CN111154076A - A kind of polyionic liquid containing triphenylamine-thiophene structure and its preparation method and application - Google Patents
A kind of polyionic liquid containing triphenylamine-thiophene structure and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种如式(I‑I)、(I‑II)所示的含三苯胺‑噻吩结构的聚离子液体及其制备方法，所述的聚离子液体中的不同阴离子可通过电化学聚合过程中电解质阴离子的选择而改变；本发明合成了新的含不同种类阴离子的具有电致变色性质的离子液体，通过电化学聚合得到了相应的聚合物薄膜，且该聚离子液体阴离子种类仅与电解质阴离子种类有关，具有离子可控的特点，可作为通用型原材料在只需调整电解质种类的情况下制备含不同阴离子的聚离子液体应用于电致变色等有机光电功能材料的制备。 The invention discloses a polyionic liquid containing triphenylamine-thiophene structure shown in formula (I-I) and (I-II) and a preparation method thereof. Different anions in the polyionic liquid can pass electricity The choice of electrolyte anions in the chemical polymerization process is changed; the present invention synthesizes new ionic liquids containing different kinds of anions with electrochromic properties, and obtains corresponding polymer films through electrochemical polymerization, and the polyionic liquid anion species It is only related to the type of electrolyte anion and has the characteristics of ion controllability. It can be used as a general-purpose raw material to prepare polyionic liquids containing different anions under the condition of only adjusting the type of electrolyte. It is used in the preparation of electrochromic and other organic optoelectronic functional materials.
Description
Technical Field
The invention relates to a poly ionic liquid containing a triphenylamine-thiophene structure, a preparation method thereof and application of the material in the field of novel photoelectric functional materials.
Background
In recent years, electrochromic materials have attracted much attention as a new type of photoelectric functional material. The material can change color reversibly under the action of an applied voltage, and has rich color types and easy processing. The organic electrochromic material has a great potential in practical application due to the diversity of the structural types.
Meanwhile, the ionic liquid is widely applied to an electrolyte part in an electrochromic material by virtue of higher ionic conductivity, wider electrochemical window and excellent electrochemical stability. However, through molecular design, the ionic liquid not only contains the property of electrolyte, but also can be used as electrochromic material. The ionic liquid material with the color changing function and the electrolyte function can optimize the design structure of an electrochromic device, reduce the assembly steps and reduce the economic cost. However, traditional polyionic liquid preparation requires that the monomer material itself contain different anions, greatly increasing the complexity of raw material preparation.
Disclosure of Invention
In order to solve the problem, the invention designs a material in which the anions of the ionic liquid are replaced by the anions in the electrolyte after electrochemical polymerization by utilizing the characteristic of material ion replacement.
The invention aims to design and synthesize a polyion liquid containing a triphenylamine-thiophene structure and a preparation method thereof, and the polyion liquid containing different anions can be prepared by changing the types of electrolytes, and the material is applied to the field of novel photoelectric functional materials.
The technical scheme of the invention is as follows:
a polyion liquid PTTPAC containing triphenylamine-thiophene structure as shown in formula (I-I) or (I-II)2IL-BF4；
The preparation method of the poly ionic liquid containing the triphenylamine-thiophene structure shown in the formula (I-I) or (I-II) is specifically prepared according to the following steps:
(1) dissolving an intermediate product shown in a formula (V), 4-dimethylaminopyridine (4-DMAP), 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride (EDCI) and 2-bromo-1-hexane in a dichloromethane solution, reacting for 12-16 h at 20-40 ℃, and after the reaction is finished, obtaining a reaction liquid A and carrying out post-treatment to obtain an intermediate product shown in a formula (VI); the ratio of the amounts of the intermediate product shown in the formula (V), 4-dimethylamino pyridine solution, 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride and 2-bromo-1-hexanol is 1: 0.5-0.75: 2-3: 1.5-2;
(2) dissolving an intermediate product shown in a formula (VI) and 1-methylimidazole in acetonitrile or dichloromethane solution, reacting for 30-36 h at 60-80 ℃, obtaining a reaction solution B after the reaction is finished, and carrying out aftertreatment to obtain an intermediate product shown in a formula (VII); the ratio of the amount of the intermediate product shown in the formula (VI) to the amount of the feed material of 1-methylimidazole is 1: 1.25 to 1.5;
