CN113336922B - Electrochromic polymer with high transmittance from neutral cyan to oxidized - Google Patents

Electrochromic polymer with high transmittance from neutral cyan to oxidized Download PDF

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CN113336922B
CN113336922B CN202110685398.7A CN202110685398A CN113336922B CN 113336922 B CN113336922 B CN 113336922B CN 202110685398 A CN202110685398 A CN 202110685398A CN 113336922 B CN113336922 B CN 113336922B
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cyan
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欧阳密
戴大程
张�诚
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides an electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state, modified 3, 4-ethylenedioxythiophene derivative monomers and modified dibromo D-A-D type monomers are copolymerized through direct arylation coupling polycondensation, and the color-changing color of the polymer is further regulated and controlled by regulating the pi conjugation degree and the energy band structure of the polymer, so that the conversion from the cyan to the transparent is realized. The polymer provided by the invention has electrochromic application potential, the material has high ionic conductivity, and a large amount of electrolyte ions are rapidly diffused into the polymer material to balance charges after voltage is applied, so that the color change speed of the material is accelerated, the response rate of the material is improved, and the contrast is improved.

Description

Electrochromic polymer with high transmittance from neutral cyan to oxidized
(I) technical field
The invention relates to the field of high molecular materials, in particular to an electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state and a preparation method thereof.
(II) background of the invention
In 1961, Platt firstly proposed the definition of electrochromism, which means that under the action of an applied voltage, oxidation-reduction reaction occurs due to the injection and extraction of charges, and simultaneously, along with the doping and the de-doping of electrolyte ions, the optical absorption of the material in a visible light-near infrared region changes, and macroscopically, the material shows reversible changes of color and transmissivity.
Early electrochromic materials mainly comprise inorganic electrochromic materials, but organic electrochromic materials come to the fore due to the advantages of rich structural types, excellent electrochromic comprehensive performance, good processing performance and the like, and show great application values in various fields such as intelligent windows, displays, electronic paper, automobile rearview mirrors, military camouflage, memory storage and the like. At present, the research on polymer materials focuses on the aspect of material color regulation, but the same ECP material is difficult to realize color change of various colors, and becomes a bottleneck limiting the popularization and application of the ECP material. The electrochromic polymer with various key colors converted into transparent colors is designed and synthesized, the control of various colors is realized, and the design is very important for promoting the development and application of ECP materials and devices in the display field.
Therefore, the method has extremely important significance for seeking a soluble organic electrochromic material and realizing the combination of the materials to achieve color control. The solubility can really realize large-scale low-cost commercial preparation production, and the development of the organic electrochromic material becomes a problem to be solved urgently.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of the invention
The invention aims to provide an electrochromic polymer with high transmittance from a neutral state cyan to an oxidized state and a preparation method thereof, and aims to solve the problems of poor solubility, non-ideal color regulation and the like of the conventional electrochromic material and promote the development and application of ECP (electron cyclotron resonance) materials and devices in the display field.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides an electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state as shown in a formula (1),
Figure BDA0003124429780000011
wherein n is 2-2000, all R are the same, R is C1-C10Alkyl or-CH2OR4，R4Is C1-C9Alkyl, preferably R is methyl and CH2OC8H17(particularly preferably
Figure BDA0003124429780000012
) All of R1Same as R1Is composed of
Figure BDA0003124429780000021
R2Is composed of
Figure BDA0003124429780000022
The invention also provides a preparation method of the electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state as shown in the formula (1), wherein the method comprises the following steps:
adding a compound shown as a formula (19), a compound shown as a formula (11), pivalic acid, palladium acetate and potassium carbonate into N, N-dimethylacetamide under a protective atmosphere A (such as nitrogen and argon, preferably nitrogen), reacting at 130-140 ℃ for 36-48 h (preferably 140 ℃ for 48 h), and carrying out aftertreatment K on the obtained reaction solution K to obtain the electrochromic polymer with high transmittance from a neutral state cyan state to an oxidation state shown as the formula (1); the mass ratio of the compound of formula (19) to the compound of formula (11) to the potassium carbonate is 1: 0.9-1.1: 1-3 (preferably 1: 1: 2); the mass ratio of the compound of formula (19) to palladium acetate is 25-50: 1 (preferably 25: 1); the amount ratio of the compound of formula (19) to the amount of the substance of pivalic acid is 2 to 10:1 (preferably 10: 3);
Figure BDA0003124429780000023
n is 2-2000 and R is C1-C10Alkyl or-CH2OR4，R4Is C1-C9Alkyl, preferably R is methyl and CH2OC8H17(particularly preferably
Figure BDA0003124429780000024
)，R1Is composed of
Figure BDA0003124429780000025
R2Is composed of
Figure BDA0003124429780000026
Preferably, the volume of the N, N-dimethylacetamide is 30-40 mL/g based on the mass of the compound of formula (11)
Further, the post-treatment K is: cooling the reaction solution K to room temperature, dripping the reaction solution K into methanol to separate out a solid, and filtering to obtain a crude product; sequentially carrying out Soxhlet extraction by using methanol, normal hexane, acetone and chloroform, collecting a chloroform part washing solution, removing the solvent by rotary evaporation and drying to obtain the compound shown in the formula (1).
