CN112500556B - Donor-receptor type electrochromic polymer, preparation method, electrochromic film and application - Google Patents
Donor-receptor type electrochromic polymer, preparation method, electrochromic film and application Download PDFInfo
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- CN112500556B CN112500556B CN201910789487.9A CN201910789487A CN112500556B CN 112500556 B CN112500556 B CN 112500556B CN 201910789487 A CN201910789487 A CN 201910789487A CN 112500556 B CN112500556 B CN 112500556B
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- 230000002441 reversible effect Effects 0.000 claims abstract description 4
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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- 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
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Abstract
The invention discloses a donor-receptor type electrochromic polymer, a preparation method, an electrochromic film and application, wherein the electrochromic polymer is the donor-receptor type electrochromic polymer, indacenodithiophene is a donor, 2,1,3-benzothiadiazole is a receptor, and four thiophenes are bridging units; according to the preparation method, stille coupling polymerization is adopted, and the polymer prepared by coupling polymerization has solubility and can be prepared into a high-purity high-quality polymer through post-treatment; the electrochromic film provided by the invention is prepared from the polymer, has stable P doping characteristic, can realize reversible conversion from infrared to transparent under the drive of lower potential, shows reasonable optical contrast, fast response speed and good color change stability, has potential application value in the field of electrochromic, and can be used for devices such as intelligent windows, electrochromic displays and self-adaptive camouflage.
Description
Technical Field
The invention relates to the technical field of synthesis and film forming of electrochromic materials, in particular to a donor-receptor type electrochromic polymer, a preparation method, an electrochromic film and application.
Background
Electrochromism refers to a phenomenon in which the absorbance or transmittance of a material reversibly changes under the action of an external electric field. The electrochromic material mainly comprises transition metal oxides (such as tungsten trioxide and the like), sandwich type coordination compounds (such as Prussian blue and the like), small organic molecules (such as viologen and the like) and conductive polymers. Compared with other types of color-changing materials, the conductive polymer has the advantages of designable structure, high response rate, high coloring efficiency, good stability and the like, and is a key research object in the field of electrochromic materials at present.
At present, a plurality of blue to transparent and yellow to transparent polymers are prepared by structural design of conductive polymers, although red to transparent polymers are reported, the types of the red to transparent polymers are still few, partial red display spectrums are difficult to cover, the color change stability is poor, and the application of related materials in the aspects of electrochromic display, material color matching and the like is limited.
Disclosure of Invention
The invention provides a donor-receptor type electrochromic polymer, a preparation method, an electrochromic film and application thereof, which are used for overcoming the defects that part of red display spectrum of a conductive polymer is difficult to cover, the color change stability is poor and the like in the prior art, realizing the conversion from red to transparent blue displayed by the film prepared from the electrochromic polymer, and having good contrast, response rate and stability.
In order to achieve the purpose, the invention provides a donor-acceptor type electrochromic polymer, wherein an indacenodithiophene unit in the electrochromic polymer is a donor, a 2,1,3-benzothiadiazole unit is an acceptor, and four thiophene units are bridging units; the structural formula of the electrochromic polymer is as follows:
wherein-C 6 H 13 Is n-hexyl; r is 1 Is C 6 -C 12 Alkyl groups of (a); n represents a polymerization degree, is a natural number, and is between 10 and 200.
In order to achieve the above object, the present invention also provides a method for preparing a donor-acceptor type electrochromic polymer, comprising the steps of:
s1: preparing 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer by bromination;
s2: the donor-acceptor type electrochromic polymer is prepared by Stille coupled polymerization.
In order to achieve the above object, the present invention further provides an electrochromic film formed by spraying the donor-acceptor type electrochromic polymer or the donor-acceptor type electrochromic polymer prepared by the above preparation method.
In order to achieve the above purpose, the present invention further provides an application of a donor-acceptor type electrochromic polymer in an electrochromic device, where the donor-acceptor type electrochromic polymer is the above donor-acceptor type electrochromic polymer or the donor-acceptor type electrochromic polymer prepared by the above preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. in the donor-receptor type electrochromic polymer provided by the invention, indacenodithiophene is used as a donor, 2,1,3-benzothiadiazole is used as a receptor, and four thiophenes are used as bridging units; the electrochromic polymer can be dissolved in common organic solvents such as chloroform, toluene, tetrahydrofuran, chlorobenzene and the like, can realize the preparation of a large-area polymer film by methods such as spraying, spin coating, printing and the like, and can realize the assembly of a large-area electrochromic device.