(3) dissolving an intermediate product shown in a formula (VII) and silver tetrafluoroborate in a methanol solution under a dark condition, reacting at room temperature for 3 hours to obtain a reaction solution C after the reaction is finished, and carrying out aftertreatment to obtain a monomer shown in a formula (VIII); the ratio of the intermediate product shown in the formula (VII) to the amount of the silver tetrafluoroborate feeding substance is 1: 1.25 to 1.5; (4) dissolving the compound represented by the formula (VIII) obtained in the step (3) as a monomer in a volume ratio of 7: 3 in a mixed solvent of acetonitrile and dichloromethane, and lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Or tetrabutyl ammonium perchlorate (TBAP) is used as electrolyte, 0-1.4V cyclic voltammetry polymerization is adopted, the polymerization sweep rate is 0.1V/s, electrochemical polymerization is carried out to obtain the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-I) or (I-II), and the electrolyte is lithium tetrafluoroborate (LiBF)4) Then, the obtained product is the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-I), and the electrolyte is lithium perchlorate (LiClO)4) Or tetrabutyl ammonium perchlorate (TBAP), the obtained product is the polyion liquid containing the triphenylamine-thiophene structure shown in (I-II); what is needed isThe dosage of the electrolyte is 0.1mol/L based on the total volume of the acetonitrile/dichloromethane mixed solvent; the dosage of the compound shown in the formula (VIII) is 1-3 mmol/L based on the total volume of the acetonitrile/dichloromethane mixed solvent;
further, in the step (1), the volume usage amount of the dichloromethane is 20-25 mL/g based on the mass of the intermediate product shown in the formula (V).
Further, in the step (1), the post-treatment method of the reaction solution a comprises: and (3) cooling the reaction liquid E to room temperature, adding water and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, and performing column chromatography separation for purity, wherein the volume ratio of dichloromethane to petroleum ether is 1: and (1) eluting with the mixed solution as a mobile phase, collecting the eluent containing the target compound, evaporating the solvent under reduced pressure, and drying to obtain the intermediate product shown in the formula (VI).
Further, in the step (2), the volume usage amount of the acetonitrile or dichloromethane is 20-25 mL/g based on the mass of the intermediate product shown in the formula (VI).
Further, in the step (2), the post-treatment method of the reaction solution B comprises: and (3) cooling the reaction liquid B to room temperature, removing acetonitrile by rotary evaporation, adding ethyl glacial acetate, filtering the obtained solid-liquid mixture, collecting a filter cake, and placing the filter cake at 60 ℃ for vacuum drying for 24 hours to obtain an intermediate product shown in the formula (VII).
Further, in the step (3), the volume usage amount of the methanol is 60-75 mL/g based on the mass of the intermediate product shown in the formula (VII).
Further, in the step (3), the post-treatment method of the reaction solution C comprises: and filtering the reaction solution C to obtain a solid-liquid mixture under the condition of keeping out of the light, collecting the filtrate, removing the solvent by rotary evaporation, and placing the filtrate at 60 ℃ for vacuum drying for 24 hours to obtain the monomer shown in the formula (VIII). . The intermediate product shown in the formula (V) is prepared according to the following steps:
1) under the protection of nitrogen, dissolving sodium hydride in N, N-dimethylformamide, fully stirring until bubbles are generated, then adding diphenylamine and p-fluorobenzonitrile, reacting for 12-16 h at 100-120 ℃, obtaining a reaction liquid A after the reaction is finished, adding water and dichloromethane for extraction after the reaction liquid D is cooled to room temperature, collecting an organic phase, drying by anhydrous magnesium sulfate, and performing column chromatography separation to obtain pure dichloromethane/petroleum ether with the volume ratio of 1: 1, eluting by taking the mixed solution as a mobile phase, collecting eluent containing a target compound, evaporating the solvent under reduced pressure, and drying to obtain an intermediate product shown in a formula (II); the ratio of the amounts of the sodium hydride, the diphenylamine and the p-fluorobenzonitrile is 2-3: 1: 1 to 1.5; the volume usage of the N, N-dimethylformamide is 27-34 mL/g based on the mass of sodium hydride;