Further, the compound of formula (19) is prepared as follows:
(1) mixing and stirring the compound (3), tributyltin chloride and tetrahydrofuran, reacting at-78 ℃ for 8-12h (preferably for 10 h), and carrying out aftertreatment D on the obtained reaction liquid D to obtain a compound shown in a formula (5); the mass ratio of the compound 3 to tributyltin chloride is 1: 1-1.3 (preferably 1: 1.2);
Figure BDA0003124429780000031
(2) mixing and stirring the compound shown in the formula (5), 4, 7-dibromo-2, 1, 3-benzothiadiazole, palladium tetrakis (triphenyl) phosphine and toluene A in a protective atmosphere B (such as nitrogen and argon, preferably nitrogen), heating at 100-110 ℃ for 16-30 hours (preferably at 110 ℃ for 24 hours), and carrying out aftertreatment F on the obtained reaction liquid F to obtain a compound shown in the formula (19); the mass ratio of the compound of the formula (5) to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 1: 2-3 (preferably 1: 2.5); the mass ratio of the compound of the formula (5) to the tetrakis (triphenyl) phosphine palladium is 20-50: 1 (preferably 25: 1);
Figure BDA0003124429780000032
in the formulae (3), (5) and (19), all R are the same and R is C1-C10Alkyl or-CH2OR4， R4Is C1-C9Alkyl, preferably R is methyl and CH2OC8H17(particularly preferably
Figure BDA0003124429780000033
)。
Preferably, the volume of the tetrahydrofuran in the step (1) is 15-20 mL/g based on the mass of the compound of the formula (3).
Further, the post-treatment D in the step (1) is as follows: and after the reaction is finished, collecting eluent containing the target compound by TLC (thin layer chromatography) with the reaction solution D by taking aluminum oxide as a stationary phase and dichloromethane as a mobile phase, and performing rotary evaporation to remove the solvent and drying to obtain the compound shown in the formula (5).
Preferably, the volume of the toluene A in the step (2) is 15-20 mL/g based on the mass of the 4, 7-dibromo-2, 1, 3-benzothiadiazole.
Further, the post-treatment G in the step (2) is as follows: extracting the reaction solution G with water and dichloromethane (3 times), collecting an extraction liquid of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1-3: 1 (preferably 2:1) as a mobile phase, collecting an eluent containing a target compound through TLC thin-layer chromatography, and performing rotary evaporation to remove a solvent to obtain the compound (19).
Further, the present invention also provides two methods for preparing the compound of formula (3):
in one aspect, R is C1-C10When alkyl, the compound (3) is prepared as follows:
mixing and stirring 3, 4-dimethoxythiophene, the compound of formula (20), p-toluenesulfonic acid and toluene B, reacting at 110-120 ℃ for 18-24 h (preferably at 110 ℃ for 18h under reflux), and carrying out post-treatment on the obtained reaction liquid B to obtain a compound of formula (3) (3, 4-ethylenedioxythiophene derivative EDOT-2R); the mass ratio of the 3, 4-dimethoxythiophene to the compound of the formula (20) is 1:2 to 3 (preferably 1: 2); the mass ratio of the 3, 4-dimethoxythiophene to the p-toluenesulfonic acid is 3-10: 1 (preferably 10: 1);
Figure BDA0003124429780000041
preferably, the volume of the toluene B is 15-20 mL/g based on the mass of the 3, 4-dimethoxythiophene.
Further, the post-treatment B is as follows: after the reaction is finished, extracting the obtained reaction liquid B with water and dichloromethane (three times), collecting dichloromethane phase extract, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1: 3-4 as a mobile phase, collecting eluent containing a target compound through TLC (thin layer chromatography), removing a solvent through rotary evaporation, and drying to obtain the compound shown in the formula (3).
