CN107814917B - Hydrogen bond crosslinking intrinsic stretchable electrochromic polymer and preparation method thereof - Google Patents
Hydrogen bond crosslinking intrinsic stretchable electrochromic polymer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
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Abstract
The invention discloses a hydrogen bond crosslinking intrinsic stretchable electrochromic polymer, which comprises a color-changing functional group and a hydrogen bond crosslinking stretchable group; the color-changing functional group is obtained by one step of Stille coupling reaction or Suzuki coupling reaction by taking 3, 4-ethylenedioxythiophene as a donor unit and a five-membered heterocyclic compound with electron deficiency performance or an aromatic compound as an acceptor group; the hydrogen bond crosslinking stretchable group is composed of pyridine-dicarboxamide derivatives or bipyridine-dicarboxamide derivatives. The invention designs and synthesizes a series of hydrogen bond crosslinking intrinsic stretchable electrochromic new materials, and provides certain theoretical guidance, materials and technical support for synthesis of stretchable electrochromic materials and research of devices.
Description
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to a hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material based on pyridine-2, 6-diamides (PDCAs) or bipyridine-diamides (DPDCCAs) groups and a preparation method thereof
Background
The flexible intelligent device is the mainstream development direction of the current electronic products, the market development prospect is huge, and the market scale is estimated to be far more than 200 billion dollars in 2020. Electrochromic materials, as one of important functional materials of display devices and parts of wearable electronic equipment, refer to energy-saving materials which can be subjected to double injection, extraction or redox reaction of electrons and ions under the action of a weak electric field, so that the color of the materials can be subjected to reversible continuous change. The material has wide application prospect in various fields, such as intelligent energy-saving windows, no-glare reflectors, low-energy-consumption display devices, information display and storage, electronic paper, color-changing skin and the like. As a representative of the next generation of electronic devices, the development of flexible display and wearable electronic devices has put higher demands on the stretchable performance, and there is an urgent need for researchers to develop stretchable electrochromic devices capable of adapting to a certain stress and maintaining excellent performance in deformation as soon as possible.
Stretchable electrochromic devices have attracted attention in recent years, and the preparation of high performance stretchable electrochromic materials is a key issue. The stretchability is an important characteristic of the next generation of electrochromic devices, however, the research challenge of the stretchability of the devices is far greater than the flexibility, which requires that the devices can be repeatedly twisted, stretched and bent, and meanwhile, the electrochromic properties of the devices are not affected and remain stable, so that the electrochromic material is preferably an elastomer, can be highly deformed, and has stable discoloration properties in the deformation process. Although the conductive polymer has a flexible long-chain molecular structure and theoretically has higher tensile resistance compared with metal oxides and organic small molecules, the currently reported experimental value is still poor. With the continuous and intensive research and the improvement of the performance requirements of stretchable devices, the preparation and development of high-performance stretchable electrochromic materials are one of the important challenges facing researchers.
The discovery and research of the non-covalent crosslinking of hydrogen bonds among conjugated polymer chains becomes an effective method for realizing high stretching and self-healing of the conductive polymer. Hydrogen bond formation is mainly due to electrostatic forces, with bond energies slightly stronger than van der waals forces, but forces and stability are significantly weaker than covalent and ionic bonds. By introducing intermolecular hydrogen bonds into the conjugated polymer structure and regulating and controlling the proportion of rigid conjugated structural units and hydrogen bond cross-linked flexible carbon chains in the material, the novel intrinsic stretchable self-healing polymer semiconductor is prepared and used for the stretchable electrochromic manufacture. The design concept is as follows: the rigidity conjugated structural unit has high crystallinity (crystal region), and can realize charge transmission of the material; the flexible carbon chain containing hydrogen bond crosslinking is in an amorphous state (amorphous region) and plays a role in softening. When the material is stretched, the hydrogen bonds can be disconnected to absorb mechanical energy, and meanwhile, the electronic transmission property of the polymer cannot be obviously reduced; when the stress is released, the keys are combined again. Although the stretchability and the mechanical durability of the material have a larger space for improvement, based on the design concept of interchain hydrogen bond non-covalent crosslinking, a large number of new highly-stretchable self-repairing conductive polymer materials with better performances can be expected to rapidly appear in the future.
