CN111072932A - Black to transparent cross-linked electrochromic polymer and preparation method thereof - Google Patents
Black to transparent cross-linked electrochromic polymer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 2-ethylhexyl Chemical group 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
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- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims abstract description 8
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- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 claims description 7
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- ZUDCKLVMBAXBIF-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 claims description 4
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- VNJOEUSYAMPBAK-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;hydrate Chemical compound O.CC1=CC=CC=C1S(O)(=O)=O VNJOEUSYAMPBAK-UHFFFAOYSA-N 0.000 claims description 3
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- 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
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/135—Cross-linked structures
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- 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
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Abstract
The invention provides a black to transparent cross-linked electrochromic polymer and a preparation method thereof, wherein the preparation method comprises the following steps: 3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, a crosslinking agent, 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, 4, 7-dibromo-2, 1, 3-benzothiadiazole were mixed and reacted under reaction conditions. The invention uses a chemical crosslinking method to carry out the crosslinking of the electrochromic polymer, and the crosslinked polymer has higher structural stability and thermal stability. Meanwhile, the invention can conveniently control the crosslinking degree by controlling the proportion of the added crosslinking agent. In addition, when the degree of crosslinking is proper, the crosslinked electrochromic polymer can still be dissolved in a solvent, and feasibility is provided for post-treatment and use of the polymer.
Description
Technical Field
The invention relates to the technical field of electrochromic polymers, in particular to a black to transparent crosslinking type electrochromic polymer and a preparation method thereof.
Background
The electrochromic polymer is a polymer which can generate reversible oxidation reduction under the action of an electric field and shows reversible color change in appearance, and is one of conductive macromolecules. Conductive polymer molecules such as polythiophene, polypyrrole, polyacetylene and the like can be used as electrochromic materials. Compared with inorganic electrochromic materials using metal oxides (tungsten trioxide, nickel oxide, etc.) as the color-changing material, the electrochromic polymer has outstanding performances in response speed, preparation method, color diversity and coloring efficiency.
Among the many colors that can be selected, black to transparent electrochromic polymers have been a challenge in the field of material synthesis. In order to realize that the electrochromic polymer presents black in a natural state, the material must have uniform and wide absorption in a visible light range of 400 to 700 nanometers, and higher requirements are put on the design and synthesis of a polymer main chain structure. Meanwhile, it is also required to be soluble in a solvent so that the relevant electrochromic device can be produced by coating, spraying, or the like; has higher structural stability so as to be used in more complex environments.
Disclosure of Invention
The invention aims to provide a black to transparent crosslinking type electrochromic polymer and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the above object, the present invention provides a black to transparent crosslinked electrochromic polymer having a structural formula:
wherein m, n, o, p, m ', n', o 'and p' are natural integers of more than 0, and R is a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, an ester group or a straight chain or branched chain alkyl group with 1-20 carbon atoms, and can be the same or different.
In order to achieve the above object, the present invention provides a method for preparing the black to transparent crosslinked electrochromic polymer, comprising the steps of:
3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, a crosslinking agent, 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, 4, 7-dibromo-2, 1, 3-benzothiadiazole were mixed and reacted under reaction conditions.
As an improvement of the preparation method of the invention, the reaction conditions are as follows: adding palladium acetate, potassium carbonate, pivalic acid and 1-methyl-2-pyrrolidone, and reacting at 110-130 deg.C for 16-28h under the condition of continuous argon gas flow.
As an improvement of the preparation method of the invention, the method also comprises the following steps before the reaction: and vacuumizing the reaction environment, introducing argon for replacement, and repeating the steps for at least 3 times.
As an improvement of the preparation method of the present invention, the preparation method further comprises:
after the reaction was completed, the temperature was lowered to room temperature, and the reaction mixture was poured into a 1: 1 methanol/1M dilute hydrochloric acid aqueous solution by volume for precipitation.
As an improvement of the preparation method of the present invention, the precipitate is separated by means of filtration to obtain the black to transparent crosslinked electrochromic polymer.
As an improvement of the preparation method of the invention, the cross-linking agent is 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep ].