On the other handR is-CH2OR4When the compound (3) is prepared as follows:
under a protective atmosphere C (preferably nitrogen), reacting a compound of formula (2) and R4OH, sodium hydride and N, N-dimethylformamide are mixed and stirred, the mixture reacts for 18 h-24 h at 130 ℃ to 140 ℃ (preferably, the reflux reaction is carried out for 18h at 135 ℃), and the obtained reaction solution C is subjected to post-treatment C to prepare a compound (3, 4-ethylenedioxythiophene derivative) shown as a formula (4); the compound of formula (2), R3The ratio of the amount of OH to the amount of sodium hydride is 1:2 to 4 (preferably 1:3: 3);
Figure BDA0003124429780000042
wherein, R is4R in OH4Is C1-C9Alkyl (preferably R)4OH is
Figure BDA0003124429780000043
)。
Preferably, the volume of the N, N-dimethylformamide is 8-15 mL/g based on the mass of the compound of the formula (II);
further, the post-treatment C is as follows: after the reaction is finished, extracting the obtained reaction liquid C with water and dichloromethane (three times), collecting dichloromethane phase extract, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1: 3-4 as a mobile phase, collecting eluent containing a target compound through TLC (thin layer chromatography), removing a solvent through rotary evaporation, and drying to obtain the compound shown in the formula (3).
Further, the compound of formula (11) is prepared as follows:
1) adding a compound shown in a formula (2), a compound shown in a formula (9), potassium iodide and potassium carbonate into N, N-dimethylformamide under a protective atmosphere D (such as nitrogen and argon, preferably nitrogen), reacting at 130-140 ℃ for 18-24 h (preferably at 140 ℃ for 36 h), and carrying out aftertreatment treatment on the obtained reaction liquid I to obtain a compound (10); the mass ratio of the compound of formula (2) to the compound of formula (9) to potassium carbonate is 1:3 to 6:3 to 5 (preferably 1:3: 5); the amount ratio of the compound of formula (2) to potassium iodide is 30 to 60:1 (preferably 60: 1);
Figure BDA0003124429780000051
2) carrying out bromination reaction on the compound of the formula (10) and N-bromosuccinimide (NBS) in chloroform at 0-20 ℃ in a dark place for 1-5 h (preferably, the reaction is carried out for 2h at 0 ℃), and carrying out aftertreatment on the obtained reaction solution J to obtain a compound of the formula (11); the ratio of the amounts of the compound (10) and NBS is 1: 2-1: 3 (preferably 1: 2.5);
Figure BDA0003124429780000052
preferably, the volume of the N, N-dimethylformamide in the step 1) is 8-15 mL/g based on the mass of the compound of the formula (9);
further, the post-treatment I in the step 1) is as follows: extracting the reaction liquid I with water and dichloromethane (three times), collecting an extraction liquid of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1: 15-20 (preferably 1:16) as a mobile phase, collecting an eluent containing a target compound through TLC (thin layer chromatography), and removing a solvent through rotary evaporation to obtain the compound of the formula (11).
Preferably, the volume of the trichloromethane in the step 2) is 10-20 mL/g based on the mass of the compound of the formula (10).
Further, the post-treatment J in the step 2) is as follows: extracting the reaction liquid J with water and dichloromethane (three times), collecting an extract of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:3 as a mobile phase, collecting an eluent containing a target compound by TLC (thin layer chromatography), removing a solvent by rotary evaporation, and drying to obtain the compound of the formula (11).
Further, the compound of formula (2) is prepared as follows:
mixing and stirring 3, 4-dimethoxythiophene, dibromoneopentyl glycol, p-toluenesulfonic acid and toluene C, reacting at 110-120 ℃ for 18-24 h (preferably at 110 ℃ for 18h under reflux), and carrying out aftertreatment A on the obtained reaction liquid A to obtain a compound (3, 4-ethylenedioxythiophene derivative EDOT-2 CH) of a formula (2)3Br); the mass ratio of the 3, 4-dimethoxythiophene to the dibromoneopentyl glycol is 1: 2-1: 3 (preferably 1: 2); the mass ratio of the 3, 4-dimethoxythiophene to the p-toluenesulfonic acid is 3:1 to 10:1 (preferably 10: 1);
Figure BDA0003124429780000061
preferably, the volume of the toluene C is 15-20 mL/g based on the mass of the 3, 4-dimethoxythiophene;
further, the post-treatment A comprises the following steps: after the reaction is finished, extracting the obtained reaction liquid A with water and dichloromethane (three times), collecting an extraction liquid of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1: 3-4 as a mobile phase, collecting an eluent containing a target compound through TLC (thin layer chromatography), removing a solvent through rotary evaporation, and drying to obtain the compound of the formula (2).
Further, the compound of formula (9) is prepared as follows:
mixing 5-hydroxyisophthalic acid, 2-ethylhexanol, concentrated sulfuric acid (the mass fraction is 98%) and toluene D, stirring, reacting at 110-120 ℃ for 18-24H (preferably at 110 ℃ for 18H by heating and refluxing), and carrying out aftertreatment H on the obtained reaction solution H to obtain a compound shown in a formula (9); the mass ratio of the 5-hydroxyisophthalic acid to the 2-ethylhexanol is 1:3 to 5 (preferably 1: 4); the volume of the concentrated sulfuric acid is 0.5-1 mL/g based on the mass of the 5-hydroxyisophthalic acid;
Figure BDA0003124429780000062
preferably, the volume of the toluene D is 15-20 mL/g based on the mass of the 5-hydroxyisophthalic acid; .