The poly (3, 4-dioxygen ethyl thiophene) material has excellent electrochromic performance and good stability, and is an ideal choice for designing and synthesizing an electrochromic new material of an intrinsic stretchable conductive polymer. Poly (3, 4-ethylenedioxythiophene) (PEDOT) is a star material in a conductive polymer family, has high conductivity, and can reach 4800S/cm at present; the environmental stability is excellent, and the conductivity hardly changes when the material is heated for 1000h at 100 ℃; the visible light transmittance is high (more than 90%); the film forming property is good. As an electrochromic material, PEDOT-based analogues, derivatives and copolymers (PEDOTs) have high coloring efficiency (which can reach 1365 cm)2C-1) Short response time: (<1s), good cycling stability (capable of cycling more than 200 ten thousand times), and capability of realizing full-color display. The basic research based on PEDOTs electrochromic materials is mature, the electrochromic properties of the materials are excellent, and part of the materials are in device, product and commercialization. Thus, it can be seen that the PEDOTs-like structural material is a designThe best choice for synthesizing the novel electrochromic material of the intrinsic stretchable conductive polymer.
Disclosure of Invention
In view of the above problems of the prior art, the present applicant provides a hydrogen bond crosslinked intrinsically stretchable electrochromic polymer and a method for preparing the same. The invention takes pyridine-dicarboxamides (PDCAs) or bipyridine-dicarboxamides (DPDCAs) units as an interchain hydrogen bond crosslinking structure, introduces the pyridine-dicarboxamides units into a poly (BisEDOTs) polymer main chain with excellent electrochromic performance, designs and synthesizes a series of hydrogen bond crosslinking intrinsic stretchable electrochromic new materials, and provides certain theoretical guidance, materials and technical support for the synthesis of stretchable electrochromic materials and the research of devices.
The technical scheme of the invention is as follows:
a hydrogen bond crosslinked intrinsically stretchable electrochromic polymer comprising a color changing functional group and a hydrogen bond crosslinked stretchable group.
The color-changing functional group is obtained by one step of Stille coupling reaction or Suzuki coupling reaction by taking 3, 4-ethylenedioxythiophene as a donor unit and a five-membered heterocyclic compound or an aromatic compound with electron deficiency as an acceptor group.
The hydrogen bond crosslinking stretchable group is composed of pyridine-dicarboxamide derivatives or bipyridine-dicarboxamide derivatives.
The reaction process of the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer comprises the following steps:
wherein m is more than 1; the stretchable group has a structure shown as A or B, wherein R1Is a hydrogen radical or a methyl radical,
R2is composed of
Wherein R is3Is hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Straight or branched chain ofAny one of an alkoxy group, a chlorine atom, or a fluorine atom.
The structure of the color-changing functional group in the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer is as follows:
any one of (a);
wherein X is S, Se or O atom; y is a C or N atom; z1Is O, S, Se, C atom or N-R4，Z2Is O, S, Se, C atom or N' R4，Z1And Z2The same or different;
the R is4、`R4Are each independently hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a straight or branched alkoxy group, a chlorine atom or a fluorine atom of (1); r4、`R4The same or different;
R5expressed as hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a straight or branched alkoxy group, a chlorine atom or a fluorine atom of (1);
R6、R7each independently is thienyl, phenyl, pyridyl, hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a linear or branched alkoxy group, a chlorine atom or a fluorine atom of (A), R6、R7The same or different;
R8、R9each independently is any one of thienyl, phenyl and pyridyl, R8、R9The same or different; r10Represented by any one of H, chlorine atom or fluorine atom.