As an improvement of the preparation process of the present invention, the crosslinking agent is prepared by:
under the reaction condition, 3, 4-dimethoxythiophene, pentaerythritol, toluenesulfonic acid monohydrate and toluene are mixed and reacted; and removing redundant toluene in the product after the reaction, and purifying the product to obtain the cross-linking agent.
As an improvement of the preparation method of the invention, the reaction conditions are as follows: reflux at 110 ℃ for 24 hours and then cool to room temperature.
As an improvement of the preparation method of the invention, the step of removing the excessive toluene in the product after the reaction comprises the following steps: removing redundant toluene in the product after reaction by a rotary evaporator; the step of purifying the subsequent product comprises: the subsequent product was purified using a silica gel-loaded column with ethyl acetate/petroleum ether as solvent.
Has the advantages that:
compared with the prior art, the invention uses a chemical crosslinking method to perform crosslinking of the polymer, and the black to colorless electrochromic polymer after crosslinking has higher structural stability and thermal stability. Meanwhile, the invention can conveniently control the crosslinking degree by controlling the proportion of the added crosslinking agent, thereby controlling the molecular weight and the solubility. When the degree of crosslinking is appropriate, the crosslinked black to colorless electrochromic polymer can still be dissolved in a solvent, providing feasibility for post-treatment and use of the polymer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction equation of a preparation method of a comparative example black to transparent non-crosslinked electrochromic polymer;
FIG. 2 is a reaction equation of an embodiment of the method for controlling the molecular weight of a black-to-transparent crosslinked electrochromic polymer according to the present invention;
FIG. 3 is a graph showing the molecular weight and distribution of the polymer in the comparative example measured by gel permeation chromatography;
fig. 4 is a graph showing the molecular weight and distribution of the black to transparent cross-linked electrochromic polymer in example 1, measured by gel permeation chromatography;
fig. 5 is a molecular weight and distribution of the black to transparent cross-linked electrochromic polymer of example 2, measured by gel permeation chromatography;
FIG. 6 is a graph of weight percent versus temperature obtained by thermogravimetric analysis of the polymers obtained in examples 1 and 2;
FIG. 7 shows the absorption curves of the polymers obtained in examples 1 to 3 by an ultraviolet-visible spectrophotometer.
Detailed Description
The present invention is described in detail below with reference to various embodiments, but it should be understood that these embodiments are not intended to limit the present invention, and those skilled in the art should be able to make modifications and substitutions on the functions, methods, or structures of these embodiments without departing from the scope of the present invention.
The technical conception of the invention is as follows: by introducing the cross-linking agent with a conjugated structure similar to a monomer into the main chain of the polymer, the structural stability and the thermal stability of the polymer are improved while the photoelectric property of the polymer is not changed. The polymer solution formed by dissolving the prepared cross-linked electrochromic polymer can be prepared into a film in a coating mode and used for preparing large-area electrochromic devices
An embodiment of the present invention is based on the above technical idea to provide a black to transparent cross-linked electrochromic polymer. The structural formula of the black to transparent cross-linked electrochromic polymer is as follows:
wherein m, n, o, p, m ', n', o ', p' are natural integers of 0 or more, and R in the embodiment may be but not limited to EtHex (2-ethylhexyl).
An embodiment of the present invention provides a preparation method for the black-to-transparent cross-linked electrochromic polymer.
As shown in fig. 2, the preparation method of this embodiment includes the following steps:
3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, a crosslinking agent, 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, 4, 7-dibromo-2, 1, 3-benzothiadiazole were mixed and reacted under reaction conditions.
The preparation method uses a chemical crosslinking method to perform crosslinking of the electrochromic polymer, and the crosslinked polymer has higher structural stability and thermal stability. Meanwhile, the invention can conveniently control the crosslinking degree by controlling the proportion of the added crosslinking agent. In addition, when the degree of crosslinking is proper, the crosslinked electrochromic polymer can still be dissolved in a solvent, and feasibility is provided for post-treatment and use of the polymer.
