CN115197400A - Water-alcohol soluble conjugated polyelectrolyte electrochromic polymer and application thereof - Google Patents
Water-alcohol soluble conjugated polyelectrolyte electrochromic polymer and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 71
- 229920000867 polyelectrolyte Polymers 0.000 title abstract description 5
- 229920006254 polymer film Polymers 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001347 alkyl bromides Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 229960001701 chloroform Drugs 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention discloses a water-alcohol soluble conjugated polyelectrolyte electrochromic polymer and an electrochromic polymer film. The invention also provides an electrochromic polymer film prepared from the electrochromic polymer, which can realize stable and reversible conversion from neutral state coloring to oxidation state high transmission under low voltage and has potential application value in the fields of displays, intelligent windows, electronic paper and the like.
Description
Technical Field
The invention relates to a water-alcohol soluble conjugated polyelectrolyte electrochromic polymer, a preparation method thereof and application thereof in preparing an electrochromic polymer film.
Background
"Electrochromism" (EC) refers to a phenomenon that optical properties of a material, such as transmittance, reflectance, absorption and the like, are stably and reversibly changed under the action of an external electric field, and macroscopically shows reversible changes in color and transparency.
Electrochromic materials are mainly divided into inorganic electrochromic materials, organic micromolecular electrochromic materials and polymer electrochromic materials. Among them, the polymer electrochromic material (PEC) has a great application value in the fields of smart windows, flat displays, information labels and the like due to its characteristics of easy structure modification, controllable energy band, good processability, excellent electrochromic comprehensive performance and the like, and is widely researched. However, most of the existing PEC materials are soluble in organic solution, have certain harm to the environment and are not beneficial to practical application.
In recent years, water-alcohol soluble polymers have attracted attention because they can be processed with green solvents (water/alcohol). Researchers have made polymers soluble in water/alcohol solvents by introducing polar groups on the side chains of the polymer. These polymers are composed of two parts, a hydrophobic polymer backbone and hydrophilic side chains, respectively. Currently, research on hydroalcoholic processed PEC materials has focused primarily on sulfonates and carboxylates. However, there have been no reports on PEC materials processed with ammonium salts like hydroalcoholic. Moreover, N in the ammonium salt and O in the ITO can form hydrogen bond interaction force, dipole moment between the material and an interface can be reduced, and meanwhile, a polymer side chain contains bromide ions, so that the oxidation voltage of the material can be further reduced. Therefore, the development of PEC materials processed by ammonium salt water-soluble alcohol has certain significance for researching the basic properties and the application of the ammonium salt materials in electrochromism.
Disclosure of Invention
In order to further improve the water-alcohol solubility of the electrochromic polymer and reduce the oxidation voltage of the electrochromic polymer, the invention provides a water-alcohol soluble conjugated polyelectrolyte electrochromic polymer and a preparation method and application thereof.
It is a first object of the present invention to provide an electrochromic polymer having ammonium salt side chains and good solubility in hydroalcoholic solvents.
A second object of the present invention is to provide a method for preparing an electrochromic polymer.
It is a third object of the present invention to provide an electrochromic polymer film.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the present invention provides an electrochromic polymer of formula (I),
wherein a is 0 or 1; a1 is 0 or 1; m is an integer of 3 to 14; x is a group having redox activity;
the X is one of the following groups:
the number average molecular weight Mn of the electrochromic polymer is = 2000-200000, the molecular weight is controlled by the polymerization reaction time, and the polydispersity D = 1.0-5.0.
Preferably, the number average molecular weight Mn of the electrochromic polymer is from 10000 to 50000.
In a second aspect, the present invention provides a method for preparing an electrochromic polymer represented by formula (I), wherein the method comprises: reacting the polymer shown in the formula 1 with alkyl bromide in an organic solvent at 25-80 ℃ (preferably 60 ℃) for 24-168h (preferably 120 h), adding a benign solvent into the reaction every 4-10h (preferably 8 h) (aiming at dissolving the precipitated but incompletely reacted ionized polymer to completely ionize the polymer), and after the reaction is finished, carrying out post-treatment on the obtained mixed solution to obtain the electrochromic polymer shown in the formula (I); the alkyl bromide is one of methyl bromide or ethyl bromide; the organic solvent is one or a mixed solvent of more than two of toluene, chloroform, tetrahydrofuran, dimethylformamide and dimethylacetamide; the benign solvent is one or a mixed solvent of methanol and DMSO (preferably methanol); the mass ratio of the polymer represented by the formula 1 to the alkyl bromide is 1 to 10 (preferably 1;
wherein a is 0 or 1; m is an integer of 3 to 14; x is a group having redox activity;
the X is one of the following groups:
preferably, the volume of the organic solvent is 1 to 20L/mol (preferably 10L/mol) based on the amount of the substance of the polymer represented by formula 1.
Preferably, the total volume of the benign solvent is 100 to 300L/mol (preferably 200L/mol) based on the amount of the substance of the polymer represented by formula 1.