The branched alkyl is any one of 2-methylpropane, 2-methylhexane, 2-ethylhexane, 2-ethylheptane, 2-hexyloctane, 2-octyldecyl, 2-octyldodecyl, 2-decyldodecyl and 2-decyltetradecyl.
The invention summarizes a series of synthesized hydrogen bond crosslinking intrinsic stretchable electrochromic polymers, and the synthesis route is designed as follows:
the invention adopts the following synthetic strategy: taking a tin-butylated BisEDOT compound and a brominated rigid five-membered heterocyclic or aromatic structure as raw materials, and carrying out palladium-catalyzed cross-coupling reaction in toluene to obtain a rigid color-changing functional group compound; and then brominating the compound, and then carrying out palladium-catalyzed coupling reaction with tin-butylated stretchable groups (PDCAs or DPDCAs) to obtain the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer in one step, wherein the stretchable performance of the stretchable polymer can be controlled by adjusting different charge ratios.
Wherein the catalyst is palladium tetratriphenylphosphine, i.e. Pd (PPh), as described above3)4Or bis-triphenylphosphine palladium dichloride, i.e. Pd (PPh)3)2Cl2(ii) a The solvent is one or more of Tetrahydrofuran (THF), toluene, and N, N-Dimethylformamide (DMF).
An intrinsic stretchable electrochromic device assembled based on hydrogen bond crosslinked intrinsic stretchable electrochromic polymer materials has the following structure: stretchable substrate (SEBS or PDMS or PEDOT: PSS self-supporting film) -conductive layer-ion storage layer-electrolyte-electrochromic layer-conductive layer-stretchable substrate (SEBS or PDMS or PEDOT: PSS self-supporting film). The intrinsic stretchable electrochromic device not only has good stretchable performance, but also has good electrochromic performance, and especially full-color change can be realized by changing color-changing functional groups.
The beneficial technical effects of the invention are as follows:
(1) the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material is based on intrinsic stretchable materials (PDCAs or DPDCAs) as a core, so that the polymer has good stretchable performance, and therefore, certain theoretical guidance, material and technical support are provided for synthesis of the intrinsic stretchable electrochromic material and research of an intrinsic stretchable electrochromic device in the field of intrinsic stretchable electrochromic.
(2) The invention introduces the color-changing functional group into the intrinsic stretchable polymer, so that the polymer realizes the full color change of the polymer color while realizing the intrinsic stretchable performance; meanwhile, by changing the color-changing functional group, the absorption spectrum of the polymer can be adjusted, and the electrochromic properties (response time, transmittance and the like) of the polymer are further changed.
(3) The hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material is obtained through chemical polymerization, compared with a polymer obtained through electrochemical polymerization, the polymer theoretically has smaller structural defects, the polymer is spin-coated on a stretchable electrode through a spin coating method, is soaked in anhydrous dichloromethane or acetonitrile, monomers on the surface of a film and some polymers with lower polymerization degrees are washed away, and then the film is dried in a vacuum box. And coating a layer of gel electrolyte between the two films, and drying in a vacuum box. Finally, the device is packaged by UV glue, and the whole device is sealed to isolate air. The assembled device structure is a stretchable substrate (SEBS or PDMS or PEDOT: PSS self-supporting film) -conductive layer-ion storage layer-electrolyte-electrochromic layer-conductive layer-stretchable substrate (SEBS or PDMS or PEDOT: PSS self-supporting film).
(4) Utilizing an ultraviolet spectrophotometer to adjust the voltage applied to the working electrode through an electrochemical workstation, and recording the variation trend of the absorption spectrum of the polymer under different voltages, namely obtaining the spectroelectrochemical spectrum of the polymer; secondly, measuring the transmittance of the polymer film in a doped state and a dedoped state under the square wave potential by using an ultraviolet-visible spectrophotometer so as to calculate the optical contrast, the response time and the like; the ultraviolet-visible spectrophotometer records a time-transmittance curve, the electrochemical workstation records a time-current curve, and the coloring efficiency can be calculated according to the two curves.
