CN118184966A - D-pi-A-pi-D conjugated polymer and preparation method and application thereof - Google Patents
D-pi-A-pi-D conjugated polymer and preparation method and application thereof Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- -1 selenophenyl Chemical group 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000006619 Stille reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 7
- 229940071182 stannate Drugs 0.000 claims description 7
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- 238000004070 electrodeposition Methods 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 claims description 2
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- 229920006254 polymer film Polymers 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
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- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 7
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
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- 238000004440 column chromatography Methods 0.000 description 6
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 6
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- SQRICDVGYLFTLO-UHFFFAOYSA-N tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane Chemical compound O1CCOC2=C([Sn](CCCC)(CCCC)CCCC)SC=C21 SQRICDVGYLFTLO-UHFFFAOYSA-N 0.000 description 3
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- XEVOZPRNEPMHAF-UHFFFAOYSA-N 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole Chemical compound BrC1=C([N+]([O-])=O)C([N+](=O)[O-])=C(Br)C2=NSN=C21 XEVOZPRNEPMHAF-UHFFFAOYSA-N 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
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- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- AOOYMUMUMFGBDO-UHFFFAOYSA-N tributyl-(4-dodecylthiophen-2-yl)stannane Chemical compound CCCCCCCCCCCCC1=CSC([Sn](CCCC)(CCCC)CCCC)=C1 AOOYMUMUMFGBDO-UHFFFAOYSA-N 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a D-pi-A-pi-D conjugated polymer and a preparation method and application thereof, and belongs to the technical field of polymer materials. The structural formula of the D-pi-A-pi-D conjugated polymer provided by the invention is shown as the following formula (I): The invention utilizes the strong electron withdrawing capability of the nitro and the unique plane structure, is beneficial to enhancing the interaction between the donor and the receptor, and the large-volume structure of the nitro is beneficial to blocking the strong intermolecular interaction of the polymer chain in space, reduces the stacking density, thereby improving the processability of the polymer; and the nitro group is adopted for symmetrical modification, the obtained 5, 6-dinitrate-2, 1, 3-benzothiadiazole is taken as a receptor unit A, and the receptor unit has high molecular binding energy and large dipole moment, is favorable for obtaining a conjugated polymer with high optical contrast and coloring efficiency, and has wide application in preparing electrochromic devices with excellent performances.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a D-pi-A-pi-D conjugated polymer, and a preparation method and application thereof.
Background
Electrochromic phenomena (Electrochromism, EC) means that the material undergoes oxidation (reduction) reaction process or charge injection or extraction in molecular structure under the action of an applied driving voltage, so that the optical properties (including transmittance, absorptivity or absorbance) of the polymer material undergo continuous reversible change in the visible light region and the infrared spectrum region, and the material appears as color or transmittance change in appearance. Materials having such color-changing properties are called electrochromic materials. The material has commercialized prospect in various fields such as low-energy display devices, electronic paper, color-changing skin, information storage display and the like, and can be used for updating and functional integration of various wearable electronic equipment.
The D-A-D (donor-acceptor-donor) type structure is one of methods for changing the color of electrochromic conductive polymer materials, and the D-A-D type structure can not only easily adjust the absorption wavelength of the polymer, but also change the bandwidth thereof. Modification of acceptor groups with halogen atoms is one of the methods to increase their usability, but the introduction of halogen atoms has some problems such as: low yields of photoelectron exchange, serious aggregation problems, difficult reaction steps, low yields, and the need for dangerous reagents, etc. How to modify the material structure better to reduce the strong intermolecular interaction of polymer chains and bulk density, and further increase the processability and optical properties of the polymer is a problem to be solved at present.
Disclosure of Invention
In order to overcome the problems of the prior art, it is an object of the present invention to provide a D-pi-a-pi-D type conjugated polymer having good processability and optical properties, and good optical contrast and coloring efficiency.
The second object of the present invention is to provide a method for preparing the conjugated polymer.
It is a further object of the present invention to provide a use of the conjugated polymer.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The first aspect of the invention provides a D-pi-A-pi-D conjugated polymer, which has a structural formula shown in the following formula (I):
In the formula (I), ar and pi are respectively and independently C6-30 aromatic hydrocarbon groups, C5-30 aromatic heterocyclic groups, C6-30 aromatic hydrocarbon groups substituted by one or more C1-50 alkyl groups and C5-30 aromatic heterocyclic groups substituted by one or more C1-50 alkyl groups; the heteroatom in the aromatic heterocyclic group includes at least one of O, S, se, N, si; n is an integer of 1 to 10000.
In the formula (I), ar is used as a donor unit D, pi is used as pi bridge, and 5, 6-dinitrate-2, 1, 3-benzothiadiazole is used as an acceptor unit A.
O, S, se, N, si in hetero atoms in the aromatic heterocyclic group are strong electron-withdrawing atoms or stable atoms, and serve as donor units or pi bridges, so that interaction between a donor and a receptor is enhanced, and the performance of the conjugated polymer is improved.