Wherein the adopted cross-linking agent is 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobi [ thieno [3, 4-b ] [1, 4] dioxep ], and the cross-linking agent is a monomer with a plurality of reactive points and does not destroy the conjugation continuity in a polymer system after polymerization. Meanwhile, the crosslinking degree of the black to transparent crosslinking type electrochromic polymer can be controlled by controlling the dosage of the crosslinking agent.
The cross-linking agent is prepared by the following method: under the reaction condition, 3, 4-dimethoxythiophene, pentaerythritol, toluenesulfonic acid monohydrate and toluene are mixed and reacted; and removing redundant toluene in the product after the reaction, and purifying the product to obtain the cross-linking agent.
Wherein the reaction conditions are as follows: reflux at 110 ℃ for 24 hours and then cool to room temperature. The step of removing the excessive toluene in the product after the reaction comprises: removing redundant toluene in the product after reaction by a rotary evaporator; the step of purifying the subsequent product comprises: the subsequent product was purified using a silica gel-loaded column with ethyl acetate/petroleum ether as solvent.
The following describes a technical scheme of a preparation method of a black to transparent cross-linked electrochromic polymer by combining a comparative example and different examples.
Comparative example [ Synthesis of comparative sample without Cross-linker ]
A three-necked round bottom flask was charged with 3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep (15g, 34.038mmol, 0.998eq), 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep (13.241g, 22.125mmol, 0.65eq), 4, 7-dibromo-2, 1, 3-benzothiadiazole (3.502g, 11.913mmol, 0.35eq), palladium acetate (0.153g, 0.681mmol, 0.02eq), potassium carbonate (12.232g, 88.500mmol, 2.6eq), pivalic acid (1.043g, 10.211mmol, 0.3eq), and 1-methyl-2-pyrrolidone (280 mL). The reaction flask was evacuated for 10 minutes and then replaced by argon gas. This evacuation-argon process was repeated 3 times. The reaction flask was then placed in a 120 ℃ oil bath and allowed to react for 24 hours with a continuous flow of argon gas therethrough. After cooling to room temperature, the reaction mixture was poured into a 1: 1 by volume methanol/1M aqueous dilute hydrochloric acid solution for precipitation, and a large amount of black solid was found to precipitate. The mixture was filtered and separated using a buchner funnel to give 19.3 g of black to clear electrochromic polymer in 73.5% yield.
Example 1 [ crosslinker molar ratio one thousandth of black to clear crosslinked electrochromic Polymer prepared ]
A500 mL three-necked flask was charged with 3, 4-dimethoxythiophene (50g, 346.8mmol), pentaerythritol (23.61g, 173.4mmol), p-toluenesulfonic acid monohydrate (6.6g, 34.7mmol), and toluene (700 mL). Reflux at 110 ℃ for 24 hours, then cool to room temperature to give a dark brown mixture. Excess toluene was removed on a rotary evaporator and purified using a silica gel-loaded column chromatography with ethyl acetate/petroleum ether (3: 7 vol.) as solvent to give 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep ]67 g as a white solid in 65.6% yield.
One thousandth of the molar ratio of crosslinker was added to a three-necked round bottom flask charged with 3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep-ane (15g, 34.038mmol, 0.998eq), 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep-ne ] (0.01g, 0.034mmol, 0.001eq), 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep-ne (13.27g, 22.169mmol, 0.65eq), 4, 7-dibromo-2, 1, 3-benzothiadiazole (3.51g, 11.937mmol, 0.35eq), palladium acetate (0.153g, 0.682mmol, 0.02eq), potassium carbonate (12.256g, 88.677mmol, 2.6eq), pivalic acid (1.045g, 10.232mmol, 0.3eq) and 1-methyl-2-pyrrolidone (280 mL). The reaction flask was evacuated for 10 minutes and then replaced by argon gas. This evacuation-argon process was repeated 3 times. The flask was then placed in a 110 ℃ oil bath and allowed to react for 16 hours with a continuous flow of argon gas therethrough. After cooling to room temperature, the reaction mixture was poured into a 1: 1 by volume methanol/1M aqueous dilute hydrochloric acid solution for precipitation, and a large amount of black solid was found to precipitate. The mixture was filtered and separated using a buchner funnel to give 24.1 g of black to clear electrochromic polymer in 93.1% yield.