(5) And (3) utilizing an ultraviolet spectrophotometer, regulating the voltage applied to the working electrode through an electrochemical workstation, and recording the variation trend of the absorption spectrum of the polymer under different voltages and different stretching lengths, namely obtaining the spectroelectrochemical spectrum of the polymer under the stretching state. Secondly, measuring the transmittance of the polymer film in a doped state and a dedoped state under the square wave potential at a specific wavelength and a specific stretching length by using an ultraviolet-visible spectrophotometer, thereby calculating the optical contrast, the response time and the like; the ultraviolet-visible spectrophotometer records a time-transmittance curve, the electrochemical workstation records a time-current curve, and the coloring efficiency under a specific stretching length can be calculated according to the two curves.
Note: coloring efficiency: refers to the ratio of the change in absorbance of the electrochromic material at a given wavelength to the time that all electrons are caused to be injected or extracted.
For an electrochromic material, the coloring efficiency is an important parameter for evaluating the material properties. Coloring efficiency research of conductive polymer the coloring efficiency of the conductive polymer is combined with the electrochemical and spectral change process of the electrochromic film, and the calculation formula is as follows:
CE＝ΔOD/Qd(1)
wherein the change in optical contrast (Δ OD) is at a specific wavelength λmaxNext, when the polymer film is electrochemically oxidized and reduced, the corresponding transmittance value (transmittance T in the doped state of the polymer film)oxAnd transmittance in neutral state Tred) Is calculated by the following formula:
ΔOD＝log(Tox/Tred) (2)
the absorption position of the polymer determines the color of the polymer, has important significance for preparing electrochromic polymers with various colors, and the response time is also an important parameter of the electrochromic material, which reveals the speed of doping ions entering a polymer main chain in the doping process.
Drawings
FIG. 1 shows the hydrogen bonding crosslinked intrinsically stretchable electrochromic Polymer of isoindigo of example 1 in MeCN-BmimPF6(0.1mol·L-1) In the system, the color change chart before and after the film is stretched;
FIG. 2 is a hydrogen bonding crosslinked intrinsically stretchable electrochromic Polymer of isoindigo of example 1 in MeCN-BmimPF6(0.1mol·L-1) In the system, the membrane is in the unstretched stateA drawing;
FIG. 3 shows hydrogen bonding cross-linked intrinsically stretchable electrochromic Polymer of isoindigo of example 1 in MeCN-BmimPF6(0.1mol·L-1) In the system, the spectrum electrochemical diagram is obtained after the membrane is stretched by 50 percent;
FIG. 4 shows hydrogen bonding cross-linked intrinsically stretchable electrochromic Polymer of isoindigo of example 1 in MeCN-BmimPF6(0.1mol·L-1) In the system, the time-transmittance curve after the film is stretched by 50%;
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A hydrogen-bond crosslinked intrinsically stretchable electrochromic polymer based on isoindigo is prepared by the following steps:
(1) synthesis of stretchable groups PDCAs
(1a) 2, 6-pyridine dicarboxylic acid (10.03g, 0.06mol) is used as a raw material and reacts with oxalyl chloride (22.85g, 0.18mol) to generate 2, 6-pyridine diformyl chloride;
(1b)2, 6-pyridine diformyl chloride (2.98g, 0.18mol) and 2-ethylamine EDOT (6.00g, 0.32mol) are mixed in triethylamine (6mL) and CH2Cl2(36mL) to synthesize PDCA short chain in one step,
(1c) the PDCA short chain (1.3g, 3.37mmol) reacts with LDA (3.37mL, 6.74mmol) and tributyltin chloride (2.19g, 6.74mmol) to obtain the tin butylated PDCAs, and the tin butylated PDCAs are separated and purified for later use.