2. According to the preparation method of the donor-receptor type electrochromic polymer, the obtained electrochromic polymer has an electrochromic function after being sprayed into a film by controlling the proportion of reactants; meanwhile, stille coupling polymerization is adopted in the preparation method, and the polymer prepared by the coupling polymerization has solubility and can be prepared into a high-purity high-quality polymer through post-treatment.
3. The electrochromic film component provided by the invention is formed by the donor-acceptor type electrochromic polymer, the electrochromic film shows reversible conversion from red to transparent blue, the electrochromic film is red at normal state, the electrochromic film can show conversion from red to transparent blue when low-potential driving is given, and the electrochromic film returns to red when low-potential driving is removed; in addition, the electrochromic film has stable P doping characteristics, can realize reversible conversion from red to transparent under the drive of lower potential, shows reasonable optical contrast, quick response rate and good color change stability, has potential application value in the field of electrochromism, and can be used for devices such as intelligent windows, electrochromic displays, self-adaptive camouflage and the like.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a nuclear magnetic hydrogen spectrum of a donor-acceptor type electrochromic polymer provided in the examples;
FIG. 2 is a cyclic voltammogram of the donor-acceptor type electrochromic film provided in the examples;
FIG. 3 is a spectral absorption curve and a color photograph of the donor-acceptor type electrochromic polymer provided in the examples in chloroform;
FIG. 4 is a spectrum electrochemical spectrum of the electrochromic film provided in the example under different applied voltages;
FIG. 5 is a photograph showing color shifts of the electrochromic film provided in the example under different applied voltages;
fig. 6 is an electrochemical stability curve of the electrochromic film provided in the examples.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
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.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of the technical solutions by those skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination of the technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a donor-acceptor type electrochromic polymer, wherein an indacenodithiophene unit in the electrochromic polymer is a donor, a 2,1,3-benzothiadiazole unit is an acceptor, and four thiophene units are bridging units; the structural formula of the electrochromic polymer is as follows:
wherein-C 6 H 13 Is n-hexyl; r 1 Is C 6 -C 12 Alkyl groups of (a); n represents a polymerization degree, is a natural number, and is between 10 and 200.
The donor-acceptor type electrochromic polymer provided by the invention is a soluble polymer, and can be dissolved in common organic solvents such as chloroform, toluene, tetrahydrofuran, chlorobenzene and the like, so that the donor-acceptor type electrochromic polymer can be used for preparing an electrochromic film component.
The donor-acceptor type structure polymer refers to a polymer which simultaneously contains an electron donor and an electron acceptor, and the band gap of the polymer can be obviously reduced due to charge transfer between the electron donor and the electron acceptor, so that the donor-acceptor type structure polymer is often lower in band gap.
The invention also provides a preparation method of the donor-receptor type electrochromic polymer, which comprises the following steps:
s1: preparing 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer by bromination;
s2: the donor-acceptor type electrochromic polymer is prepared by Stille coupled polymerization.
The reaction route of the preparation method is as follows:
the method comprises the following specific steps:
s1: under inert atmosphere and no illumination condition, placing 4,7-di (4-alkyl-bithiophene) -2,1,3-benzothiadiazole and N-bromosuccinimide (NBS) solution in an organic solvent for bromination reaction and purification treatment to obtain 4,7-di (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer;
the purpose of the bromination reaction is to introduce Br into 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole, wherein the Br is introduced for the next polymerization reaction; n-bromosuccinimide is used to provide Br; the organic solvent is used for dissolving 4,7-di (4-alkyl-bithiophene) -2,1,3-benzothiadiazole and N-bromosuccinimide, so that bromination reaction of the two is facilitated.
The bromination reaction is carried out under the condition of no light, and Br (bromine) is prevented from being decomposed by light.
The inert atmosphere is preferably nitrogen or argon.
The purification treatment can lead to higher purity of the obtained monomer.
Preferably, the solvent of the N-bromosuccinimide solution is N, N-Dimethylformamide (DMF) or the like;
preferably, the organic solvent is chloroform, has good dissolving effect and is a common solvent.