2) dissolving an intermediate product shown in a formula (II) and N-bromosuccinimide in N, N-dimethylformamide under a dark condition, reacting at room temperature for 20-24 hours to obtain a reaction liquid E, cooling the reaction liquid E to room temperature, adding water and dichloromethane for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and performing column chromatography for separation, wherein the volume ratio of dichloromethane to petroleum ether is 1: 1, eluting by taking the mixed solution as a mobile phase, collecting eluent containing a target compound, evaporating the solvent under reduced pressure, and drying to obtain an intermediate product shown in a formula (III); the ratio of the amount of the intermediate product shown in the formula (II) to the amount of the N-bromosuccinimide feeding material is 1: 2-3; the volume consumption of the N, N-dimethylformamide is 10-15 mL/g based on the mass of the intermediate product shown in the formula (II);
3) under the protection of nitrogen, dissolving an intermediate product shown in a formula (III), potassium carbonate, bis (triphenylphosphine) palladium dichloride and 2-thiopheneboronic acid in a mixed solvent of methanol and toluene, reacting at 90-110 ℃ for 20-24 h, obtaining a reaction solution F after the reaction is finished, cooling the reaction solution F to room temperature, adding water and dichloromethane for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and performing column chromatography separation for purity, wherein the volume ratio of dichloromethane to petroleum ether is 1: 1, eluting by taking the mixed solution as a mobile phase, collecting eluent containing a target compound, evaporating the solvent under reduced pressure, and drying to obtain an intermediate product shown in a formula (IV); the amount ratio of the intermediate product shown in the formula (III), potassium carbonate, bis (triphenylphosphine) palladium dichloride and 2-thiopheneboronic acid is 1: 3-4: 0.1-0.15: 2.5-3; the total volume usage of the methanol and the toluene is recorded as 13-15 mL/g of the mass of the intermediate product shown in the formula (III); the volume ratio of the methanol to the toluene is 1: 0.9 to 1.1;
4) dissolving an intermediate product shown in a formula (IV) in absolute ethyl alcohol and NaOH solution with the mass fraction of 25%, reacting for 12-16 h at 70-90 ℃, obtaining reaction liquid G after the reaction is finished, adding HCl for acidification after the reaction liquid G is cooled to room temperature, filtering out a precipitated yellow solid product, washing with deionized water, and placing at 60 ℃ for vacuum drying for 24h to obtain an intermediate product shown in a formula (V); the mass of the intermediate product represented by the formula (IV) added with the total amount of the absolute ethyl alcohol and the NaOH solution is recorded as 16-20 mL/g; the volume ratio of the absolute ethyl alcohol to the NaOH solution is 1: 0.9 to 1.1;
the target product is characterized by Nuclear Magnetic Resonance (NMR), gas mass spectrometry (GC-MS) and infrared (FTIR). And an electrochemical workstation 660E is adopted, and the ultraviolet-visible absorption spectrum represents the electrochemical and optical properties of the obtained polyion liquid film. The polyion liquid film prepared by the invention has good oxidation-reduction property, and polyion liquid containing the same anions (electrolyte anions) can be prepared due to the ion replacement effect after monomers of different anions are subjected to electrochemical polymerization under the same electrolyte.
The invention relates to application of the poly ionic liquid containing the triphenylamine-thiophene structure shown in the formula (I-I) or (I-II) in preparing electrochromic materials.
The material disclosed by the invention has the characteristics of high contrast, quick response and controllable ions, can be applied to the fields of electrochromism, energy storage and the like, and has potential application prospects in the fields of intelligent windows, displays and the like.
Compared with the prior art, the invention has the beneficial effects that: the novel ionic liquid containing different types of anions and having electrochromic property is synthesized, the corresponding polymer film is obtained through electrochemical polymerization, and the anionic species of the polyion liquid is only related to the anionic species of the electrolyte, has the characteristic of ion controllability, and can be used as a universal raw material to prepare the polyion liquid containing different anions under the condition of only adjusting the anionic species of the electrolyte.