(2) Synthesis of the Donor group BisEDOT
(2a) EDOT (7.50g, 50mmol) as a raw material and THF (50mL) as a solvent were reacted with n-butyllithium (53mL, 85.00mmol) at-78 ℃ for two hours, followed by addition of CuCl2 for 12 hours to give BisEDOT;
(2b) BisEDOT (1.5g, 5.0mol) was reacted with n-butyllithium (4.0mL, 6.3mmol) at-78 deg.C for two hours, followed by the addition of tributyltin chloride (2.05g, 6.3mmol) for 12 hours to yield tin-butylated BisEDOT for later use.
(3) Synthesis of hydrogen bond crosslinking intrinsic stretchable polymer with isoindigo as color-changing functional group
(3a) Taking 6-bromoindole-2, 3-dione (6.0g, 13.4mmol) and 6-bromoindole-2-ketone (6.4g, 13.4mmol) as raw materials, and synthesizing dibromo 3, 3' -biindolidione in one step under the acidic condition of a mixed solution of acetic acid and hydrochloric acid;
(3b) dibromo 3, 3' -biindolidione (2.0g, 4.5mmol) was dissolved in DMF (50.0mL), potassium carbonate was provided in a slightly alkaline environment, and 1-bromohexane (1.6g, 9.6mmol) was introduced onto the N atom on the lactam ring to enhance solubility to give IDOH (hexylisoindigo);
(3c) in a toluene solution, IDOH (0.6g, 1.0mmol) and tin butylated BisEDOT (2.8g, 5.0mmol) undergo a Stille cross-coupling reaction in a palladium tetratriphenylphosphine (0.12g, 10% mmol) catalytic environment to synthesize BisEDOT-IDOH (hexyl isoindigo) -BisEDOT monomer,
(3d) BisEDOT-IDOH (hexylisoindigo) -BisEDOT monomer (0.2g, 0.2mmol) was brominated with NBS (0.09g, 0.4mmol) in CH2Cl2 solution to give dibromo-BisEDOT-IDOH (hexylisoindigo) -BisEDOT for later use.
(4) Synthesis of hydrogen bond crosslinking intrinsic stretchable polymer based on IDOH type as color-changing functional group
(4a) Tin butylated PDCAs (0.61g, 0.85mmol) and dibromo BisEDOT-IDOH (hexylisoindigo) -BisEDOT (0.2g, 0.17mmol) are subjected to Stille cross-coupling reaction in a solvent environment of Pd2(dba)3(0.04g, 5% mmol), P (o-tal)3(0.12g, 40 mmol%) as a catalyst to synthesize a hydrogen-bond crosslinked intrinsic stretchable polymer material mixture based on isoindigo;
(4b) and (3) carrying out a recrystallization experiment on the mixture in petroleum ether to precipitate a solid, washing the obtained solid mixture with diethyl ether and acetone in sequence, and drying to obtain the hydrogen bond crosslinking intrinsic stretchable polymer material based on isoindigo.
Example 2
A hydrogen bond crosslinking intrinsic stretchable electrochromic polymer based on benzotriazole is prepared by the following steps:
(1) synthesis of stretchable groups PDCAs
(1a) 2, 6-pyridine dicarboxylic acid (10.03g, 0.06mol) is used as a raw material and reacts with oxalyl chloride (22.85g, 0.18mol) to generate 2, 6-pyridine diformyl chloride;
(1b)2, 6-pyridine diformyl chloride (2.98g, 0.18mol) and 2-ethylamine EDOT (6.00g, 0.32mol) are mixed in triethylamine (6mL) and CH2Cl2(36mL) to synthesize PDCA short chain in one step,
(1c) the PDCA short chain (1.3g, 3.37mmol) reacts with LDA (3.37mL, 6.74mmol) and tributyltin chloride (2.19g, 6.74mmol) to obtain the tin butylated PDCAs, and the tin butylated PDCAs are separated and purified for later use.