Example 2 [ molar ratio of crosslinking agent three thousandths of a black to transparent crosslinked electrochromic Polymer prepared ]
The procedure for the preparation of the crosslinking agent was the same as in example 1.
Three thousandths of a polymer, crosslinker, molar ratio, was charged to 3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep (15g, 34.038mmol, 0.994eq), 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep ] (0.03g, 0.103mmol, 0.003eq), 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep (13.321g, 22.258mmol, 0.65eq), 4, 7-dibromo-2, 1, 3-benzothiadiazole (3.523g, 11.985mmol, 0.35eq), palladium acetate (0.154g, 0.685mmol, 0.02eq), potassium carbonate (12.305g, 89.034mmol, 2.6eq), pivalic acid (1.049g, 10.273mol, 0.3eq) and 1-methyl-2-pyrrolidone (280 mL). The reaction flask was evacuated for 10 minutes and then replaced by argon gas. This evacuation-argon process was repeated 3 times. The flask was then placed in a 120 ℃ oil bath and allowed to react for 22 hours with a continuous flow of argon gas therethrough. After cooling to room temperature, the reaction mixture was poured into a 1: 1 by volume methanol/1M aqueous dilute hydrochloric acid solution for precipitation, and a large amount of black solid was found to precipitate. The mixture was filtered and separated using a buchner funnel to give 24.4 g of a black to clear electrochromic polymer at 94.2% yield
Example 3 [ crosslinker molar ratio five thousandths of a black to transparent crosslinked electrochromic Polymer prepared ]
Five thousandths of a polymer as crosslinker molar ratio was charged into a three-necked round bottom flask with 3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep-ane (15g, 34.038mmol, 0.990eq), 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep-ne ] (0.051g, 0.172mmol, 0.005eq), 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep-ne (13.375g, 22.348mmol, 0.65eq), 4, 7-dibromo-2, 1, 3-benzothiadiazole (3.538g, 12.034mmol, 0.35eq), palladium acetate (0.154g, 0.688mmol, 0.02eq), potassium carbonate (12.355g, 89.394mmol, 2.6eq), pivalic acid (1.053g, 10.315mmol, 0.3eq) and 1-methyl-2-pyrrolidone (280 mL). The reaction flask was evacuated for 10 minutes and then replaced by argon gas. This evacuation-argon process was repeated 3 times. The reaction flask was then placed in an oil bath at 130 ℃ and allowed to react for 28 hours with a continuous flow of argon. After cooling to room temperature, the reaction mixture was poured into a 1: 1 by volume aqueous solution of methanol/1M dilute hydrochloric acid and precipitated, and a large amount of black solid was found to precipitate. The mixture was filtered and separated using a buchner funnel to give 24.8 g of black to clear electrochromic polymer in 95.8% yield.
As shown in Table 1, it is understood from the comparative examples and examples 1 and 2 that the reaction results are obtained when different proportions of the crosslinking agent are used. It can be seen that as the amount of the crosslinking agent used increases, the polymerization reaction yield increases, i.e., the reaction yield increases. At the same time, a significant increase in the molecular weight of the polymer also occurs.
| Ratio of crosslinking agent | Reaction yield | Mn (Dalton) | Mw (Dalton) | PDI | |
| Comparative example | 0 | 70％ | 18573 | 29738 | 1.6 |
| Example 1 | 0.1％ | 81％ | 32680 | 53577 | 1.6 |
| Example 2 | 0.3％ | 87％ | 50485 | 107999 | 2.1 |
| Example 3 | 0.5％ | 92％ | Not measured | Not measured | Not measured |
TABLE 1
Further, the molecular weights and the distributions of the polymers obtained in examples 1 to 3 were measured by gel permeation chromatography, respectively. Wherein, the reference sample is styrene, the solvent is tetrahydrofuran, the ordinate in the figure is the detected intensity, and the abscissa is the retention time. As can be seen from fig. 3 to 5, as the amount of the crosslinking agent used increases, the molecular weight of the black to transparent crosslinked electrochromic polymer also increases significantly.