Further, the method for treating H after reaction comprises the following steps: after the reaction is finished, extracting the reaction liquid H with water and dichloromethane (three times), collecting an extraction liquid of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1-2: 1 (preferably 2:1) as a mobile phase, collecting an eluent containing a target compound through TLC (thin layer chromatography), performing rotary evaporation to remove a solvent, and drying to obtain the compound of the formula (9);
the toluene A, B, C, D of the present invention is toluene, here designated A, B, C, D, for ease of description only to distinguish the toluene from the different steps.
Compared with the prior art, the invention has the beneficial effects that: the invention provides an electrochromic polymer with high transmittance from a neutral state cyan to an oxidized state, which has a molecular structural general formula as follows:
Figure BDA0003124429780000071
wherein n is 2-2000, R is C1-C10Alkyl or-CH2OR4， R4Is C1-C9Alkyl, preferably R is methyl and CH2OC8H17(particularly preferably
Figure BDA0003124429780000072
)，R1Is composed of
Figure BDA0003124429780000073
R2Is composed of
Figure BDA0003124429780000074
The invention copolymerizes the modified 3, 4-ethylenedioxythiophene derivative monomer and the modified dibromo D-A-D type monomer through direct arylation coupling polycondensation, and regulates the color-changing color of the polymer by regulating the pi conjugation degree and the energy band structure of the polymer, thereby realizing the conversion from cyan to transparent. The polymer provided by the invention has electrochromic application potential, the material has high ionic conductivity, and a large amount of electrolyte ions are rapidly diffused into the polymer material to balance charges after voltage is applied, so that the color change speed of the material is accelerated, the response rate of the material is improved, and the contrast is improved.
(IV) description of the drawings
FIG. 1 is a synthetic route for the neutral cyan to oxidized high transmittance electrochromic polymer of example 1;
FIG. 2 is a synthetic route for the neutral cyan to oxidized high transmittance electrochromic polymer of example 2;
FIG. 3 is a graph of the UV-VIS absorption spectra at different voltages for a neutral cyan to oxidized high transmittance electrochromic polymer film of example 1;
FIG. 4 is a graph of the UV-VIS absorption spectra at different voltages for a neutral cyan to oxidized high transmittance electrochromic polymer film of example 2;
figure 5 is the electrochromic properties of the neutral cyan to oxidized high transmittance electrochromic polymer thin film of example 1.
Figure 6 is the electrochromic properties of the neutral cyan to oxidized high transmittance electrochromic polymer thin film of example 2.
Fig. 7 is the color of the neutral cyan to oxidized high transmittance electrochromic polymer film of example 1 in the neutral state.
Fig. 8 is the color of the neutral cyan to oxidized high transmittance electrochromic polymer film of example 2 in the neutral state.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1:
a molecular structural formula is
Figure BDA0003124429780000081
Wherein n is 2 to 2000, R is a cyan electrochromic polymer based on a 3, 4-ethylenedioxythiophene derivative of (1)1Is composed of
Figure BDA0003124429780000082
R2Is composed of
Figure BDA0003124429780000083
The reaction synthesis formula is shown as follows:
Figure BDA0003124429780000084
the preparation steps are as follows:
(1) sequentially adding 1.44g (10mmol) of 3, 4-dimethoxythiophene, 5.24g (20mmol) of dibromo neopentyl glycol, 0.18g (1mmol) of p-toluenesulfonic acid and 30mL of toluene into a 100mL two-neck flask, heating to react at 110 ℃ for 24 hours, extracting with water and dichloromethane three times after the reaction is finished, concentrating the extract, removing water by using anhydrous sodium sulfate, performing column chromatography purification, and performing column chromatography purification by using silica gel as a stationary phase, dichloromethane and petroleum ether as mobile phases and the volume ratio of dichloromethane to petroleum ether of 1:3, collecting the eluent containing the target compound, removing the solvent by rotary evaporation and drying to obtain the compound (3.0g, the yield is 90%) of the formula (2); the characteristic structure of the confirmed substances is as follows: 1H NMR (500MHz, CDCl)3)δ6.50(s,2H),4.10(s,4H),3.61(s,4H)。
