CN112430312B - Electrochromic polymer containing carbazole structure, preparation method, polymer film and application - Google Patents
Electrochromic polymer containing carbazole structure, preparation method, polymer film and application Download PDFInfo
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Abstract
The invention discloses an electrochromic polymer containing carbazole structure, a preparation method, a polymer film and application, wherein the electrochromic polymer is a donor-acceptor type soluble electrochromic polymer which can be dissolved in organic solvents such as chloroform, tetrahydrofuran, toluene and the like, and the electrochromic polymer is dissolved in the organic solvents and sprayed on the surface of a conductive material to form a film capable of realizing reversible color change; the film has the characteristics of low driving potential, obvious color change, good stability, solution treatment and the like, and can be used in electrochromic devices; the preparation method is suitable for large-scale production, and electrochromic polymers with excellent performance can be prepared.
Description
Technical Field
The invention relates to the technical field of synthesis and film formation of electrochromic materials, in particular to an electrochromic polymer containing a carbazole structure, a preparation method, a polymer film and application.
Background
The electrochromic material is a material which can reversibly change optical characteristics (reflectivity, transmissivity, absorptivity) and the like under the action of an external electric field, and has good application prospect in the fields of intelligent windows, electrochromic display, self-adaptive camouflage and the like. Compared with inorganic electrochromic materials, the conductive polymer electrochromic materials have the advantages of rich colors, easiness in structural design, high color change rate, good stability and the like, and are widely paid attention to by researchers.
Generally electrochromic polymers comprise a rigid backbone of conjugated structure, in particular the incorporation of thiophene units, which significantly reduces their solubility and thus is limited in the preparation of large area devices.
Disclosure of Invention
The invention provides an electrochromic polymer containing carbazole structure, a preparation method, a polymer film and application thereof, which are used for overcoming the defects that the polymer is difficult to dissolve and the like in the prior art and obtaining a soluble electrochromic polymer.
To achieve the above object, the present invention provides an electrochromic polymer containing carbazole structure, wherein the electrochromic polymer has one of the structural formulas P (Cz-TzP), P (Cz-Th-Tz) and P (Cz-BTh-Tz):
wherein, -C 8 H 17 Is n-octyl, -C 6 H 13 Is a positive hexyl group; n represents a natural number and is a natural number between 8 and 100.
In order to achieve the above object, the present invention also provides a method for preparing an electrochromic polymer containing carbazole structure, comprising the following steps:
s1: preparing 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer through bromination reaction;
s2: 4, 7-bis (4-hexyl-dithienyl) -2,1, 3-benzothiadiazole monomer is prepared through reflux reaction;
s3: obtaining 4, 7-bis (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer through bromination reaction;
s4: and obtaining electrochromic polymer P (Cz-Tz) or P (Cz-Th-Tz) or P (Cz-BTh-Tz) containing carbazole structure through Suzuki coupling polymerization.
In order to achieve the above purpose, the present invention further provides a polymer film, which is formed by spraying the electrochromic polymer containing carbazole structure or the electrochromic polymer containing carbazole structure prepared by the preparation method; the thickness of the polymer film is 100-800 nm.
In order to achieve the above purpose, the invention also provides an application of the electrochromic polymer containing the carbazole structure in an electrochromic device, wherein the polymer is the electrochromic polymer containing the carbazole structure or the electrochromic polymer containing the carbazole structure prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the electrochromic polymer containing the carbazole structure, as the carbazole unit N atom and the thiophene unit can be introduced into the flexible alkyl chain, the interaction between polymer molecular chains can be weakened, so that the solubility of the polymer in an organic solvent is improved; the electrochromic polymer provided by the invention can be dissolved in common organic solvents such as chloroform, toluene, tetrahydrofuran, chlorobenzene and the like, can be used for preparing a large-area polymer film by spraying, spin coating, printing and the like, and can be used for assembling a large-area electrochromic device.
2. According to the preparation method of the electrochromic polymer containing the carbazole structure, provided by the invention, the ratio of reactants is controlled, so that the obtained electrochromic polymer has an electrochromic function after being sprayed into a film; meanwhile, the preparation method adopts Suzuki coupling polymerization, the polymer prepared by the coupling polymerization not only has solubility, but also can carry out purification treatment on the coupled polymerization product so as to realize the preparation of high-purity polymer.
3. The polymer film provided by the invention is prepared from the electrochromic polymer containing the carbazole structure, and the absorption spectrum of the polymer is adjusted by using thiophene units embedded in the polymer, so that the film prepared from the polymer has various color displays; meanwhile, the polymer contains a carbazole structure, and the carbazole structure enables the polymer film to be in obvious colors in a neutral state and an oxidation state, to be yellow, golden yellow, dark green or pink in the neutral state and to be transparent or light blue in the oxidation state; the polymer film can realize reversible change from yellow, golden or pink to transparent under lower driving voltage, and has the advantages of rapid response rate, higher optical contrast and good electrochemical stability; experiments prove that the transmittance contrast ratio of the polymer film provided by the invention can reach 20-30%, the response time is 1.5-3.6 s, meanwhile, the polymer film has good color-changing stability, the transmittance contrast ratio is attenuated by more than 1000 times and is within 5%, and the polymer film has potential application value in the electrochromic field and can be used for devices such as electrochromic windows, electrochromic displays and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a synthetic route and a chemical structure of an electrochromic polymer containing carbazole structure according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of 4, 7-bis (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer in example of the present invention;
FIG. 3a is a nuclear magnetic resonance spectrum of an electrochromic polymer containing carbazole structures of the P (Cz-Tz) type provided in the examples;
FIG. 3b is a nuclear magnetic resonance spectrum of the electrochromic polymer containing carbazole structure of the P (Cz-Th-Tz) type provided in the example;
FIG. 3c is a nuclear magnetic resonance spectrum of the electrochromic polymer containing carbazole structure of P (Cz-BTh-Tz) provided in the example;
FIG. 4 is a cyclic voltammogram of a polymer film obtained in an example of the present invention;
FIG. 5 is a spectrum absorption diagram and a color photograph of an electrochromic polymer containing carbazole structure in a solution state according to an embodiment of the present invention;
FIG. 6 is a spectral electrochemical spectrum of a polymer film obtained in the example of the present invention at different potentials;
FIG. 7 is a photograph showing the color change of the polymer film obtained in the example of the present invention at different electric potentials;
FIG. 8 is a graph of voltage step timing transmittance and stability of polymer films made from P (Cz-Th-Tz) polymers in examples of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention.