Preferably, the mass ratio of the N-bromosuccinimide to 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole is 2.2-5, the yield is high and raw materials are not wasted under the proportional relationship, the mass ratio can be 2.2, 2.5, 2.8, 3, 3.5, 3.8, 4, 4.5, 5 and the like, and can be properly adjusted according to actual needs; the addition amount of the organic solvent is 20-30 ml, and the raw materials can be fully dissolved by adding a proper amount of the organic solvent, so that the waste of the solvent is avoided, and the cost is saved.
Preferably, the bromination reaction time is 22-48 h, and the temperature is 20-30 ℃; the proper reaction time ensures the reaction to be complete, and the proper temperature can improve the reaction efficiency without causing too much increase of the production cost.
S2: mixing 4,7-di (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer and indacenobithiophene di-stannide in an inert atmosphere under anhydrous and anaerobic conditions, adding a catalyst and an organic solvent, performing Stille coupling polymerization, and purifying to obtain the donor-acceptor type electrochromic polymer.
Step S2, reacting metallic tin with a halogen group; the Stille coupling polymerization has regular chain growth, less by-products and simple purification.
The inert atmosphere is preferably nitrogen or argon.
The reaction is carried out under anhydrous and anaerobic conditions, because oxygen and water cause reaction termination; the purification treatment can make the obtained product have higher purity.
Preferably, the organic solvent is toluene, has a good dissolving effect and is a common solvent; the catalyst is a palladium catalyst, the catalytic effect is obvious, other catalysts with better effect can be selected, such as palladium acetate and the like, the selected catalysts are different, the addition amount needs to be adjusted, and the catalyst is obtained according to the test result.
Preferably, palladium acetate or the like can be used as the palladium catalyst.
Preferably, the amount ratio of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer to indacenobithiophene distannide is 1, and the yield is high and raw materials are not wasted under the proportional relation; the addition amount of the catalyst is 6-16% of the amount of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer substance, preferably 6%, 8%, 10%, 12%, 14% and 16%, and can also be adjusted adaptively. The addition of a proper amount of palladium catalyst is beneficial to promoting the Stille coupling polymerization, and the addition amount is too small, so that the promotion effect on the Stille coupling polymerization is not ideal; too much amount of addition may adversely hinder the progress of Stille coupling polymerization.
Preferably, the time of the Stille coupling polymerization is 36-96 h, and the reflux temperature of the Stille coupling polymerization is above the boiling temperature of the used organic solvent. The proper reaction time ensures the reaction to be complete, and the proper temperature can improve the reaction efficiency without causing too much increase of the production cost.
The conductive polymer is mainly prepared by methods such as electrochemical polymerization, chemical oxidative polymerization, chemical coupling and the like. The electrochemical polymerization can directly deposit the polymer on the conductive substrate without secondary film-forming treatment, but the polymer prepared by the method is difficult to dissolve and difficult to prepare a large-area film; the polymer prepared by chemical oxidation polymerization has solubility, is easy for large-area film forming treatment, but the prepared polymer has wide molecular weight distribution and more impurities; the polymer prepared by chemical coupling has solubility, and can realize the preparation of high-purity and high-quality polymer by post-treatment. Therefore, the invention adopts a Stille coupling polymerization method for preparation, and the obtained product not only has solubility, but also can obtain the electrochromic polymer with high purity and high quality through post-treatment such as Soxhlet extraction and the like.
The invention also provides an electrochromic film which is formed by spraying the donor-receptor type electrochromic polymer or the donor-receptor type electrochromic polymer prepared by the preparation method.
Preferably, the electrochromic film is red at an external potential of 0.2V or less, and is transparent blue at 0.5V or more.
Preferably, the film forming method of the electrochromic film is as follows: dissolving an electrochromic polymer in an organic solvent to prepare a polymer solution with the concentration of 2-15 mg/ml, and coating the polymer solution on the surface of a conductive material to form an electrochromic film with the thickness of 100-800 nm and the absorbance of 0.6-1.2.
Preferably, the organic solvent may be chloroform, tetrahydrofuran, toluene, or the like.
Preferably, in order to ensure the uniformity of film formation, the preparation environment temperature of the electrochromic film is between 0 and 30 ℃.
The invention also provides an application of the donor-receptor type electrochromic polymer in an electrochromic device, wherein the donor-receptor type electrochromic polymer is the donor-receptor type electrochromic polymer or the donor-receptor type electrochromic polymer prepared by the preparation method.