(2) Synthesis of the Donor group BisEDOT
(2a) EDOT (7.50g, 50mmol) as a raw material and THF (50mL) as a solvent were reacted with n-butyllithium (53mL, 85.00mmol) at-78 ℃ for two hours, followed by addition of CuCl2 for 12 hours to give BisEDOT;
(2b) BisEDOT (1.5g, 5.0mol) was reacted with n-butyllithium (4.0mL, 6.3mmol) at-78 deg.C for two hours, followed by the addition of tributyltin chloride (2.05g, 6.3mmol) for 12 hours to yield tin-butylated BisEDOT for later use.
(3) Synthesis of BisEDOT-BTzH (hexyl benzotriazole) -BisEDOT rigid color-changing functional group
(3a) 3, 4-dinitrobenzene (0.32g,3.0mmol) is used as a raw material to react with sodium nitrite (0.30g,3.3mmol) in glacial acetic acid (12ml) to generate benzotriazole;
(3b) benzotriazole (0.26g,2.2mmol) and 1-bromohexane (0.413g,2.5mmol) react in DMF (30ml) to obtain hexyl benzotriazole (BTzH), and the introduction of N atom can increase the solubility of the material;
(3c) BTzH (0.30g,1.5mmol), liquid bromine (0.56g,3.5mmol) are used as raw materials, hydrobromic acid (10ml) is used as a solvent, and the brominated BTzH is prepared through one-step reaction;
(3d) taking brominated BTzH (0.52g,1.45mmol), tin butylated BisEDOT (4.15g,7.25mmol) as a raw material, toluene (50ml) as a solvent, and tetratriphenylphosphine palladium (0.12g, 10% mmol) as a catalyst to perform a Stille cross-coupling reaction to synthesize a BisEDOT-BTzH (hexylbenzotriazole) -BisEDOT polymer precursor;
(3e) BisEDOT-BTzH (hexyl benzotriazole) -BisEDOT polymer precursor (1.9g,2.5mmol) and NBS (0.89g,5mmol) are used as raw materials and react in dichloromethane (50ml) to obtain dibromo-BisEDOT-BTzH (hexyl benzotriazole) -BisEDOT for later use.
(4) Synthesis of hydrogen bond crosslinking intrinsic stretchable polymer based on BTzH type as color-changing functional group
(4a) Tin butylated PDCAs (0.61g, 0.85mmol) and dibromo-BisEDOT-BTzH (hexylbenzotriazole) -BisEDOT (0.156g, 0.17mmol) were added to Pd2(dba)3(0.04g，5％mmol)、P(o-tal)3(0.12g, 40 mmol%) as a catalyst, and performing Stille cross-coupling reaction in an environment with chlorobenzene as a solvent to synthesize the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material based on benzotriazole.
(4b) The polymer post-treatment mode is as follows: and pouring the mixture into a large volume of petroleum ether to separate out a solid polymer mixture, washing the solid mixture by using diethyl ether and acetone in sequence, and drying to obtain the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material based on the benzotriazole.
Example 3
A hydrogen bond crosslinked intrinsically stretchable electrochromic polymer based on PEDOT oligomers is prepared by the following steps:
(1) synthesis of stretchable groups PDCAs
(1a) 2, 6-pyridine dicarboxylic acid (10.03g, 0.06mol) is used as a raw material and reacts with oxalyl chloride (22.85g, 0.18mol) to generate 2, 6-pyridine diformyl chloride;
(1b)2, 6-pyridine diformyl chloride (2.98g, 0.18mol) and 2-ethylamine EDOT (6.00g, 0.32mol) are mixed in triethylamine (6mL) and CH2Cl2(36mL) to synthesize PDCA short chain in one step,
(1c) the PDCA short chain (1.3g, 3.37mmol) reacts with LDA (3.37mL, 6.74mmol) and tributyltin chloride (2.19g, 6.74mmol) to obtain the tin butylated PDCAs, and the tin butylated PDCAs are separated and purified for later use.