Preferably, in the formula (I), ar and pi are each independently at least one of thienyl, furyl, selenophenyl, pyrrolyl, thiazolyl, phenyl, fluorenyl, carbazolyl, silafluorenyl, benzodithiophene, benzodiselenophenyl, benzodifuranyl, bithiophene, and furanyl, thienocyclopentadienyl, thienopyrrolyl, thienothilolyl, 3, 4-methylenedioxythienyl, 3, 4-ethylenedioxythienyl, 3, 4-propylenedioxythienyl, 3, 4-methylenedioxyselenophenyl, 3, 4-ethylenedioxyselenophenyl, 3, 4-propylenedioxyselenophenyl, thieno [3,4-b ] [1,4] oxathialkyl, thieno [3,4-b ] [1,4] oxazinyl, or substituted with one or more C1-50 alkyl groups.
Preferably, in the formula (I), ar and pi are each independently of the other the following structure:
wherein R1 is H or C1-50 alkyl; p is an integer of 1 to 3.
Further preferably, ar and pi are each independently of the other the following structure:
wherein R1 is H or C1-50 alkyl; p is an integer of 1 to 3.
Still more preferably, ar and pi are each independently of the following structure:
wherein R1 is H or C1-50 alkyl; p is an integer of 1 to 3.
In the structural formulae of Ar and pi, R1 is preferably H or a C5-40 alkyl group, more preferably H or a C8-30 alkyl group, and still more preferably H or a C10-20 alkyl group.
In the above structural formulae of Ar and pi, P is preferably 2 or 3, and more preferably 2.
In some embodiments of the invention, ar is the following structure:
wherein R1 is H; p is 2.
In some embodiments of the invention, pi is the following structure:
Wherein R1 is C10-20 alkyl; p is 2.
In some embodiments of the invention, the conjugated polymer has a structural formula as shown in any one of formulas (1) to (3):
In the formulas (1) to (3), n is an integer of 1 to 10000.
A second aspect of the present invention provides a method for preparing a conjugated polymer according to the first aspect of the present invention, comprising the steps of: mixing 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide, stannate containing pi units and stannate containing Ar units for Stille reaction to obtain a polymerization precursor, and carrying out electrochemical polymerization on the polymerization precursor to obtain the conjugated polymer.
Preferably, in the preparation method of the conjugated polymer, 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide and stannate containing pi units are mixed for Stille reaction to obtain a first intermediate containing pi units, and the first intermediate is brominated and then added into stannate containing Ar units for mixing for Stille reaction to obtain the polymer precursor.
Preferably, in the preparation method of the conjugated polymer, the molar ratio of the 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide to the tin compound containing pi units is 1: (2-5); further preferably 1: (2.2-4); still more preferably 1: (2.4-3).
Preferably, in the preparation method of the conjugated polymer, the molar ratio of the 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide to the stannate containing Ar unit is 1: (2-5); further preferably 1: (2.2-4); still more preferably 1: (2.4-3).
Preferably, in the preparation method of the conjugated polymer, the temperature of the Stille reaction is 100-140 ℃; further preferably 105 to 135 ℃; still more preferably 110 to 130 ℃.
Preferably, in the preparation method of the conjugated polymer, the Stille reaction time is 36-60 h; further preferably 40 to 56 hours; more preferably 44 to 52 hours.
Preferably, in the preparation method of the conjugated polymer, the Stille reaction is performed in a protective gas atmosphere. The protective gas in the Stille reaction preferably comprises at least one of nitrogen, argon and helium; argon is more preferred.
Preferably, in the preparation method of the conjugated polymer, the Stille reaction is carried out in a solvent and a catalyst; the solvent in the Stille reaction preferably comprises toluene, N-dimethylformamide or a mixed solution thereof, and more preferably a mixed solution of toluene and N, N-dimethylformamide; the catalyst in the Stille reaction is preferably bis (triphenylphosphine) palladium chloride.
Preferably, in the preparation method of the conjugated polymer, the electrochemical polymerization is: and (3) taking the solution containing the polymerization precursor as electrolyte, and performing electrodeposition in a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode to obtain the polymer on the working electrode.
Preferably, in the electrochemical polymerization, the concentration of the polymerization precursor in the electrolyte is 0.001-0.1 mol/L; further preferably 0.005 to 0.05mol/L; still more preferably 0.008 to 0.02mol/L.
Preferably, in the electrochemical polymerization, the solvent of the electrolyte includes at least one of dichloromethane (CH 2Cl2), chloroform (CHCl 3) or acetonitrile (MeCN); further preferred is dichloromethane.
Preferably, in the preparation method of the polymer, the electrolyte is further contained in the electrolyte.
Preferably, in the electrolyte, the electrolyte includes at least one of tetrabutylammonium hexafluorophosphate (PF 6), tetrabutylammonium tetrafluoroborate (BF 4), or lithium perchlorate; further preferred is tetrabutylammonium hexafluorophosphate.
Preferably, the concentration of the electrolyte in the electrolyte is 0.01 to 1mol/L; further preferably 0.05 to 0.5mol/L; still more preferably 0.08 to 0.2mol/L.
In the preparation method of the polymer, the reference electrode is preferably an Ag/AgCl electrode; the counter electrode is preferably a platinum electrode; the working electrode is preferably a Pt/ITO conductive glass electrode.