Preferably, the post-treatment comprises the following steps: the mixed solution is concentrated (for the purpose of facilitating the subsequent solid precipitation, the volume is up to half in the embodiment of the invention, but the skilled person knows that the purpose can be achieved within a proper range), the rest mixture is poured into a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the mixed solvent is 0.5-1.5 (preferably 1).
In a third aspect, the invention provides an application of an electrochromic polymer shown in a formula (I) in preparing an electrochromic polymer film.
Preferably, the electrochromic polymer film is obtained by processing the electrochromic polymer into a film from a solution.
As a further preferred method, the electrochromic polymer film is prepared as follows: dissolving an electrochromic polymer shown in a formula (I) in a solvent to obtain a polymer solution, and coating the polymer solution on a conductive substrate to obtain the electrochromic polymer film. More preferably, the solvent is one or a mixture of two or more of methanol, ethanol and water.
Further, the concentration of the electrochromic polymer shown in the formula (I) in the polymer solution is 5mg/mL.
In the invention, the coating mode can be spraying, spin coating, screen printing and the like. The conductive substrate can be ITO glass, FTO glass, an ITO-PET substrate, an FTO-PET substrate and the like.
The electrochromic polymer film obtained by the invention has potential application value in the fields of intelligent windows, displays, electronic paper and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer has ammonium salt side chains, has good solubility in environment-friendly solvents such as water alcohol and the like, and can realize large-area preparation of the film material by an environment-friendly solution processing method.
(2) The polymers of the present invention have ammonium side chains that lower the electrochromic onset voltage of the polymer compared to alkyl side chains and ammonium-based side chains.
(3) The polymer film prepared by the invention can realize stable and reversible transformation from neutral state coloring to oxidation state high transmission under low voltage, and has potential application value in the fields of displays, intelligent windows, mobile phone shells and the like.
Drawings
FIG. 1: the side chain used for comparison in the patent is the structural formula of a polymer of alkyl and amine;
FIG. 2 is a schematic diagram: optical absorption of the polymer film prepared in example 1 at different voltages;
FIG. 3: the curve of the transmittance over time at specific wavelengths for a multi-potential step from 0 to 1.1V for the polymer film prepared in example 1;
FIG. 4 is a schematic view of: CV of the polymer film prepared in example 1 and the polymer film whose side chains are alkyl and amine as a comparative example thereof.
Detailed Description
The technical solution of the present invention is further described below with specific examples, but the scope of the present invention is not limited thereto.
Example 1
The synthesis and molecular structure of the conjugated polymers used are shown below:
p1 (0.097g, 1eq.) and bromoethane (0.545g, 50eq.) were added to 10mL of a chloroform solution and reacted at 60 ℃ for 120 hours, with 1.3mL of methanol added every 8 hours during the reaction. After the reaction is finished, the mixed solution is decompressed and concentrated, and then poured into 50ml of mixed solution of ethyl acetate and n-hexane (volume ratio is 1.
Preparation of polymer film:
and dissolving the polymer in methanol, and spraying the solution on an ITO substrate to prepare a membrane, wherein the concentration of the solution is 5mg/mL, and the spraying usage amount is 0.5mL.
Electrochromic properties of the resulting polymer films: the electrochemical workstation and the uv-vis spectrophotometer were used in combination to test the uv-vis absorption of the prepared film at different voltages, the relationship between the transmittance at specific wavelength and time and the stability of the film at step voltage in 0.1M tetrabutylammonium hexafluorophosphate/dichloromethane solution, respectively, and the data processing results are shown in fig. 2 and 3. It can be seen from FIG. 2 that the polymer film had a magenta color in a neutral state at 0V and a high transmission state after oxidation at a voltage of 1.1V. From FIG. 3, it can be seen that the film has a contrast ratio of 42.6% at 560 nm. The film coloration time and fading time were 2.4s and 1.2s, respectively. FIG. 4 shows CV of electrochromic conjugated polymer with three different side chains, where P1 is the target polymer prepared in this patent, P2 is the polymer with alkyl side chain, and P3 is the polymer with amine side chain (formula shown in FIG. 1). As can be seen from CV of the three polymers, the target polymer has ammonium salt side chain, and N in the ammonium salt and O in ITO can form hydrogen bond interaction force, so that the dipole moment between the material and the interface can be reduced. And secondly, the side chain contains bromide ions, so that the oxidation voltage of the material is reduced. Therefore, the introduction of ammonium salt side chains and bromide ions greatly reduces the discoloration initiation oxidation voltage of the electrochromic polymer.
The synthesis of the precursor polymer P3, illustrated by way of comparison and synthesizing P1, is as follows:
reference to the synthesis of monomeric FN [ adv. Mater.2011,23,1665-1669]The synthesis process of P3 is as follows: FN (0.634g, 1eq.) and PBTP (0.500g, 1eq.) were added to a solution of pivalic acid (30mg, 0.3eq.) and cesium carbonate (0.812g, 2.5eq.) in 5ml of THF, and finally ligand P (o-MeOPh) 3 (10mg, 0.03eq.) and Pd (dba) as a catalyst 3 . CHCl 3 (30mg, 0.03eq.) and reacted at 80 ℃ for 24 hours. After the reaction is finished, pouring the solution into 200ml of methanol, filtering, drying a filter cake, sequentially extracting with methanol, acetone, hexane and chloroform, collecting the polymer dissolved in the chloroform, and spin-drying. Polymer GPC test results (Mn =12.2kda, d = 2.01).