(2) Under the protection of nitrogen, sequentially adding a compound (2g, 6mmol) of a formula (2), 2-ethylhexanol (2.34g, 18mmol), sodium hydride (0.576g, 24mmol) and 20mL of N, N-dimethylformamide into a 100mL two-neck flask, heating to react at 110 ℃ for 24 hours, extracting with water and dichloromethane three times after the reaction is finished, concentrating an extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, using silica gel as a stationary phase, dichloromethane and petroleum ether as a mobile phase, and using the volume ratio of dichloromethane to petroleum ether as 1:3, collecting the eluent containing the target compound, removing the solvent by rotary evaporation and drying to obtain the compound (2.24g, the yield is 85%) of the formula (4);1H NMR(500MHz,CDCl3)δ6.45(s,2H),4.02(s,4H),3.48(s,4H),3.29(d,J＝5.7 Hz,4H),1.57(s,12H),1.27(s,18H)。
(3) under the protection of nitrogen, the compound of formula (4) (2g, 4.5mmol) was dissolved in 20mL of anhydrous and oxygen-free Tetrahydrofuran (THF), 1.9mL (4.8mmol n-butyllithium, 2.5M) of an n-hexane solution of n-butyllithium was added dropwise at-78 deg.C, and stirring was continued for 1 hour under constant temperature, after which 1.6mL (6.0mmol) of tributyltin chloride was added, and stirring was continued for 1 hour under constant temperature, followed by natural warming to room temperature and stirring for 12 hours. After the reaction is finished, taking aluminum oxide as a stationary phase and dichloromethane as a mobile phase, collecting eluent containing the target compound, and evaporating to remove the solvent to obtain a compound (2.76g, with the yield of 84%) shown in the formula (6);
(4) 4, 7-dibromo-2, 1, 3-benzothiadiazole (0.26g, 0.9mmol), tetrakis (triphenylphosphine) palladium (30mg, 0.026mmol) were charged into a 100mL two-necked flask, and the compound of formula (6) (2g, 2.7mmol) and 20mL of toluene were added under nitrogen and heated to react at 110 ℃ for 24 hours. After the reaction is finished, extracting the mixture for three times by using water and dichloromethane, concentrating the extract, removing water by using anhydrous sodium sulfate, and carrying out column chromatography purification, wherein silica gel is used as a stationary phase, dichloromethane and petroleum ether are used as mobile phases, and the volume ratio of dichloromethane to petroleum ether is 2:1, collecting the eluent containing the target compound, removing the solvent by rotary evaporation and drying to obtain a compound (0.64g, the yield is 70%) of a formula (8); the characteristic structure of the confirmed substances is as follows: 1H NMR (500MHz, CDCl)3)δ8.29(s,2H),6.66(s,2H), 4.20(s,4H),4.10(s,4H),3.54(s,8H),3.31(d,J＝5.7Hz,8H),1.56(s,24H), 1.34-1.21(m,36H)。
(5) 1.82g (10mmol) of 5-hydroxyisophthalic acid, 5.2g (40mmol) of 2-ethylhexanol, 0.2mL (98% as a catalyst) of concentrated sulfuric acid, and 30mL of toluene were sequentially added to a 100mL two-neck flask, heated to react at 110 ℃ for 24 hours, after the reaction was completed, the mixture was extracted three times with water and methylene chloride, the extract was concentrated and then dehydrated with anhydrous sodium sulfate, column chromatography purification was performed, silica gel was used as a stationary phase, methylene chloride and petroleum ether were used as mobile phases, and the volume ratio of methylene chloride to petroleum ether was 2:1, and the eluate containing the objective compound was collected, and the solvent was removed by rotary evaporation and dried to obtain a compound of formula (9) (3.65g, yield 90%). The characteristic structure of the confirmed substances is as follows:1H NMR(500MHz,CDCl3)δ8.22(t,J＝1.4Hz,1H),7.76(d,J＝ 1.4Hz,2H),6.65(s,1H),4.26(qd,J＝11.0,5.7Hz,4H),1.71(dd,J＝12.2,6.0Hz, 2H),1.50-1.27(m,16H),0.97-0.86(m,12H)。
(6) the compound of formula (2) (2g, 6mmol), the compound of formula (9) (7.3g, 18mmol), potassium iodide (0.17g, 0.1mmol), and potassium carbonate (4.14g, 30mmol) were added to a solvent of N, N-dimethylformamide (20mL) under a nitrogen-protected atmosphere, and heated to react at 140 ℃ for 24 hours. After the reaction, water and dichloromethane are used for extraction for three times, the extract is concentrated and then water is removed by using anhydrous sodium sulfate, column chromatography purification is carried out, silica gel is used as a stationary phase, dichloromethane and petroleum ether are used as mobile phases, the volume ratio of dichloromethane to petroleum ether is 1:16, eluent containing the target compound is collected, solvent is removed by rotary evaporation, and drying is carried out, so that the compound (4.17g, the yield is 70%) of the formula (10) is obtained.1H NMR(500MHz,CDCl3)δ8.26(t,J＝1.3Hz,2H), 7.75(d,J＝1.4Hz,4H),6.51(s,2H),4.37(m,4H),4.24(m,4H)4.15(d,8H), 1.74-1.71(m,4H),1.47–1.27(m,32H),0.94-0.90(d,J＝9.7,4.2Hz,24H)。