(2) Synthesis of the Donor group BisEDOT
(2a) EDOT (7.50g, 50mmol) as a raw material and THF (50mL) as a solvent were reacted with n-butyllithium (53mL, 85.00mmol) at-78 ℃ for two hours, followed by addition of CuCl2 for 12 hours to give BisEDOT;
(2b) BisEDOT (1.5g, 5.0mol) was reacted with n-butyllithium (4.0mL, 6.3mmol) at-78 deg.C for two hours, followed by the addition of tributyltin chloride (2.05g, 6.3mmol) for 12 hours to yield tin-butylated BisEDOT for later use.
(3) Synthesis of PentaEDOT rigid color-changing functional group
(3a) dibromo-EDOT was generated in one step in THF (50.0mL) using EDOT (1.42g, 40.0mmol) as the starting material and NBS (4.09g, 23.0mmol) as the brominating agent;
(3b) carrying out Stille cross-coupling reaction on dibromo EDOT (1.3g, 4.0mmol) and tin-butylated BisEDOT (5.0g, 8.74mmol) in a toluene environment by taking palladium (0.12g, 10% mmol) of tetratriphenylphosphine as a catalyst to obtain a PentaEDOT monomer in one step;
(3c) NBS (0.09g, 0.4mmol) is used as a brominating agent, bromine is used for substituting PentaEDOT (0.14g, 0.2mmol) to obtain dibromo PentaEDOT through bromination reaction, and the dibromo PentaEDOT is used later.
(4) Synthesis of hydrogen bond crosslinking intrinsic stretchable polymer with PentaEDOT as color-changing functional group
(4a) Tin-butylated PDCAs (0.61g, 0.85mmol) and dibromo PentaEDOT (0.36g, 0.42mmol) were combined in Pd in toluene solution2(dba)3(0.04g，5％mmol)、P(o-tal)3(0.12g, 40 mmol%) as a catalyst, and performing Stille cross-coupling reaction in an environment with chlorobenzene as a solvent to synthesize the PEDOT-based hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material.
(4b) And (3) performing a recrystallization experiment on the mixture in petroleum ether to obtain a solid mixture, washing the solid mixture with diethyl ether and acetone in sequence, and drying to obtain the PEDOT-based hydrogen bond crosslinking intrinsic stretchable electrochromic polymer material.
Test example:
the hydrogen bond crosslinked intrinsic stretchable electrochromic polymer based on isoindigo prepared in example 1 of the present invention was dissolved in toluene (3mg/mL), spin-coated on PET (polyethylene terephthalate) after ultraviolet surface treatment at 2000 RMP. Then carrying out high-temperature 120 ℃ annealing treatment in a vacuum oven to obtain a stable polymer film, and then carrying out electrochromic property test and tensile property test on the polymer film:
(1) electrochemical testing
An electrochemical workstation three-electrode system is utilized to carry out doping and dedoping experimental test on the hydrogen bond crosslinking intrinsic stretchable electrochromic polymer, the test voltage is minus 0.5V dedoping, and +1.5V is doping voltage, and the color of the polymer has obvious change under the doping and dedoping states and changes from dark green to blue-violet. After stretching it by 50%, the film still showed a significant color change at the same transformation voltage. The results are shown in FIG. 1.
(2) Spectroscopic test in the unstretched state:
the spectrogram of the intrinsically stretchable polymer film based on IDOH hydrogen bond crosslinking in a stretched and unstretched state is tested, the voltage changes are respectively from-0.5V, -0.3V, -0.1V, 0.1V, 0.3V, 0.5V, 0.7V, 0.9V, 1.1V, 1.3V and 1.5V, and the spectral change conditions are sequentially tested, and the test result is shown in figure 2.
As can be seen from fig. 2: under the de-doping state of-0.5V voltage, the polymer has two obvious absorption peaks respectively positioned between 400nm and 600-700 nm, and the polymer film shows dark green; as the absorption peak before the voltage rise gradually disappears, a new absorption peak (500 nm-600 nm) appears, and the color of the polymer film is blue-violet.