The electrochromic polymer provided by the invention can be used for researching and developing electrochromic devices such as information display devices, electrochromic intelligent light-adjusting windows, no-glare reflectors, electrochromic information memories, color-changing mirrors, high-resolution photoelectric cameras and the like, and is used as the electrochromic layer of the electrochromic device.
Example 1
The embodiment provides a preparation method of a donor-acceptor type electrochromic polymer, which comprises the following steps:
s1: under the protection of nitrogen, 0.1mmol of 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole is dissolved in 20mL of chloroform in a 100mL double-mouth bottle, the double-mouth bottle is coated by tinfoil paper to achieve the effect of avoiding light, 0.3mmol of NBS is dissolved in 10mL of DMF (N, N-dimethylformamide) and is slowly injected into the double-mouth bottle through a syringe, the stirring reaction is carried out for 36h (at the temperature of 25 ℃), the reaction solution is washed by water, the organic phase and the water phase are separated, the organic phase is collected, the water phase is extracted twice by 20mL of dichloromethane, and the obtained extraction liquid is combined with the organic phase; drying the combined organic phases with anhydrous magnesium sulfate; loading the mixture to a silica gel column by adopting a dry method, wherein an eluting agent is a mixed solution of dichloromethane and n-hexane, collecting an eluent (the eluting agent after passing through the silica gel column and a dissolved target product), and drying the eluent in a nitrogen environment to obtain a dark red solid, namely 4,7-bis (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer with the yield of 73% (the general yield of the prior art is 40%); corresponding nuclear magnetic hydrogen spectrum 1 H-NMR(400MHz,CDCl 3 ):δ7.96(s,2H),7.83(s,2H),7.06(d,2H),6.98(d,2H),2.79(d,4H),1.71(s,4H),1.43(s,4H),1.34(s,8H),0.91(s,6H)。
S2: placing 0.1mmol of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole, 0.1mmol of indacenobithiophene di-stannide and 0.006mmol of palladium acetate in a 25mL double-neck bottle, pumping and injecting nitrogen, injecting 15mL of anhydrous toluene, pumping and injecting nitrogen, heating to 120 ℃ and performing Stille coupling polymerization for 72h, cooling to room temperature after the reaction is finished, dropping the reaction liquid into cold methanol for precipitation, filtering and drying the precipitate, performing Soxhlet extraction on the dried precipitate by using methanol, n-hexane and chloroform respectively, wherein each extraction time is 24h to finally obtain a chloroform extracting solution, concentrating the chloroform extracting solution to 15mL, dropping into cold methanol for precipitation to obtain a black solid, filtering and drying to obtain the target polymer: the yield of the donor-acceptor type electrochromic polymer is 82% (the prior art generally has 60%). As shown in figure 1 of the drawings, in which, 1 H-NMR(400MHz,CDCl 3 ):δ8.04(br,s,2H),7.82(br,s,2H),7.41(br,s,2H),7.34(br,s,2H),7.25(br,s,8H),7.20(br,s,2H),7.17(br,s,2H),7.10(br,s,8H),2.86(br,s,4H),2.57(br,s,8H),1.75(br,s,4H),1.60(br,s,8H),1.29-1.45(br,s,36H),0.87(br,s,18H)，Mw(Da):58300，Mn(Da):23000，PDI:2.54。
electrochemical performance and solution spectrum tests were performed on the donor-acceptor type electrochromic polymer prepared in this example:
the electrochromic polymer was dissolved in chloroform to make up a concentration of 2 x 10 -4 As shown in FIG. 3, the absorption curve and the photograph of the solution of mg/mL are shown in FIG. 3, because the electrochromic polymer contains a donor-acceptor structure, double absorption peaks exist at 463nm and 557nm, and because four thiophene units are introduced, the wave trough between the double absorption peaks is small, and the electrochromic polymer solution is dark red.
The embodiment provides an electrochromic film, and the preparation method comprises the following steps: the electrochromic polymer prepared in the embodiment is dissolved in chloroform to prepare a polymer solution of 2mg/ml, insoluble substances are removed through filtering by a filter tip, the polymer solution is placed in a spray gun, the air pressure is controlled to be 2MPa, the electrochromic film is formed by spraying on conductive glass, the absorbance of the electrochromic film is controlled to be about 0.8, the thickness of the electrochromic film is 300nm, and the polymer solution is placed in a vacuum drying oven to be dried in vacuum at 40 ℃ for standby after spraying.