Drawings
FIG. 1: in example 8 of the present invention, monomers were separately in electrolyte LiBF4、LiClO4Cyclic voltammetric polymerization curves in TBAP;
FIG. 2: cyclic voltammograms of films 1, 2, 3 in example 8 of the invention;
FIG. 3: the full-wave-band ultraviolet absorption curves of the films 1, 2 and 3 in the embodiment 8 of the invention;
FIG. 4: contrast and response time of films 1, 2, 3 of inventive example 8.
Detailed Description
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 14 Synthesis of- (Diphenylamino) benzonitrile
Sodium hydride (1.496g,62.3mmol) was dissolved in DMF (40mL) under nitrogen and stirred well until no air bubbles were generated. Diphenylamine (5.11g,30.2mmol) is added into the solution, after the temperature is raised to 110 ℃ and the solution is stabilized, p-fluorobenzonitrile (4.49g,37.1 mmol) is slowly added, and the system is refluxed for 12 hours. After the reaction is finished, cooling the reaction liquid to room temperature, adding saturated saline and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, concentrating the organic phase under reduced pressure, and performing column chromatography separation and purification. Taking 300-400-mesh silica gel as a stationary phase, and taking the volume ratio of dichloromethane/petroleum ether as 1: the mixture 1 was eluted with a mobile phase, and the eluate containing the objective compound was collected, evaporated under reduced pressure to remove the solvent and dried to obtain 4.75g of an intermediate 4 (dianilino) benzonitrile compound (II) as a white powder in 58.2% yield.1H NMR(500 MHz,CDCl3):δ7.43(t,2H),7.35(d,4H),7.18(d,2H),7.16(t,4H),6.97 (d,2H)；MS(EI):m/z(％):271.1.
EXAMPLE 24 Synthesis of bis (4-bromophenyl) amino) benzonitrile
The intermediate 4 (dianilino) benzonitrile compound (4g,14.8 mmol) was dissolved in DMF (30mL) under exclusion of light, and a solution of NBS (6.59g,37.1mmol) dissolved in DMF (15mL) was added dropwise and reacted at room temperature for 24 h. After the reaction is finished, cooling the reaction liquid to room temperature, adding saturated saline and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, concentrating the organic phase under reduced pressure, and performing column chromatography separation and purification. Taking 300-400-mesh silica gel as a stationary phase, and taking the volume ratio of dichloromethane/petroleum ether as 1: the mixture 1 was eluted with a mobile phase, and the eluate containing the objective compound was collected, evaporated under reduced pressure to remove the solvent and dried to obtain 6.01g of intermediate 4 (bis (4-bromophenyl) amino) benzonitrile compound (III) as a white powder in 95.6% yield.1H NMR(500MHz,CDCl3):δ7.45(d,6H), 7.00(d,6H)；MS(EI):m/z(％):428.9.
Example 34 Synthesis of bis (4- (thiophene-2) phenyl) amino) benzonitrile
The intermediate 4- (bis (4-bromophenyl) amino) benzonitrile (3.75 g,8.76mmol), potassium carbonate (5.4g,39.12mmol), bis (triphenylphosphine) palladium dichloride (780mg,1.11mmol), 2-thiopheneboronic acid (3.9g,30.47mmol) were dissolved in a mixed solution of methanol (50mL) and toluene (50mL) under nitrogen and reacted at 100 ℃ for 24 h. After the reaction is finished, cooling the reaction liquid to room temperature, adding saturated saline and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, concentrating the organic phase under reduced pressure, and performing column chromatography separation and purification. Taking 300-400-mesh silica gel as a stationary phase, and taking the volume ratio of dichloromethane/petroleum ether as 1: eluting with mixed solution 1 as mobile phase, collecting eluate containing target compound, distilling under reduced pressure to remove solvent, and drying to obtain white powdery intermediate 4- (di (4- (thiophene-2) phenyl) amino) benzonitrile compound (IV) 2.79g with high yieldThe content was 73.2%.1H NMR(500MHz, CDCl3):δ7.59(m,4H),7.48(d,2H),7.30(d,4H),7.17(d,4H),7.10(d, 2H),7.08(d,2H)；MS(EI):m/z(％):434.8.