Preferably, in the preparation method of the polymer, the electrodeposition mode is a potentiostatic method; further preferably, the potentiostatic method is a galvanostatic method or cyclic voltammetry.
Preferably, in the preparation method of the polymer, the electric potential of the electrodeposition is 1-2V; more preferably 1.1 to 1.5V.
Preferably, in the method for producing a polymer, the electrodeposition is performed under a protective gas atmosphere. The protective gas in the electrodeposition preferably comprises at least one of nitrogen, argon, helium; further preferably nitrogen.
A third aspect of the invention provides the use of a conjugated polymer according to the first aspect of the invention in the manufacture of an electrochromic device.
Preferably, the electrochromic device comprises one or both of a display device or a light transmitting device; further preferably, the electrochromic device comprises at least one of a display, electrochromic glazing, smart window or rear view mirror.
The beneficial effects of the invention are as follows:
The invention utilizes the strong electron withdrawing capability of the nitro and the unique plane structure, is beneficial to enhancing the interaction between the donor and the receptor, and the large-volume structure of the nitro is beneficial to blocking the strong intermolecular interaction of the polymer chain in space, reduces the stacking density, thereby improving the processability of the polymer; and the nitro group is adopted for symmetrical modification, the obtained 5, 6-dinitrate-2, 1, 3-benzothiadiazole is taken as a receptor unit A, and the receptor unit has high molecular binding energy and large dipole moment, is favorable for obtaining a conjugated polymer with high optical contrast and coloring efficiency, and has wide application in preparing electrochromic devices with excellent performances.
In addition, the introduction of pi units can increase the conjugation length of the precursor, reduce the polymerization potential of the precursor, regulate the band gap of the polymer, obtain a conjugated polymer with lower band gap, influence the electronic structure and the interaction between the D and A units, and the increased intermolecular charge transmission is also beneficial to realizing higher molar absorptivity.
Drawings
FIG. 1 is a spectroelectrochemical diagram of the conjugated polymer of example 1.
FIG. 2 is a kinetic plot of the conjugated polymer of example 1.
FIG. 3 is a short term memory map of the conjugated polymer of example 1.
FIG. 4 is a spectroelectrochemical diagram of the conjugated polymer of example 2.
FIG. 5 is a kinetic plot of the conjugated polymer of example 2.
FIG. 6 is a short term memory map of the conjugated polymer of example 2.
FIG. 7 is a spectroelectrochemical diagram of the conjugated polymer of example 3.
FIG. 8 is a kinetic plot of the conjugated polymer of example 3.
FIG. 9 is a short term memory map of the conjugated polymer of example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
In order to realize the practical application of electrochromic materials, the method has important significance in measuring and evaluating the parameters and indexes of the material performance. The invention is assessed by the following parameters and indexes:
(1) Color (optical absorption): the color has a close relationship with the light. The appearance color of the electrochromic material can be represented by a color scale, a spectrum electrochemical curve is a microscopic reaction of the color of the electrochromic material, and the oxidation-reduction process of the electrochromic material and the accompanying change of chemical structure and optical absorption can be recorded. It is worth noting that the color is only a representation of the electrochromic material performance, and has no direct relation with the quality of the material performance.
(2) Optical contrast (Electrochromic contrast): refers To the difference in optical transmittance (To and Tn) between the oxidation state (Oxidated) and the Neutral state (Neutral) of an electrochromic material at a single wavelength, which is an important parameter for measuring the electrochromic properties of the material. The single wavelength is determined according to the absorption spectrum of the material, i.e. the wavelength corresponding to the maximum absorption peak of the material in the oxidized state or the neutral state. The absorption spectrum of the material refers to a time curve of absorbance or transmittance of a substance corresponding to different wavelengths, which is used for measuring the color change of the material, and a spectroelectrochemical experiment can be used for generating single polarons or dual polarons (free radical cations/anions or double cations/anions) in the reaction material.
(3) Response time: the time required for an electrochromic material or device to complete one oxidation or reduction transition (transition of colored state to faded state) can be divided into a colored response time and a faded response time. The shorter the response time of the material means the faster the rate of change of color, and the response time of the material is generally different between the coloring process and the decoloring process. Considering that the actual products have different requirements on response time, the response time is only used as a standard for judging the performance of the electrochromic material, and the quality of the material cannot be measured by the response time.
(4) Coloring efficiency (Coloration efficiency, CE): refers to the ratio of the change in absorbance per unit area of a conductive polymer film injected with a certain amount of electricity to the charge density of the transmittance conversion that occurs in an electrochromic material at a specific wavelength. The value of the coloring efficiency of the same polymer film is unchanged during an oxidation or reduction process, irrespective of the thickness of the film. The coloring efficiency calculation formula is:
CE＝ΔOD/Qd；
Wherein Δod is an optical density change value, which refers to the logarithm of the transmittance ratio of the oxidation state to the reduction state of the polymer film at a specific wavelength, and the calculation formula is as follows: Δod=log (T ox/Tred);Qd is charge density, referring to the amount of charge injected per unit area).