Meanwhile, with respect to examples 1 and 2, the resulting polymers were also subjected to thermogravimetric analysis. As can be seen from FIG. 6, with the addition of the crosslinking agent, the stability of the polymer is significantly improved, and the temperature corresponding to 5% of the weight loss by heat is increased by 25 ℃.
In addition, UV measurements were performed on the polymers prepared in examples 1-3. The polymer was dissolved in chloroform to prepare a 0.2mg/ml solution, and the absorption curve of the polymer in the solution was measured using an ultraviolet-visible spectrophotometer. As a result, as shown in FIG. 7, the polymer solution uniformly and evenly absorbs between 450 nm and 650 nm, and the absorption peaks are nearly overlapped, so that it can be seen that the addition of the cross-linking agent does not greatly affect the absorption of the polymer in the ultraviolet and visible light portions, and the prepared polymer solution appears as a nearly black liquid in appearance.
In conclusion, the invention uses a chemical crosslinking method to perform crosslinking on the electrochromic polymer, and the crosslinked polymer has higher structural stability and thermal stability. Meanwhile, the invention can conveniently control the crosslinking degree by controlling the proportion of the added crosslinking agent. In addition, when the degree of crosslinking is proper, the crosslinked electrochromic polymer can still be dissolved in a solvent, and feasibility is provided for post-treatment and use of the polymer.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A black to transparent crosslinked electrochromic polymer, wherein the structural formula of the black to transparent crosslinked electrochromic polymer is as follows:
wherein m, n, o, p, m ', n', o 'and p' are natural integers of more than 0.
2. A method for preparing the black to transparent crosslinked electrochromic polymer according to claim 1, comprising the steps of:
3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, a crosslinking agent, 6, 8-dibromo-3, 3-bis [ [ (2-ethylhexyl) oxy ] methyl ] -3, 4-dihydro-2H-thieno [3, 4-b ] [1, 4] dioxep le, 4, 7-dibromo-2, 1, 3-benzothiadiazole were mixed and reacted under reaction conditions.
3. The method for preparing a black-to-transparent crosslinked electrochromic polymer according to claim 2, wherein the reaction conditions are: adding palladium acetate, potassium carbonate, pivalic acid and 1-methyl-2-pyrrolidone, and reacting at 110-130 deg.C for 16-28h under the condition of continuous argon gas flow.
4. The method of preparing a black-to-transparent crosslinked electrochromic polymer according to claim 2, further comprising, before the reacting: and vacuumizing the reaction environment, introducing argon for replacement, and repeating the steps for at least 3 times.
5. The method of preparing a black-to-transparent crosslinked electrochromic polymer according to claim 2, further comprising:
after the reaction was completed, the temperature was lowered to room temperature, and the reaction mixture was poured into a 1: 1 methanol/1M dilute hydrochloric acid aqueous solution by volume for precipitation.
6. The method of claim 5, wherein the black-to-transparent crosslinked electrochromic polymer is obtained by separating precipitates by filtration.
7. The method of claim 2, wherein the crosslinking agent is 2, 2 ', 4, 4 ' -tetrahydro-3, 3 ' -spirobis [ thieno [3, 4-b ] [1, 4] dioxep ].
8. The method for preparing a black to transparent cross-linked electrochromic polymer according to claim 7, wherein the cross-linking agent is prepared by:
under the reaction condition, 3, 4-dimethoxythiophene, pentaerythritol, toluenesulfonic acid monohydrate and toluene are mixed and reacted; and removing redundant toluene in the product after the reaction, and purifying the product to obtain the cross-linking agent.
9. The method for preparing a black to transparent crosslinked electrochromic polymer according to claim 8, wherein the reaction conditions are: reflux at 110 ℃ for 24 hours and then cool to room temperature.
10. The method of claim 8, wherein the step of removing the excessive toluene from the resultant product comprises: removing redundant toluene in the product after reaction by a rotary evaporator; the step of purifying the subsequent product comprises: the subsequent product was purified using a silica gel-loaded column with ethyl acetate/petroleum ether as solvent.
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