EXAMPLE 44 Synthesis of (bis (4- (thien-2-yl) phenyl) amino) benzoic acid
The intermediate 4- (bis (4- (thiophene-2) phenyl) amino) benzonitrile compound (2.3 g,5.30mmol) was dissolved in a mixture of absolute ethanol (40mL) and 25% NaOH solution (40mL) and reacted at 80 ℃ for 14 h. After the reaction is finished, cooling the reaction solution to room temperature, adding 3MHCl (75mL) for acidification, changing the solution from clear and transparent to yellow flocculent suspension, performing suction filtration, collecting a filter cake, washing with deionized water, placing at 60 ℃ for vacuum drying for 24h to obtain 2.21g of a yellow powdery intermediate product 4 (bis (4- (thiophene-2-yl) phenyl) amino) benzoic acid compound shown as (V), wherein the yield is 91.6%.1H NMR(500MHz,CDCl3):δ7.95 (d,2H),7.58(m,4H),7.29(d,4H),7.20(d,4H),7.11(d,2H),7.09(d,2H)；MS(EI):m/z(％):454.2。
EXAMPLE 52 Synthesis of bromoethyl 4 (bis (4- (thien-2-yl) phenyl) amino) benzoate
The intermediate 4 (bis (4- (thien-2-yl) phenyl) amino) benzoic acid compound (1g,2.2mmol), 4-DMAP (0.14g,1.1mmol), EDCI (1.27g,6.6mmol), 2-bromo-1-hexanol (0.6g,3.3mmol) were dissolved in DCM (25mL) and reacted at 30 ℃ for 15 h. After the reaction is finished, cooling the reaction liquid to room temperature, adding saturated saline and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, concentrating the organic phase under reduced pressure, and performing column chromatography separation and purification. Taking 300-400-mesh silica gel as a stationary phase, and taking the volume ratio of dichloromethane/petroleum ether as 1: 1, eluting with mobile phase, collecting eluate containing target compound, distilling under reduced pressure to remove solvent, and drying to obtain intermediate 2-bromohexyl 4 (VI)Bis (4- (thien-2-yl) phenyl) amino) benzoate compound 1.19g, yield 87.8%.1H NMR(500MHz,CDCl3):δ7.93(d,2H),7.57(d,4H), 7.30(d,4H),7.17(d,4H),7.11(d,2H),7.10(d,2H),4.62(t,2H),3.65(t, 2H)(Fig.S1)；MS(EI):m/z:562.2.
Example Synthesis of 61- (2- (4- (bis (4- (thiophen-2-yl) phenyl) amino) benzoyl) oxycaproyl) -3-methyl-imidazole bromate
The intermediate 2-bromohexyl 4 (bis (4- (thiophen-2-yl) phenyl) amino) benzoate compound (690mg,1.12mmol) and 1-methylimidazole (83.3mg,1.01mmol) were dissolved in acetonitrile (15mL) and reacted at 70 ℃ for 32 hours. After the reaction, the reaction mixture was cooled to room temperature, acetonitrile was removed by rotary evaporation and ethyl glacial acetate was added, the resulting solid-liquid mixture was filtered, the filter cake was collected and placed under vacuum at 60 ℃ for 24 hours to obtain 630mg of the intermediate 1- (2- (4- (bis (4- (thiophen-2-yl) phenyl) amino) benzoyl) oxycyclohexyl) -3-methyl-bromoimidazole compound in the form of a yellow viscous liquid as shown in (VII) with a yield of 88.9%.1H NMR(500MHz,DMSO):δ9.11(s,1H),7.85(d,2H),7.77(d,1H),7.70 (d,1H),7.68(m,4H),7.55(d,2H),7.49(d,2H),7.17(d,4H),7.15(d,2H), 7.05(d,2H),4.24(t,2H),4.16(t,2H),3.84(s,3H)
Example Synthesis of 71- (2- (4- (bis (4- (thien-2-yl) phenyl) amino) benzoyl) oxycyclohexyl) -3-methylimidazolium tetrafluoroborate
The intermediate 1- (2- (4- (bis (4- (thiophen-2-yl) phenyl) amino) benzoyl) oxycyclohexyl) -3-methyl-bromoimidazole compound (276mg) and silver tetrafluoroborate (109mg) were dissolved in a methanol (20mL) solution under exclusion of light and reacted at room temperature for 3 hours. After the reaction is finished, filtering the obtained solid-liquid mixture under the condition of keeping out of the sun, collecting filtrate, removing methanol by rotary evaporation, placing at 60 ℃ for vacuum drying for 24h to obtain orange yellow as shown in (VIII)The product, 1- (2- (4- (bis (4- (thiophen-2-yl) phenyl) amino) benzoyl) oxycyclohexyl) -3-methylimidazolium tetrafluoroborate compound, 240mg, yield 86.0%.1H NMR(500MHz,DMSO):δ9.11(s,1H),7.85(d,2H),7.77(d,1H),7.70(d,1H),7.68 (m,4H),7.55(d,2H),7.49(d,2H),7.17(d,4H),7.15(d,2H),7.05(d,2H), 4.24(t,2H),4.16(t,2H),3.84(s,3H)
Example 8 electrochemical polymerization and Performance characterization
0.1mol/L LiBF is added4、LiClO4TBAP is dissolved in acetonitrile/dichloromethane in a volume ratio of 7: 3 (100mL) as a blank solution. 1- (2- (4- (bis (4- (thiophen-2-yl) phenyl) amino) benzoyl) oxyhexyl) -3-methylimidazolium tetrafluoroborate compound (2mmol/L) was dissolved in 10mL of a blank solution as a monomer solution, and the monomer solution was dispersed uniformly with ultrasound before use. And (2) performing cyclic voltammetry polymerization on the monomer solution at the polymerization sweep rate of 0.1V/s by adopting 0-1.4V, and performing electrochemical polymerization to obtain corresponding polyion liquid 1, polyion liquid 2 and polyion liquid 3 respectively. All subsequent electrochemical tests were performed in a blank solution.