(5) Open optical memory effect (Open circuit memory): refers to the ability of an electrochromic material to retain the color of the oxidized or reduced state of the polymer without the application of an external voltage, and is operable to test the optical transmission of the polymer with the application of an external voltage for a period of time, and then to test the optical transmission by breaking the external voltage, the change being the memory of the material or device.
(6) Stability: stability is the activity that the electrochromic material maintains after multiple transitions between a colored state and a decolored state, the higher the activity that is maintained, the better the stability of the electrochromic material. The activity of electrochromic materials is generally characterized by a time-transmittance curve, and the test time for stability is dependent on the time for some properties of the material to decay.
The invention is further illustrated by the following examples.
Example 1
Preparation of symmetrical D-pi-A-pi-D conjugated polymer P (Th-EDOT-2 NO 2 -BT):
Based on the preparation of a polymeric precursor (structure (c), th-EDOT-2NO 2 -BT) of 5, 6-dinitro-4, 7-bis (7- (thiophen-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole, the chemical reaction scheme is shown below, the specific reaction steps and reaction conditions are as follows:
(1) Preparation of Compound (a)
4, 7-Dibromo-5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole (0.6 g,1.56 mmol), tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) stannane (1.69 g,3.90 mmol) and bis (triphenylphosphine) palladium chloride (0.044 g,0.063 mmol) were placed in a 250mL flask. After flushing the apparatus with argon, 80mL of a mixture of toluene and 20mL of n, n-dimethylformamide was added to the flask under negative pressure. Subsequently, the mixture was heated to 120 ℃ and stirred under reflux for 48 hours. The mixture was cooled to room temperature, toluene was removed by rotary evaporation, extracted with dichloromethane and washed with saturated sodium chloride solution. The methylene chloride was removed by rotary evaporator to give a crude product. The red solid (0.71 g) was obtained by column chromatography in 90% yield. 1H NMR(400MHz,CDCl3 Delta) 6.77 (s, 2H), 4.26-4.23 (m, 4H), 4.21-4.19 (m, 4H).
(2) Preparation of Compound (b)
Compound (a) (0.384 g,0.753 mmol) and N-bromosuccinimide (0.312 g,1.76 mmol) were placed in a 50mL flask, followed by N, N-dimethylformamide (10 mL) and acetonitrile (5 mL). The mixture was heated to 65℃in the dark, hydrobromic acid was added and stirred for 3 hours, and the same amount of N-bromosuccinimide (0.312 g,1.76 mmol) was added and stirred for 2 hours. Suction filtration through a Buchner funnel afforded the crude product, which was repeatedly rinsed with pure water and methanol to afford a dark red solid (0.21 g) in 42% yield. 1H NMR(400MHz,CDCl3 Delta) 4.32 (s, 4H), 4.22 (s, 4H).
(3) Preparation of Compound (c)
Compound (b) (0.15 g,0.226 mmol), tributyl (thiophen-2-yl) stannane (0.21 g, 0.560 mmol) and bis (triphenylphosphine) palladium chloride (0.0064 g,0.009 mmol) were placed in a 250mL flask. After flushing the apparatus with argon, 80mL of a mixture of toluene and 20mL of n, n-dimethylformamide was added to the flask under negative pressure. Subsequently, the mixture was heated to 120 ℃ and stirred under reflux for 48 hours. The mixture was cooled to room temperature, toluene was removed by rotary evaporation, extracted with dichloromethane and washed with saturated sodium chloride solution. The methylene chloride was removed by rotary evaporator to give a crude product. Purple solid (0.108 g) was obtained by column chromatography in yield 71.5％.1H NMR(400MHz,CDCl3,δ):7.87-7.83(m,2H),7.48(dd,J＝6.3,3.2Hz,2H),6.99(dd,J＝12.1,6.6Hz,2H),4.39(s,8H).
(4) Preparation of D-pi-A-pi-D conjugated polymers
The 5, 6-binitro-4, 7-bis (7- (thiophene-2-yl) -2, 3-dihydro-thieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor is electrochemically polymerized into a corresponding polymer, and the chemical reaction flow is shown as follows, and specific reaction steps and reaction conditions are as follows:
Under the protection of nitrogen, dissolving 10mL of a compound (c) (5, 6-binitro-4, 7-bis (7- (thiophen-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole) prepared in the step (3) in refined dichloromethane to serve as an electrolyte, and preparing a polymerization precursor with the concentration of 0.01mol/L and tetrabutylammonium hexafluorophosphate with the concentration of 0.1mol/L serving as the electrolyte; stirring uniformly, continuously introducing argon to protect for 20 minutes, keeping the solution under argon atmosphere, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, and depositing on the ITO conductive glass under a constant potential of 1.15V to obtain the 5, 6-dinitro-4, 7-bis (7- (thiophene-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer.
Application example 1
The conjugated polymer material obtained in example 1 is used in the electrochromic field as an example.
The following examples illustrate the 5, 6-dinitro-4, 7-bis (7- (thiophen-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymers and their application processes in the electrochromic field provided by the present invention, but the present invention is not limited to the examples.