1. And (3) carrying out electrochemical performance test on the electrochromic film:
three-electrode system and electrolyte: the method adopts a three-electrode system with an electrochromic film as a working electrode, a stainless steel sheet as a counter electrode and a calibrated silver wire as a reference electrode, and the supporting electrolyte is as follows: 0.2mol/L lithium perchlorate propylene carbonate solution.
The cyclic voltammetry curve of the electrochromic film is shown in fig. 2, and the scanning voltage range is-1.8V-1.2V. As can be seen from the figure, the electrochromic film can complete oxidation doping in the range of 0.3-1.0V and can complete reduction doping in the range of-0.7V to-1.8V.
2. And (3) carrying out photoelectric performance test on the electrochromic film:
three-electrode system and electrolyte: the method adopts a three-electrode system with an electrochromic film as a working electrode, a stainless steel sheet as a counter electrode and a calibrated silver wire as a reference electrode, and the supporting electrolyte is as follows: 0.2mol/L lithium perchlorate propylene carbonate solution.
The spectral absorption curve and the color conversion photograph of the electrochromic film under the action of different potentials are shown in fig. 4 and fig. 5 respectively. The single absorption peak of the electrochromic film in a neutral state is located at 483nm, and the absorption of the electrochromic film in a visible light area is weakened after oxidation, so that the electrochromic film respectively presents dark red (0V), transparent gray (0.4V) and transparent blue (0.8V). Electrochemical stability of the electrochromic film, as shown in fig. 6, the film electrical activity remained 74% after 500 cycles.
The embodiments show that the novel red to transparent blue donor-receptor type electrochromic polymer is prepared, has the advantages of easy dissolution, low driving potential, high oxidation state transparency, good stability and the like, can be used for color matching application of electrochromic materials, and has potential application prospects in the aspects of intelligent windows, electrochromic display and self-adaptive camouflage.
Example 2
The embodiment provides a preparation method of a donor-acceptor type electrochromic polymer, which comprises the following steps:
s1: under the protection of nitrogen, 0.1mmol of 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole is dissolved in 25mL of chloroform in a 100mL double-mouth bottle, the double-mouth bottle is coated by tinfoil paper to achieve the effect of avoiding light, 0.22mmol of NBS is dissolved in 10mL of DMF (N, N-dimethylformamide) and is slowly injected into the double-mouth bottle through a syringe, the reaction solution is stirred for 22 hours (at 30 ℃), the reaction solution is washed by water, the organic phase and the aqueous phase are separated, the organic phase is collected, the aqueous phase is extracted twice by 20mL of dichloromethane, and the obtained extraction liquid is combined with the organic phase; drying the combined organic phases with anhydrous magnesium sulfate; and (2) loading the mixture to a silica gel column by adopting a dry method, wherein an eluting agent is a mixed solution of dichloromethane and n-hexane, collecting an eluent (the eluting agent after passing through the silica gel column and a dissolved target product), and drying the eluent in a nitrogen environment to obtain a dark red solid, namely 4,7-di (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer.
S2: placing 0.1mmol of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole, 0.1mmol of indacenobithiophene di-stannide and 0.01mmol of palladium acetate in a 25mL double-mouth bottle, pumping and exchanging gas, injecting nitrogen, injecting 15mL of anhydrous toluene, pumping and exchanging gas and filling nitrogen, heating to 120 ℃ Stille coupling polymerization for 36h, cooling to room temperature after the reaction is finished, dropping the reaction liquid into cold methanol for precipitation, filtering and drying the precipitate, performing Soxhlet extraction on the dried precipitate by using methanol, n-hexane and chloroform respectively, wherein each extraction time is 24h, finally obtaining a chloroform extracting solution, concentrating the chloroform extracting solution to 15mL, dropping into cold methanol for precipitation to obtain a black solid, filtering and drying to obtain the target polymer: a donor-acceptor type electrochromic polymer.