The step voltage of cyclic voltammetry, spectroelectrochemistry and electrochromism tests is 0-1.2V, and test results show that different anions of the polyion liquid have influence on the electrochromism property of the polyion liquid. FIG. 4 shows the optical contrast and response time of polyionic liquids 1, 2 and 3. At 1100nm, the contrast of polyionic liquid 1 is 35%, the response time is 1.49s and 0.78s, the contrast of polyionic liquid 2 is 35%, the response time is 0.88s and 0.30s, the contrast of polyionic liquid 3 is 37%, and the response time is 0.82s and 0.29 s. Under 420nm, the contrast of the polyionic liquid 1 is 30%, the response time is 2.08s and 0.48s, the contrast of the polyionic liquid 2 is 29%, the response time is 1.63s and 0.39s, the contrast of the polyionic liquid 3 is 30%, and the response time is 1.66s and 0.44 s. Under similar optical contrast, polyion liquid 2 and polyion liquid 3 have faster response time, which shows that perchlorate ions can promote the material to change color rapidly compared with tetrafluoroborate ions.
Claims (9)
1. A poly ionic liquid containing triphenylamine-thiophene structure as shown in formula (I-I) or (I-II),
2. a method for preparing the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-I) or (I-II) as claimed in claim 1, which comprises: the method comprises the following steps:
(1) dissolving an intermediate product shown in a formula (V), 4-dimethylaminopyridine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 2-bromo-1-hexane in a dichloromethane solution, reacting at 20-40 ℃ for 12-16 h, and after the reaction is finished, obtaining a reaction liquid A and performing post-treatment to obtain an intermediate product shown in a formula (VI); the ratio of the amounts of the intermediate product shown in the formula (V), 4-dimethylamino pyridine solution, 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride and 2-bromo-1-hexanol is 1: 0.5-0.75: 2-3: 1.5-2;
(2) dissolving an intermediate product shown in a formula (VI) and 1-methylimidazole in acetonitrile or dichloromethane solution, reacting for 30-36 h at 60-80 ℃, obtaining a reaction solution B after the reaction is finished, and carrying out aftertreatment to obtain an intermediate product shown in a formula (VII); the ratio of the amount of the intermediate product shown in the formula (VI) to the amount of the feed material of 1-methylimidazole is 1: 1.25 to 1.5;
(3) dissolving an intermediate product shown in a formula (VII) and silver tetrafluoroborate in a methanol solution under a dark condition, reacting at room temperature for 3 hours to obtain a reaction solution C after the reaction is finished, and carrying out aftertreatment to obtain a monomer shown in a formula (VIII); the ratio of the intermediate product shown in the formula (VII) to the amount of the silver tetrafluoroborate feeding substance is 1: 1.25 to 1.5;
(4) dissolving the compound represented by the formula (VIII) obtained in the step (3) as a monomer in a volume ratio of 7: 3, in the acetonitrile/dichloromethane mixed solvent, taking lithium tetrafluoroborate, lithium perchlorate or tetrabutyl ammonium perchlorate as electrolyte, adopting 0-1.4V cyclic voltammetry polymerization, wherein the polymerization sweep rate is 0.1V/s, and electrochemically polymerizing to obtain the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-I) or (I-II); when the electrolyte is lithium tetrafluoroborate, the obtained product is the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-I), and when the electrolyte is lithium perchlorate or tetrabutyl ammonium perchlorate, the obtained product is the polyion liquid containing the triphenylamine-thiophene structure shown in the formula (I-II); the dosage of the electrolyte is 0.1mol/L based on the total volume of the acetonitrile/dichloromethane mixed solvent; the dosage of the compound shown in the formula (VIII) is 1-3 mmol/L based on the total volume of the acetonitrile/dichloromethane mixed solvent;
3. the method of claim 2, wherein: in the step (1), the volume usage amount of the dichloromethane is 20-25 mL/g based on the mass of the intermediate product shown in the formula (V).