(1) Spectroelectrochemical
Depositing the polymer prepared in the example 1 on ITO conductive glass to form a polymer film, and placing the ITO conductive glass covered with the polymer film in a three-electrode electrolytic cell, wherein a methylene dichloride solution in which tetrabutylammonium hexafluorophosphate is dissolved is arranged in the electrolytic cell; wherein the working electrode is ITO conductive glass attached with a polymer film, the counter electrode is a platinum sheet, and the reference electrode is an Ag/AgCl electrode. And regulating the voltage applied to the working electrode by using a constant potential method through an electrochemical workstation, and recording the change trend of the absorption spectrum of the polymer under different voltages by using an ultraviolet-visible spectrometer to obtain the spectrum electrochemical spectrum of the polymer. FIG. 1 is a spectroelectrochemical diagram of the conjugated polymer of example 1, showing three absorption peaks at 421nm, 615nm and 845nm, respectively, assigned to pi-pi transitions, donor and acceptor molecule charge transfer and polaron absorption peaks. As the voltage increases, the 422nm absorption peak intensity of the polymer decreases or even disappears, and a new absorption peak due to polaron absorption gradually appears in the near infrared region, and the color of the polymer changes from gray to light green.
(2) Kinetic stability study of Polymer films
And measuring the transmittance of the polymer film in an oxidation state and a reduction state under a specific wavelength by using an ultraviolet-visible spectrophotometer, so as to calculate the optical contrast, influence 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. The 5, 6-dinitro-4, 7-bis (7- (thiophen-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer prepared in example 1 was tested for kinetic stability study patterns at 421nm, 845nm and 1100nm, respectively, with square wave potential intervals of 5s. FIG. 2 is a graph showing the kinetics of the conjugated polymer of example 1, as in FIG. 2, with transmittance values of about 2.88%, 8.04%, and 8.31% for the polymer, and the transmittance values remained 2.58%, 6.89%, and 4.93% after 300s of scanning.
(3) Short term memory effect study of polymer films
And applying 10s voltage and 2s voltage every 100s on a working electrode by using a constant potential method through an electrochemical workstation, and recording the change trend of the transmittance of the polymer in the oxidation state and the reduction state under the maximum absorption peak by using an ultraviolet-visible spectrometer at the same time, thus obtaining the short-term memory effect map of the polymer. The change in the transmittance of the polymer in the oxidized state is evident from FIG. 3, while the change in the transmittance in the reduced state is smaller, as shown in FIG. 3, by applying 0.2V and 1V voltages at 1100nm to the 5, 6-dinitro-4, 7-bis (7- (thiophen-2-yl) -2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) benzo [ c ] [1,2,5] thiadiazole-symmetrical donor-pi-acceptor-pi-donor type conjugated polymer film prepared in example 1, respectively.
Example 2
Preparation of symmetrical D-pi-A-pi-D conjugated polymer P (2 EDOT-2NO 2 -BT):
based on the preparation of 5, 6-dinitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor (structure (c), 2EDOT-2NO 2 -BT), the chemical reaction scheme is shown below, and specific reaction steps and reaction conditions are as follows:
(1) Preparation of Compound (a)
In accordance with the preparation of compound (a) of example 1. 1H NMR(400MHz,CDCl3 Delta) 6.77 (s, 2H), 4.26-4.23 (m, 4H), 4.21-4.19 (m, 4H).
(2) Preparation of Compound (b)
In accordance with the preparation of compound (b) of example 1. 1H NMR(400MHz,CDCl3 Delta) 4.32 (s, 4H), 4.22 (s, 4H).
(3) Preparation of Compound (c)
Compound (b) (0.15 g,0.226 mmol), tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) stannane (0.24 g,0.56 mmol) and bis (triphenylphosphine) palladium chloride (0.006g, 0.009 mmol) were placed in a 250mL flask. After flushing the apparatus with argon, 80mL of a mixture of toluene and 20mL of n, n-dimethylformamide was added to the flask under negative pressure. Subsequently, the mixture was heated to 120 ℃ and stirred under reflux for 48 hours. The mixture was cooled to room temperature, toluene was removed by rotary evaporation, extracted with dichloromethane and washed with saturated sodium chloride solution. . The methylene chloride was removed by rotary evaporator to give a crude product. A black solid (0.1354 g) was obtained by column chromatography in 76% yield. 1H NMR(400MHz,CDCl3 Delta) 6.40 (s, 2H), 4.38 (s, 8H), 4.26 (s, 8H).
(4) Preparation of D-pi-A-pi-D conjugated polymers
The 5, 6-binitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor is electrochemically polymerized into corresponding polymer, and the chemical reaction flow is shown as follows, and specific reaction steps and reaction conditions are as follows:
under the protection of nitrogen, dissolving 10mL of 5, 6-binitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor prepared in the example 2 in refined dichloromethane as electrolyte to prepare polymer precursor with the concentration of 0.01mol/L and tetrabutylammonium hexafluorophosphate with the concentration of 0.1mol/L as electrolyte; stirring uniformly, continuously introducing argon to protect for 20 minutes, keeping the solution under argon atmosphere, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, and depositing on the ITO conductive glass under a constant potential of 1V to obtain the 5, 6-dinitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer.
Application example 2
The conjugated polymer material obtained in example 2 is used in the electrochromic field as an example.
The following examples illustrate the 5, 6-dinitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymers and their use in electrochromic applications provided herein, but the invention is not limited to the examples.