(3) Spectroscopic test under 50% elongation
The spectrogram of the intrinsically stretchable polymer film based on IDOH hydrogen bond crosslinking under the state of stretching 50% is tested, the voltage changes are respectively from-0.5V, -0.3V, -0.1V, 0.1V, 0.3V, 0.5V, 0.7V, 0.9V, 1.1V, 1.3V and 1.5V, and the spectral change conditions are sequentially tested. The test results are shown in fig. 3.
As can be seen from fig. 3: under the de-doping state of-0.5V voltage, the polymer has two obvious absorption peaks respectively positioned between 400nm and 600-700 nm, and the polymer film shows dark green; as the absorption peak before the voltage rise gradually disappears, a new absorption peak (500 nm-600 nm) appears, and the color of the polymer film is blue-violet.
From the spectrum, the absorption peak position value of the polymer is basically not changed before and after stretching, which indicates that the breaking phenomenon of conjugated chains does not occur in the polymer during the stretching process, and indicates that the IDOH hydrogen bond crosslinking intrinsic stretchable polymer has better stretchability.
(4) Polymer film transmittance test
Testing a transmittance curve of the IDOH-based hydrogen bond crosslinking intrinsic stretchable polymer film in a 50% stretching state, wherein the voltage change is changed from-0.5V to 1.5V, and testing the change condition of the transmittance of the polymer film in a doping and dedoping state under the wavelength of 1000 nm; with a time interval of 20 s. The test results are shown in fig. 4. As can be seen from fig. 4: the polymer film had a transmittance of 43.5% in the oxidized state (doped state) and 56.5% in the reduced state (undoped state), and the transmittance of the polymer film was maintained at about 13% during the transition between the doping voltage and the dedoping voltage.
Claims (3)
1. A hydrogen bond crosslinked intrinsically stretchable electrochromic polymer, characterized in that the polymer comprises a color changing functional group and a hydrogen bond crosslinked stretchable group; the color-changing functional group is obtained by one step of Stille coupling reaction by taking bis (3, 4-ethylenedioxythiophene) as a donor unit and a five-membered heterocyclic compound or an aromatic compound with electron deficiency performance as an acceptor group; the hydrogen bond crosslinking stretchable group consists of pyridine-dicarboxamide derivatives or bipyridine-dicarboxamide derivatives;
the reaction scheme of the polymer is as follows:
wherein m is more than 1; the stretchable group has a structure shown as A or B, wherein R1Is a hydrogen radical or a methyl radical,
R2is composed of
Wherein R is3Is C1～12Straight or branched alkyl of (2), C1～12Any one of a straight or branched alkoxy group, a chlorine atom or a fluorine atom of (2).
2. The polymer of claim 1, wherein said color-changing functional group has the structure:
any one of (a);
wherein X is S, Se or O atom; y is a C or N atom; z1Is O, S, Se, C atom or N-R4，Z2Is O, S, Se, C atom or N' R4，Z1And Z2The same or different;
the R is4、`R4Are each independently hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a straight or branched alkoxy group, a chlorine atom or a fluorine atom of (1); r4、`R4The same or different;
R5expressed as hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a straight or branched alkoxy group, a chlorine atom or a fluorine atom of (1);
R6、R7each independently is thienyl, phenyl, pyridyl, hydrogen radical, C1～12Straight or branched alkyl of (2), C1～12Any one of a linear or branched alkoxy group, a chlorine atom or a fluorine atom of (A), R6、R7The same or different;
R8、R9each independently is any one of thienyl, phenyl and pyridyl, R8、R9The same or different; r10Represented by any one of H, chlorine atom or fluorine atom.
3. The polymer according to claim 1 or 2, characterized in that the branched alkyl group is any one of 2-methylpropyl, 2-methylhexanyl, 2-ethylhexanyl, 2-ethylheptanyl, 2-hexyloctanyl, 2-octyldecyl, 2-octyldodecyl, 2-decyldodecyl, 2-decyltetradecyl.
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