(7) Adding the compound 10(2g, 2mmol), NBS (0.9g, 5mmol) and trichloromethane (30mL) into a 100mL double-mouth bottle in sequence, reacting for 2 hours at 0 ℃ in the absence of light, extracting with water and dichloromethane three times after the reaction is finished, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, taking silica gel as a stationary phase and dichloromethane and petroleum ether as a mobile phase at a volume ratio of 1:3, collecting the eluent containing the target compound, and performing rotary evaporation to remove the solvent and drying to obtain the compound (2.2g, 95% yield) of the formula (11).1H NMR(600MHz,CDCl3)δ8.26(t,2H,J＝1.2Hz),δ7.71 (d,4H,J＝1.2Hz),δ4.38-4.19(m,16H),δ1.72(m,4H),δ1.60-1.26(m,32H),δ 0.97-0.79(m,24H)。
(8) Under a nitrogen atmosphere, compound 8(0.50g, 0.5mmol), compound 11(0.58g, 0.5mmol), potassium carbonate (0.14g, 1mmol) and palladium acetate (4.49mg, 0.02mmol) were added to a solvent of N, N-dimethylacetamide (20ml), and heated under reflux at 120 ℃ for 48 hours; cooling to room temperature, dropping the reaction liquid into methanol solvent to separate out solid, and filtering to obtain a crude product; sequentially carrying out Soxhlet extraction by using methanol, n-hexane, acetone and chloroform solvents, collecting chloroform part washing liquid, and carrying out spin drying to obtain a cyan electrochromic polymer 1(0.79g, the yield is 80%) based on the 3, 4-ethylenedioxythiophene derivative; the GPC data are as follows: mn 1.2kDa, Mw 3.0kDa, PDI 2.49.
Dissolving the neutral cyan to oxidized electrochromic polymer 1 with high transmittance prepared in the embodiment 1 in a chloroform solvent, spin-coating the solution on an ITO glass substrate, and drying the ITO glass substrate to obtain a polymer film; taking n-tetrabutylammonium hexafluorophosphate as an electrolyte and acetonitrile as a solvent, adopting a three-electrode system, coating a polymer film on ITO in a spinning way as a working electrode, taking a platinum wire as a counter electrode and taking a silver wire as a reference electrode; the spectroelectrochemistry was measured to obtain a spectroelectrochemistry map (shown in figure 3). The color change properties of the polymer film indicate that the polymer film of this example can change from a cyan color in the neutral state to a colorless color in the oxidized state. As shown in FIG. 5, the electrochromic properties of the polymer film were 0.7s in the coloration time, 0.3s in the discoloration time, and 48% in the contrast ratio, respectively, at 675 nm. As shown in FIG. 7, the color of the polymer film in the neutral state is cyan, and the color number is R22G124B 142.
Example 2:
a molecular structural formula is
Figure BDA0003124429780000101
Wherein n is 2-2000, R is a soluble electrochromic polymer based on 3, 4-ethylenedioxythiophene derivatives of (1)1Is composed of
Figure BDA0003124429780000102
R2Is composed of
Figure BDA0003124429780000103
The reaction synthesis formula is shown as follows:
Figure BDA0003124429780000111
the preparation steps are as follows:
(1) adding 1.44g (10mmol) of 3, 4-dimethoxythiophene, 2.08g (20mmol) of neopentyl glycol, 0.18g (1mmol) of p-toluenesulfonic acid and 30mL of toluene into a 100mL two-neck flask in sequence, heating to react at 110 ℃ for 24 hours, extracting with water and dichloromethane three times after the reaction is finished, concentrating the extract, removing water with anhydrous sodium sulfate, performing column chromatography purification, and performing column chromatography purification by using silica gel as a stationary phase, dichloromethane and petroleum ether as mobile phases and the volume ratio of dichloromethane to petroleum ether being 1:3, the eluate containing the objective compound was collected, and the solvent was removed by rotary evaporation and dried to obtain a compound of formula (3) (1.66g, 90%).1H NMR(500MHz,CDCl3) δ6.47(s,2H),3.73(s,4H),1.57(s,6H).