(1) Spectroelectrochemical
Depositing the polymer prepared in the example 2 on ITO conductive glass to form a polymer film, and placing the ITO conductive glass covered with the polymer film in a three-electrode electrolytic cell, wherein a methylene dichloride solution in which tetrabutylammonium hexafluorophosphate is dissolved is arranged in the electrolytic cell; wherein the working electrode is ITO conductive glass attached with a polymer film, the counter electrode is a platinum sheet, and the reference electrode is an Ag/AgCl electrode. And regulating the voltage applied to the working electrode by using a constant potential method through an electrochemical workstation, and recording the change trend of the absorption spectrum of the polymer under different voltages by using an ultraviolet-visible spectrometer to obtain the spectrum electrochemical spectrum of the polymer. FIG. 4 is a spectroelectrochemical diagram of the conjugated polymer of example 2, showing three absorption peaks at 461nm, 319 nm and 854nm respectively, respectively attributed to pi-pi transition, donor and acceptor molecule charge transfer and polaron absorption peaks. As the voltage increases, the 461nm absorption peak intensity of the polymer decreases or even disappears, and a new absorption peak due to polaron absorption gradually appears in the near infrared region, and the color of the polymer changes from dark green to blue.
(2) Kinetic stability study of Polymer films
And measuring the transmittance of the polymer film in an oxidation state and a reduction state under a specific wavelength by using an ultraviolet-visible spectrophotometer, so as to calculate the optical contrast, influence 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. The conjugated polymers of the 5, 6-dinitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type prepared in example 2 were tested for kinetic stability at 461nm, 854nm and 1100nm, respectively, with square wave potential intervals of 5s. FIG. 5 is a graph of the kinetics of the conjugated polymer of example 2, as seen in FIG. 5, the transmittance values of the polymer are approximately 16.4%, 4.88% and 9.06%, and the transmittance values remain 14.05%, 4.80% and 7.84% after 300 seconds of scanning.
(3) Short term memory effect study of polymer films
And applying 10s voltage and 2s voltage every 100s on a working electrode by using a constant potential method through an electrochemical workstation, and recording the change trend of the transmittance of the polymer in the oxidation state and the reduction state under the maximum absorption peak by using an ultraviolet-visible spectrometer at the same time, thus obtaining the short-term memory effect map of the polymer. The 5, 6-dinitro-4, 7-bis (2, 2', 3' -tetrahydro- [5,5' -bithiophene [3,4-b ] [1,4] dioxin ] -7-yl) benzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer film prepared in example 2 was applied with voltages of 0V and 1.2V at 1100nm, respectively, and FIG. 6 is a short-term memory map of the conjugated polymer of example 2, and it can be seen from FIG. 6 that the change of the transmittance of the polymer in an oxidized state was small and the transmittance in a reduced state was gradually decreased.
Example 3
Preparation of symmetrical conjugated polymer P of the D-pi-A-pi-D type (EDOT-C 12Th-2NO2 -BT):
Based on the preparation of 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ C ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor (structure (C), EDOT-C 12Th-2NO2 -BT), the chemical reaction scheme is shown below, and specific reaction steps and reaction conditions are as follows:
(1) Preparation of Compound (a)
4, 7-Dibromo-5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole (0.6 g,1.56 mmol), tributyl (4-dodecylthiophen-2-yl) stannane (2.12 g,3.90 mmol) and bis (triphenylphosphine) palladium chloride (0.044 g,0.0625 mmol) were placed in a 250mL flask. After flushing the apparatus with argon, 80mL of a mixture of toluene and 20mL of n, n-dimethylformamide was added to the flask under negative pressure. Subsequently, the mixture was heated to 120 ℃ and stirred under reflux for 48 hours. The mixture was cooled to room temperature, toluene was removed by rotary evaporation, extracted with dichloromethane and washed with saturated sodium chloride solution. The methylene chloride was removed by rotary evaporator to give a crude product. Orange-red solid (0.57 g) was obtained by column chromatography in yield 50.26％.1H NMR(400MHz,CDCl3,δ):7.32(s,2H),7.26(s,2H),2.66(t,J＝7.7Hz,4H),1.64-1.56(m,4H),1.35-1.24(m,36H),0.91-0.86(m,6H).
(2) Preparation of Compound (b)
Compound (a) (0.4 g,0.55 mmol) and N-bromosuccinimide (0.22 g,1.21 mmol) were placed in a 50mL flask, followed by N, N-dimethylformamide (15 mL) and acetonitrile (15 mL). The mixture was heated to 60℃under dark conditions and stirred for 6 hours. Pouring into 200mL of pure water, suction-filtering with a Buchner funnel to obtain crude product, and column chromatography to obtain red solid (0.2 g) with yield 41％.1H NMR(400MHz,CDCl3,δ):7.17(s,2H),2.61(t,J＝7.6Hz,4H),1.37-1.26(m,36H),0.87(t,J＝6.7Hz,6H).