Example 3
S1: under the protection of nitrogen, 0.1mmol of 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole is dissolved in 30mL of chloroform in a 100mL double-mouth bottle, the double-mouth bottle is coated by tinfoil paper to achieve the effect of avoiding light, 0.5mmol of NBS is dissolved in 10mL of DMF (N, N-dimethylformamide) and is slowly injected into the double-mouth bottle through a syringe, the stirring reaction is carried out for 48 hours (at the temperature of 20 ℃), the reaction solution is washed by water, the organic phase and the water phase are separated, the organic phase is collected, the water phase is extracted twice by 20mL of dichloromethane, and the obtained extraction liquid is combined with the organic phase; drying the combined organic phases with anhydrous magnesium sulfate; and (2) loading the mixture on a silica gel column by adopting a dry method, wherein the eluting agent is a mixed solution of dichloromethane and n-hexane, collecting eluent (the eluting agent after passing through the silica gel column and a dissolved target product), and drying the eluent in a nitrogen environment to obtain a dark red solid, namely 4,7-bis (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer.
S2: placing 0.1mmol of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole, 0.1mmol of indacenobithiophene distannide and 0.016mmol of palladium acetate in a 25mL double-neck bottle, pumping and injecting nitrogen, injecting 15mL of anhydrous toluene, pumping and injecting nitrogen, heating to 120 ℃ and performing Stille coupling polymerization for 96h, cooling to room temperature after the reaction is finished, dripping the reaction liquid into cold methanol for precipitation, filtering and drying the precipitate, respectively carrying out Soxhlet extraction on the dried precipitate by using methanol, n-hexane and chloroform for 24h each time to finally obtain a chloroform extract, concentrating the chloroform extract to 15mL, dripping into cold methanol for precipitation to obtain a black solid, filtering and drying to obtain the target polymer: a donor-acceptor type electrochromic polymer.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or any other related technical fields, which are directly or indirectly applied to the present invention, are included in the scope of the present invention.
Claims (6)
1. The application of a donor-acceptor type electrochromic polymer in preparing a red-to-transparent-blue reversible conversion electrochromic film is characterized in that the electrochromic film is formed by spraying the donor-acceptor type electrochromic polymer, and the preparation method of the donor-acceptor type electrochromic polymer comprises the following steps:
s1: under inert atmosphere and no illumination condition, placing 4,7-di (4-alkyl-bithiophene) -2,1,3-benzothiadiazole and N-bromosuccinimide solution in an organic solvent for bromination reaction and purification treatment to obtain 4,7-di (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer;
s2: mixing 4,7-di (5' -bromo-4-alkyl-bithiophene) -2,1,3-benzothiadiazole monomer with indacenobithiophene di-stannide in an inert atmosphere under anhydrous and anaerobic conditions, adding a catalyst and an organic solvent, performing Stille coupling polymerization, and performing purification treatment to obtain the donor-acceptor type electrochromic polymer;
in the electrochromic polymer, an indacenodithiophene unit is a donor, a 2,1,3-benzothiadiazole unit is an acceptor, and four thiophene units are bridging units; the structural formula of the electrochromic polymer is as follows:
wherein-C 6 H 13 Is n-hexyl; r 1 Is C 6 -C 12 Alkyl groups of (a); n represents a polymerization degree, is a natural number, and is between 10 and 200.
2. The use according to claim 1, wherein in S1, the organic solvent is chloroform;
in the S2, the organic solvent is toluene; the catalyst is a palladium catalyst.
3. The use according to claim 1,
in the S1, the mass ratio of the N-bromosuccinimide to 4,7-di (4-alkyl-bithienyl) -2,1,3-benzothiadiazole is 2.2-5; the adding amount of the organic solvent is 20-30 ml;
in the S2, the quantity ratio of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer to the material of indacenobithiophene distannide is 1; the addition amount of the catalyst is 6-16% of the amount of 4,7-di (5' -bromo-4-alkyl-bithienyl) -2,1,3-benzothiadiazole monomer substance.
4. The use according to claim 1,
in the S1, the bromination reaction time is 22-48 h, and the temperature is 20-30 ℃;
in the S2, the time of the Stille coupling polymerization is 36-96 h, and the reflux temperature of the Stille coupling polymerization is above the boiling point temperature of the used organic solvent.
5. The use according to claim 1, wherein the electrochromic film is red at an external potential of 0.2V or less and transparent blue at 0.5V or more.
6. The use according to claim 1, wherein the electrochromic film is formed by a method comprising: dissolving an electrochromic polymer in an organic solvent to prepare a polymer solution with the concentration of 2-15 mg/ml, and coating the polymer solution on the surface of a conductive material to form an electrochromic film with the thickness of 100-800 nm and the absorbance of 0.6-1.2.
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