The synthesis and molecular structure of P2 for comparison in the examples are shown below:
f (0.492g, 1eq.) and PBTP (0.500g, 1eq.) were added to a solution of 5ml of THF containing pivalic acid (30mg, 0.3eq.) and cesium carbonate (0.812g, 2.5eq.), and finally ligand P (o-MeOPh) 3 (10mg, 0.03eq.) and catalyst Pd (dba) 3.CHCl3 (30mg, 0.03eq.) were added and reacted at 80 ℃ for 24 hours. After the reaction is finished, pouring the solution into 200ml of methanol, filtering, taking a filter cake, drying, sequentially carrying out Soxhlet extraction by using methanol, acetone, hexane and trichloromethane, collecting a polymer dissolved in the trichloromethane, and carrying out spin drying. Polymer GPC test results (Mn =39.9kda, d = 2.66).
Preparation of polymer film:
and dissolving the P2 and P3 polymers in chloroform, and spraying the solution with the concentration of 5mg/ml on an ITO substrate to prepare a film, wherein the volume of the solution taken once is 0.5ml.
Electrochromic properties of the resulting polymer films: the CV curves of the prepared films were tested in a 0.1M tetrabutylammonium hexafluorophosphate/acetonitrile solution using an electrochemical workstation and compared to P1.
Claims (10)
1. An electrochromic polymer of formula (I),
wherein a is 0 or 1; a1 is 0 or 1; m is an integer of 3 to 14;
the X is one of the following groups:
the number average molecular weight Mn of the electrochromic polymer is between 2000 and 200000.
2. Electrochromic polymer according to formula (I) according to claim 1, characterized in that: the number average molecular weight Mn of the electrochromic polymer is = 10000-50000.
3. A process for the preparation of an electrochromic polymer of formula (I) according to claim 1, characterized in that the process is: reacting the polymer shown in the formula 1 with alkyl bromide in an organic solvent at 25-80 ℃ for 24-168h, adding a benign solvent into the reaction every 4-10h, and after the reaction is finished, carrying out post-treatment on the obtained mixed solution to obtain the electrochromic polymer shown in the formula (I); the alkyl bromide is one of methyl bromide or ethyl bromide; the organic solvent is one or a mixed solvent of more than two of toluene, chloroform, tetrahydrofuran, dimethylformamide and dimethylacetamide, and the benign solvent is one or a mixed solvent of two of methanol and DMSO; the mass ratio of the polymer shown in the formula 1 to the alkyl bromide is 1;
wherein a is 0 or 1; m is an integer of 3 to 14;
the X is one of the following groups:
4. a process for the preparation of an electrochromic polymer of formula (I) according to claim 3, characterized in that: the volume of the organic solvent is 1-20L/mol based on the substance amount of the polymer shown in formula 1.
5. A process for the preparation of an electrochromic polymer of formula (I) according to claim 3, characterized in that: the total volume of the benign solvent is 100 to 300L/mol based on the amount of the substance of the polymer represented by formula 1.
6. A process for the preparation of an electrochromic polymer of formula (I) according to claim 3, characterized in that the post-treatment is: and (3) concentrating the mixed solution, pouring the residual mixture into a mixed solvent of n-hexane and ethyl acetate with the volume ratio of 0.5-1.5, filtering, taking a filter cake, and drying to obtain the electrochromic polymer shown in the formula (I).
7. Use of an electrochromic polymer of formula (I) according to claim 1 for the preparation of electrochromic polymer films.
8. The use of claim 7, wherein: the electrochromic polymer film is obtained by processing the electrochromic polymer into a film through a solution.
9. The use of claim 8, wherein: the electrochromic polymer film is prepared by the following method: dissolving an electrochromic polymer shown in a formula (I) in a solvent to obtain a polymer solution, and coating the polymer solution on a conductive substrate to obtain an electrochromic polymer film; the solvent is one or a mixed solvent of more than two of methanol, ethanol and water.
10. The use of claim 9, wherein: the coating mode is spray coating, spin coating or screen printing.
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| CN114349937A (en) * | 2021-12-31 | 2022-04-15 | 浙江工业大学 | Water-alcohol-soluble electrochromic polymer and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUANG, F. ET AL.: "Novel Electroluminescent Conjugated Polyelectrolytes Based on Polyfluorene" * |
| HUANG, F. ET AL.: "Water/alcohol soluble conjugated polymers as highly efficient electron transporting/injection layer in optoelectronic devices" * |
| WANG, H.ET AL.: "A Water-Soluble π-Conjugated Polymer with up to 100 mg • mL−1 Solubility" * |
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Application publication date: 20221018 |