4. The method of claim 2, wherein: in the step (1), the post-treatment method of the reaction solution A comprises the following steps: and (3) cooling the reaction liquid E to room temperature, adding water and dichloromethane for extraction, collecting an organic phase, drying the organic phase by anhydrous magnesium sulfate, and performing column chromatography separation for purity, wherein the volume ratio of dichloromethane to petroleum ether is 1: and (1) eluting with the mixed solution as a mobile phase, collecting the eluent containing the target compound, evaporating the solvent under reduced pressure, and drying to obtain the intermediate product shown in the formula (VI).
5. The method of claim 2, wherein: in the step (2), the volume usage amount of the acetonitrile or dichloromethane is 20-25 mL/g based on the mass of the intermediate product shown in the formula (VI).
6. The method of claim 2, wherein: in the step (2), the post-treatment method of the reaction solution B comprises the following steps: and (3) cooling the reaction liquid B to room temperature, removing acetonitrile by rotary evaporation, adding ethyl glacial acetate, filtering the obtained solid-liquid mixture, collecting a filter cake, and placing the filter cake at 60 ℃ for vacuum drying for 24 hours to obtain an intermediate product shown in the formula (VII).
7. The method of claim 2, wherein: in the step (3), the volume consumption of the methanol is 60-75 mL/g based on the mass of the intermediate product shown in the formula (VII).
8. The method of claim 2, wherein: in the step (3), the post-treatment method of the reaction solution C comprises the following steps: and filtering the reaction solution C to obtain a solid-liquid mixture under the condition of keeping out of the light, collecting the filtrate, removing the solvent by rotary evaporation, and placing the filtrate at 60 ℃ for vacuum drying for 24 hours to obtain the monomer shown in the formula (VIII).
9. The polyion liquid containing the triphenylamine-thiophene structure as shown in the formula (I-I) or (I-II) as claimed in claim 1 is applied to preparation of electrochromic materials.
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| JPH10226707A (en) * | 1996-10-03 | 1998-08-25 | Alain Vallee | Polyionic polymer compound, is production and use as a photoinitiator |
| CN106543415A (en) * | 2016-09-29 | 2017-03-29 | 浙江工业大学 | Thin polymer film based on chi structure conjugated molecule and preparation method and application |
| CN109096507A (en) * | 2018-07-09 | 2018-12-28 | 浙江工业大学 | A kind of material and the preparation method and application thereof of the triphen amine derivant based on imidazole type ion liquid modification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10226707A (en) * | 1996-10-03 | 1998-08-25 | Alain Vallee | Polyionic polymer compound, is production and use as a photoinitiator |
| CN106543415A (en) * | 2016-09-29 | 2017-03-29 | 浙江工业大学 | Thin polymer film based on chi structure conjugated molecule and preparation method and application |
| CN109096507A (en) * | 2018-07-09 | 2018-12-28 | 浙江工业大学 | A kind of material and the preparation method and application thereof of the triphen amine derivant based on imidazole type ion liquid modification |
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