
wherein R is an amine, alkyl or aryl group; e is sulfur, selenium or tellurium; n is 1, 2, 3; x — Is Cl — 、Br — 、I — 、CF 3 SO 2 O — 、PF 6 — 、CH 3 COO — Or OTf — 。
2. Use of the thiophene-bridged viologen ionic liquids of claim 1 in the preparation of electrochromic elastomers.
3. A method for preparing an electrochromic elastomer, comprising: preparing a polyethylacrylate-based polymer matrix by photo-initiated free radical polymerization, and then soaking the polyethylacrylate-based polymer matrix in an ethanol solution containing 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonimide salt and the thiophene-bridged viologen ionic liquid of claim 1 to prepare the electrochromic elastomer through a swelling process.
4. The method for preparing an electrochromic elastomer according to claim 3, characterized in that the polyethylacrylate-based polymer matrix is prepared by photo-initiated free radical polymerization, as follows:
dissolving ethyl acrylate, ethylene glycol dimethacrylate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide in toluene to obtain a mixed solution, adding the mixed solution into a PVDF (polyvinylidene fluoride) mould, placing the PVDF mould under an ultraviolet lamp for reacting for 1 hour, taking out a polyethylacrylate film from the mould, soaking the polyethylacrylate film in a toluene/n-hexane mixed solvent to remove residual reactants, and drying to obtain mono-network polyethylacrylate;
soaking the mono-network polyethyl acrylate in a mixed system of ethyl acrylate, ethylene glycol dimethacrylate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, standing for 24 hours, taking out, placing under an ultraviolet lamp for reacting for 1 hour, and drying to obtain a bi-network polyethyl acrylate matrix, namely a polyethyl acrylate-based polymer matrix.
5. The method for preparing an electrochromic elastomer according to claim 3, wherein the polyethylacrylate-based polymer matrix is immersed in an ethanol solution containing 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt and the thiophene-bridged viologen ionic liquid according to claim 1 for 24 hours and dried to obtain the electrochromic elastomer.
6. An electrochromic elastomer prepared by the method for preparing an electrochromic elastomer according to any one of claims 3 to 5.
7. Use of the electrochromic elastomer of claim 6 in the preparation of an encapsulation-free electrochromic device.
8. The use according to claim 7, for the preparation of an encapsulation-free electrochromic device, wherein the electrochromic elastomer is placed between two conductive substrates and the electrochromic device is obtained without encapsulation.
9. The use according to claim 8, wherein the conductive substrate is an ITO conductive glass or a flexible ITO-PET conductive film.
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| JP2009048142A (en) * | 2007-08-23 | 2009-03-05 | Sony Corp | Electrochromic compound, intermediate compound, method for manufacturing these compounds, and optical device using the electrochromic compound |
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| JP2009048142A (en) * | 2007-08-23 | 2009-03-05 | Sony Corp | Electrochromic compound, intermediate compound, method for manufacturing these compounds, and optical device using the electrochromic compound |
| CN113214235A (en) * | 2021-03-22 | 2021-08-06 | 西安交通大学 | Thienyl and selenophenyl viologen derivatives, and synthetic method and application thereof |
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