(3) Preparation of Compound (c)
Compound (b) (0.15 g,0.17 mmol), tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) stannane (0.18 g,0.42 mmol) and bis (triphenylphosphine) palladium chloride (0.0047 g, 0.0070 mmol) were placed in a 250mL flask. After flushing the apparatus with argon, 80mL of a mixture of toluene and 20mL of n, n-dimethylformamide was added to the flask under negative pressure. Subsequently, the mixture was heated to 120 ℃ and stirred under reflux for 48 hours. The mixture was cooled to room temperature, toluene was removed by rotary evaporation, extracted with dichloromethane and washed with saturated sodium chloride solution. . The methylene chloride was removed by rotary evaporator to give a crude product. The purple solid (0.0753 g) was obtained by column chromatography in yield 44％.1H NMR(400MHz,CDCl3,δ):7.53(d,J＝8.0Hz,2H),6.27(s,2H),4.33(s,8H),2.26-2.15(m,4H),1.64(d,J＝3.0Hz,4H),1.25(s,37H),0.92(s,6H).
(4) Preparation of D-pi-A-pi-D conjugated polymers
The electrochemical polymerization of 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursors into corresponding polymers is carried out, and the chemical reaction schemes are shown below, and specific reaction steps and reaction conditions are as follows:
Under the protection of nitrogen, dissolving 10mL of 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthiophen-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer precursor prepared in the example 3 in refined dichloromethane to be taken as electrolyte to prepare a polymerization precursor with the concentration of 0.01mol/L and 0.1mol/L of tetrabutylammonium hexafluorophosphate as electrolyte; stirring uniformly, continuously introducing argon to protect for 20 minutes, keeping the solution under argon atmosphere, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, and depositing on the ITO conductive glass under constant potential of 0.9V to obtain the 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-receptor-pi-donor type conjugated polymer.
Application example 3
The conjugated polymer material obtained in example 3 is used in the electrochromic field as an example.
The following examples illustrate the 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymers provided by the present invention and their processes of application in the electrochromic field, but the present invention is not limited to the examples illustrated.
(1) Spectroelectrochemical
Depositing the polymer prepared in the example 3 on ITO conductive glass to form a polymer film, and placing the ITO conductive glass covered with the polymer film in a three-electrode electrolytic cell, wherein a methylene dichloride solution in which tetrabutylammonium hexafluorophosphate is dissolved is arranged in the electrolytic cell; wherein the working electrode is ITO conductive glass attached with a polymer film, the counter electrode is a platinum sheet, and the reference electrode is an Ag/AgCl electrode. The electrochemical workstation is used for regulating the voltage applied to the working electrode by utilizing a constant potential method, and simultaneously, an ultraviolet-visible spectrometer is used for recording the change trend of the absorption spectrum of the polymer under different voltages, so that the spectroelectrochemical spectrum of the polymer is obtained, and fig. 7 is a spectroelectrochemical diagram of the conjugated polymer in example 3, wherein three absorption peaks appear at the positions of 529nm,620nm and 897nm and are respectively attributed to pi-pi transition, polaron absorption peak and dual-polaron absorption peak. As the voltage increases, the 529nm absorption peak intensity of the polymer decreases or even disappears, and a new absorption peak due to polaron absorption gradually appears in the near infrared region, and the color of the polymer changes from purple to bluish.
(2) Kinetic stability study of Polymer films
And measuring the transmittance of the polymer film in an oxidation state and a reduction state under a specific wavelength by using an ultraviolet-visible spectrophotometer, so as to calculate the optical contrast, influence 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. The 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymers prepared in example 3 were tested for kinetic stability at 529nm, 897nm and 1100nm, respectively, with square wave potential intervals of 5s. FIG. 8 is a graph of the kinetics of the conjugated polymer of example 3, showing that the transmittance values of the polymer are approximately 22.25%, 16% and 33.24%, and the transmittance values remain 22.20%, 15.65% and 31.86% after 300 seconds of scanning.
(3) Short term memory effect study of polymer films
And applying 10s voltage and 2s voltage every 100s on a working electrode by using a constant potential method through an electrochemical workstation, and recording the change trend of the transmittance of the polymer in the oxidation state and the reduction state under the maximum absorption peak by using an ultraviolet-visible spectrometer at the same time, thus obtaining the short-term memory effect map of the polymer. The 4, 7-bis (5- (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) -4-dodecylthien-2-yl) -5, 6-dinitrobenzo [ c ] [1,2,5] thiadiazole symmetrical donor-pi-acceptor-pi-donor type conjugated polymer film prepared in example 3 was applied with voltages of-0.6V and 0.8V at 1100nm, and FIG. 9 is a short-term memory diagram of the conjugated polymer of example 3, and it was found that the change in transmittance of the polymer in the oxidized state was small and the change in transmittance in the reduced state was large.
Comparative example 1
An asymmetric D-pi-A-pi-D conjugated polymer P (EDOT-Th-NO 2 -BT) is specifically as follows:
The mononitro and dinitrate are respectively introduced into benzothiadiazole to synthesize polymerization precursors (EDOT-Th-NO 2 -BT and EDOT-Th-2NO 2- BT) taking mononitrated/dinitrated benzothiadiazole as an acceptor and thiophene as pi bridge and EDOT (3, 4-ethylenedioxythiophene) as a donor, and the polymers P (EDOT-Th-NO 2 -BT) and P (EDOT-Th-2 NO 2 -BT) are obtained after polymerization by an electrochemical method. See in detail Tong Tong,Shuo Wang,Daize Mo*,Kuirong Deng*.Electrochimica Acta 470(2023)143327.DOI:https://doi.org/10.1016/j.electacta.2023.143327.