(2) Under the protection of nitrogen, the compound of formula (3) (2g, 10.9mmol) was dissolved in 20mL of anhydrous and oxygen-free Tetrahydrofuran (THF), 4.57mL (11.4mmol, 2.5M) of n-butyl lithium n-hexane solution was added dropwise at-78 deg.C, stirring was continued for 1 hour under constant temperature, 3.84mL (14.17mmol) of tributyltin chloride was added, stirring was continued under constant temperature for 1 hour, followed by natural warming to room temperature and stirring for 12 hours. After the reaction is finished, taking aluminum oxide as a stationary phase and dichloromethane as a mobile phase, collecting eluent containing the target compound, and evaporating the solvent to obtain a liquid compound of the formula (5);
(3) 4, 7-dibromo-2, 1, 3-benzothiadiazole (0.26g, 0.9mmol), tetrakis (triphenylphosphine) palladium (30mg, 0.026mmol) were charged into a 100mL two-necked flask, and the compound of formula (5) (1.3g, 2.7mmol) and 20mL of toluene were added under nitrogen and heated to react at 110 ℃ for 24 hours. After the reaction is finished, extracting the mixture for three times by using water and dichloromethane, concentrating the extract, removing water by using anhydrous sodium sulfate, and carrying out column chromatography purification, wherein silica gel is used as a stationary phase, dichloromethane and petroleum ether are used as mobile phases, and the volume ratio of dichloromethane to petroleum ether is 2:1, the eluate containing the objective compound was collected, and the solvent was removed by rotary evaporation and dried to obtain a compound of formula (7) (0.34g, 75%) as a rose-red solid.1H NMR(500MHz,CDCl3)δ8.28(s,2H),6.71(s,2H),3.95(s,4H),3.86(s, 4H),1.56(d,J＝4.8Hz,12H)。
(4) A compound of the formula (7) (0.25g, 0.5mmol), a compound of the formula (11) (0.58g, 0.5mmol) obtained in example 1, potassium carbonate (0.14g, 1mmol) and palladium acetate (4.49mg, 0.02mmol) were added to a solvent of N, N-dimethylacetamide (20ml) under a nitrogen atmosphere, and heated under reflux at 140 ℃ for 48 hours; cooling to room temperature, dripping the reaction liquid into methanol solvent to separate out solid, and filtering to obtain a crude product; soxhlet extraction was sequentially carried out with methanol, n-hexane, acetone and chloroform, and the chloroform fraction was collected and spin-dried to obtain polymer 1(0.69g, 70%) based on a 3, 4-ethylenedioxythiophene derivative. The GPC data are as follows: mn 1.1 kDa, Mw 2.4kDa, PDI 2.14.
Dissolving the soluble electrochromic polymer 1 based on the 3, 4-ethylenedioxythiophene derivative prepared in the embodiment 2 in a chloroform solvent, spin-coating the solution on an ITO glass substrate, and drying the ITO glass substrate to obtain a polymer film; taking n-tetrabutylammonium hexafluorophosphate as an electrolyte and acetonitrile as a solvent, adopting a three-electrode system, coating a polymer film on ITO in a spinning way as a working electrode, taking a platinum wire as a counter electrode and taking a silver wire as a reference electrode; the spectroelectrochemistry was measured to obtain a spectroelectrochemistry map (shown in figure 4). The color change properties of the polymer film indicate that the polymer film of this example can change from a cyan color in the neutral state to a colorless color in the oxidized state. As shown in FIG. 6, the electrochromic properties of the polymer film were 0.24s in coloration time, 0.34s in discoloration time, and 48% in contrast, respectively, at 675 nm. As shown in FIG. 8, the color of the polymer film in the neutral state was cyan, with color number R46G91B 84.
Comparative example 1:
Figure BDA0003124429780000121
in the document Navy-to-transmissive electrochromic polymer base on 3, 4-propylenedioxythiopene (a dark blue to transparent electrochromic polymer based on 3, 4-propylenedioxythiophene), the response speed is 3.5s, and only 65% transmittance is achieved in the oxidized state, whereas in this example zhon gives the prepared electrochromic polymer I based on 3, 4-ethylenedioxythiophene derivatives a faster response speed and a high projection is achieved in the oxidized state.