After testing, the asymmetric D-pi-A-pi-D conjugated polymer P (EDOT-Th-NO 2 -BT) has shorter response time, but the asymmetric P (EDOT-Th-NO 2 -BT) shows smaller optical contrast and coloring efficiency compared with the symmetric P (EDOT-Th-2 NO 2 -BT) due to the twist angle caused by the asymmetric structure. Compared with the symmetrical D-pi-A-pi-D conjugated polymers 2EDOT-2NO 2 -BT and EDOT-C 12Th-2NO2 -BT synthesized in the embodiment of the application, the pi bridge of P (EDOT-Th-2 NO 2 -BT) is a thiophene unit, the optical contrast ratio is smaller (delta T max =23.3%) and the coloring efficiency is lower (CE max＝129C-1cm2).
The electrochromic performance test of the p-dinitrodiazosulfide derivative polymer shows that the symmetrical D-pi-A-pi-D conjugated polymer in the embodiment of the invention has good electrochromic performance such as low optical band gap, obvious color change, higher optical contrast, shorter response time, higher coloring efficiency and the like, and the polymer can be applied to practical applications such as smart windows and the like.
In summary, the invention utilizes the strong electron withdrawing capability of the nitro and the unique plane structure, is beneficial to enhancing the interaction between the donor and the receptor, and the large volume structure of the nitro is beneficial to blocking the strong intermolecular interaction of the polymer chain in space, thereby reducing the stacking density and improving the processability of the polymer; and the nitro group is adopted for symmetrical modification, the obtained 5, 6-dinitrate-2, 1, 3-benzothiadiazole is taken as a receptor unit A, and the receptor unit has high molecular binding energy and large dipole moment, is favorable for obtaining a conjugated polymer with high optical contrast and coloring efficiency, and has wide application in preparing electrochromic devices with excellent performances.
Claims (10)
1. The D-pi-A-pi-D conjugated polymer is characterized in that the conjugated polymer has a structural formula shown in the following formula (I):
In the formula (I), ar and pi are respectively and independently C6-30 aromatic hydrocarbon groups, C5-30 aromatic heterocyclic groups, C6-30 aromatic hydrocarbon groups substituted by one or more C1-50 alkyl groups and C5-30 aromatic heterocyclic groups substituted by one or more C1-50 alkyl groups; the heteroatom in the aromatic heterocyclic group includes at least one of O, S, se, N, si; n is an integer of 1 to 10000.
2. The conjugated polymer of claim 1, wherein Ar and pi are each independently thienyl, furyl, selenophenyl, pyrrolyl, thiazolyl, phenyl, fluorenyl, carbazolyl, silafluorenyl, benzodithiophene, benzodiselenophenyl, benzodifuranyl, bithiophene, and furanyl, thienocyclopentadienyl, thienopyrrolyl, thienothiloyl, 3, 4-methylenedioxythienyl, 3, 4-ethylenedioxythienyl, 3, 4-propylenedioxythienyl, 3, 4-methylenedioxyselenophenyl, 3, 4-ethylenedioxyselenophenyl, 3, 4-propylenedioxyselenophenyl, thieno [3,4-b ] [1,4] oxathialkyl, thieno [3,4-b ] [1,4] oxazinyl, or at least one of the foregoing substituted with one or more C1-50 alkyl groups.
3. The conjugated polymer of claim 2, wherein Ar and pi are each independently of the other of the following structures:
wherein R1 is H or C1-50 alkyl; p is an integer of 1 to 3.
4. A conjugated polymer according to claim 3, wherein R1 is H or C5-40 alkyl.
5. The conjugated polymer according to any one of claims 1 to 4, wherein the conjugated polymer has a structural formula shown in any one of formulas (1) to (3):
In the formulas (1) to (3), n is an integer of 1 to 10000.
6. The method for producing a conjugated polymer according to any one of claims 1 to 5, comprising the steps of: mixing 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide, stannate containing pi units and stannate containing Ar units for Stille reaction to obtain a polymerization precursor, and carrying out electrochemical polymerization on the polymerization precursor to obtain the conjugated polymer.
7. The method of claim 6, wherein the molar ratio of 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide to pi-unit containing tin compound is 1: (2-5);
And/or, the molar ratio of the 5, 6-dinitrate-2, 1, 3-benzothiadiazole bromide to the Ar unit-containing tin compound is 1: (2-5).
8. The preparation method according to claim 6, wherein the temperature of the Stille reaction is 100-140 ℃;
And/or the Stille reaction time is 36-60 h.
9. The method of claim 6, wherein the electrochemical polymerization is: and (3) taking the solution containing the polymerization precursor as electrolyte, and performing electrodeposition in a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode to obtain the polymer on the working electrode.
10. Use of a conjugated polymer according to any one of claims 1 to 5 for the preparation of an electrochromic device.
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