Claims (10)

1. An electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state as shown in a formula (1),
Figure FDA0003490799760000011
wherein n is 2-2000, all R are the same, R is C1-C10Alkyl or-CH2OR4，R4Is C1-C9Alkyl, all of R1Same as R1Is composed of
Figure FDA0003490799760000012
R2Is composed of
Figure FDA0003490799760000013
2. A process for the preparation of a high transmittance electrochromic polymer from the neutral cyan to the oxidized state according to formula (1) as claimed in claim 1, characterized in that the process is:
adding a compound shown as a formula (19), a compound shown as a formula (11), pivalic acid, palladium acetate and potassium carbonate into N, N-dimethylacetamide under a protective atmosphere A, reacting for 36-48 h at 130-140 ℃, and carrying out aftertreatment K on the obtained reaction liquid K to obtain an electrochromic polymer with high transmittance from a neutral state cyan to an oxidized state shown as a formula (1); the mass ratio of the compound of formula (19) to the compound of formula (11) to the potassium carbonate is 1: 0.9-1.1: 1-3; the mass ratio of the compound of formula (19) to palladium acetate is 25-50: 1; the amount ratio of the compound of formula (19) to the amount of the substance of pivalic acid is 2 to 10: 1;
Figure FDA0003490799760000014
Figure FDA0003490799760000015
n is 2-2000, all R are the same, R is C1-C10Alkyl or-CH2OR4，R4Is C1-C9Alkyl, all of R1Same as R1Is composed of
Figure FDA0003490799760000021
R2Is composed of
Figure FDA0003490799760000022
3. A process for the preparation of a high transmittance electrochromic polymer from the neutral state cyan to the oxidized state represented by formula (1) according to claim 2, characterized in that: the volume of N, N-dimethylacetamide is 30-40 mL/g based on the mass of the compound of formula (11).
4. The process for the preparation of the electrochromic polymer of formula (1) from the neutral cyan to the oxidized high transmission according to claim 2, characterized in that the aftertreatment K is: cooling the reaction solution K to room temperature, dripping the reaction solution K into methanol to separate out a solid, and filtering to obtain a crude product; sequentially carrying out Soxhlet extraction by using methanol, normal hexane, acetone and chloroform, collecting a chloroform part washing solution, removing the solvent by rotary evaporation and drying to obtain the electrochromic polymer with high transmittance from a neutral state cyan to an oxidation state shown in the formula (1).
5. The process for preparing a high transmittance electrochromic polymer from the neutral cyan to the oxidized state according to formula (1) of claim 2, wherein: the protective atmosphere A is nitrogen.
6. A process for the preparation of a high transmittance electrochromic polymer from the neutral state cyan to the oxidized state, according to formula (1) as claimed in claim 2, characterized in that the compound of formula (19) is prepared as follows:
(1) mixing and stirring the compound (3), tributyltin chloride and tetrahydrofuran, reacting at-78 ℃ for 8-12h, and carrying out aftertreatment D on the obtained reaction liquid D to obtain a compound shown as a formula (5); the mass ratio of the compound 3 to the tributyltin chloride is 1: 1-1.3;
Figure FDA0003490799760000023
(2) under a protective atmosphere B, mixing and stirring a compound shown as a formula (5), 4, 7-dibromo-2, 1, 3-benzothiadiazole, tetrakis (triphenylphosphine) palladium and toluene A, heating at 100-110 ℃ for 16-30 hours, and carrying out aftertreatment on an obtained reaction solution F to obtain a compound shown as a formula (19); the mass ratio of the compound shown in the formula (5) to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 1: 2-3; the mass ratio of the compound of the formula (5) to the tetrakis (triphenylphosphine) palladium is 20-50: 1;
Figure FDA0003490799760000024
in the formulae (3), (5) and (19), all R are the same and R is C1-C10Alkyl or-CH2OR4，R4Is C1-C9An alkyl group.
7. The method for preparing electrochromic polymer having high transmittance from a neutral state cyan to an oxidized state as shown in formula (1) in claim 6, wherein the volume of the tetrahydrofuran in step (1) is 15 to 20mL/g based on the mass of the compound of formula (3).
8. The process for preparing an electrochromic polymer of formula (1) from the neutral cyan to the oxidized high transmission according to claim 6, characterized in that the post-treatment D in step (1) is: and after the reaction is finished, collecting eluent containing the target compound by TLC (thin layer chromatography) by using aluminum oxide as a stationary phase and dichloromethane as a mobile phase, and performing rotary evaporation to remove the solvent and drying to obtain the compound shown in the formula (5).
9. The process for preparing a high transmittance electrochromic polymer from the neutral cyan to the oxidized state according to formula (1) of claim 6, wherein: the volume of the toluene A in the step (2) is 15-20 mL/g based on the mass of 4, 7-dibromo-2, 1, 3-benzothiadiazole; the protective atmosphere A is nitrogen.
10. The process for preparing a high transmittance electrochromic polymer from a neutral state cyan to an oxidized state according to formula (1) of claim 6, wherein the post-treatment G in step (2) is: and extracting the reaction solution G with water and dichloromethane, collecting an extract of a dichloromethane phase, concentrating, removing water with anhydrous sodium sulfate, performing column chromatography purification by using silica gel as a stationary phase and a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1-3: 1 as a mobile phase, collecting an eluent containing a target compound by TLC (thin layer chromatography), and removing a solvent by rotary evaporation to obtain the compound (19).
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