The drugs/reagents used are all commercially available without specific description.
The invention provides an electrochromic polymer containing a carbazole structure, which has the structural formula of one of P (Cz-TzP), P (Cz-Th-Tz) and P (Cz-BTh-Tz):
wherein, -C 8 H 17 Is n-octyl, -C 6 H 13 Is a positive hexyl group; n represents a natural number and is a natural number between 8 and 100.
Preferably, the electrochromic polymer is a donor-acceptor type soluble electrochromic polymer in which carbazole units are donor units, 2,1, 3-benzothiadiazole is an acceptor unit, and thiophene units are bridge units and donor units.
The polymer containing carbazole structure generally has the characteristics of high band gap, high charge and high electron migration rate, and the light emitted by the polymer is mainly in a visible light region under the stimulation of an external power supply, so that the carbazole structure has wide application in the synthesis of the polymer in the electroluminescent field. When carbazole units are used for synthesizing electrochromic polymers, the formed high band gap polymers have the characteristic of rich discoloration, namely, obvious colors are shown in a neutral state and an oxidation state.
The donor-acceptor type structural polymer refers to a polymer which contains an electron donor and an electron acceptor, and the band gap of the polymer can be remarkably reduced due to charge migration between the electron donor and the electron acceptor, so that the donor-acceptor type polymer often has a lower band gap. The carbazole structure and the receptor unit are combined to neutralize the influence of band gap, and simultaneously, the optical regulation and control performance is higher. Carbazole units in the electrochromic polymer containing carbazole structures can be used as donor units, 2,1, 3-benzothiadiazole can be used as acceptor units, and thiophene units can be used as bridging units and donor units.
The polythiophene is used as the most common electrochromic material, has the characteristics of rich color change, high response speed, good stability and the like, is an effective means for regulating and controlling the electrochromic performance of the polymer by bridging thiophene units onto the polymer, and can further neutralize the influence of carbazole high band gap by connecting the thiophene units to the second position and the seventh position of carbazole, and simultaneously introduces the performance characteristics of the polythiophene.
By soluble it is meant that the electrochromic polymer is soluble in common organic solvents such as chloroform, toluene, tetrahydrofuran, chlorobenzene, and the like.
The invention also provides a preparation method of the electrochromic polymer containing the carbazole structure, the synthetic route is shown in figure 1, and the preparation method comprises the following steps:
s1: preparing 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer through bromination reaction;
s2: 4, 7-bis (4-hexyl-dithienyl) -2,1, 3-benzothiadiazole monomer is prepared through reflux reaction;
s3: obtaining 4, 7-bis (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer through bromination reaction;
s4: and obtaining electrochromic polymer P (Cz-Tz) or P (Cz-Th-Tz) or P (Cz-BTh-Tz) containing carbazole structure through Suzuki coupling polymerization.
The method comprises the following specific steps:
s1: in inert atmosphere and in the absence of illumination, 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole and N-bromosuccinimide (NBS) are placed in an organic solvent for bromination reaction and purification treatment, so as to obtain 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer; the reaction route is as follows:
the purpose of the bromination reaction is to introduce Br into the 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole, which is to be used for the next polymerization reaction, and N-bromosuccinimide is used for providing Br; chloroform is used as an organic solvent to dissolve 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole and N-bromosuccinimide, so that the bromination reaction of the two is facilitated.
The bromination reaction is carried out under the condition of no illumination, so that Br (bromine) visible light decomposition is avoided.
The inert atmosphere is preferably nitrogen or argon.
The purification treatment may result in higher purity of the resulting monomer.
Preferably, the organic solvent is chloroform, which has good dissolution effect and is a common solvent.
Preferably, the mass ratio of the N-bromosuccinimide to the 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole is 2.2-3.5, and the yield is high and the raw materials are not wasted under the proportional relation; 10-20 mL of chloroform, preferably 10mL,12mL,15mL,18mL and 20mL of chloroform is added to each millimole of 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole, so as to ensure that the raw materials are dissolved completely to facilitate bromination reaction, and the solvent is not wasted.
Preferably, the bromination reaction is carried out for 24 to 48 hours at a temperature of 20 to 30 ℃. Proper reaction time ensures that the reaction is completely carried out, and proper temperature can improve the reaction efficiency without causing too much increase of the production cost.
S2: mixing 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer with thiophene tributyltin in an inert atmosphere under anhydrous and anaerobic conditions, adding a catalyst and an organic solvent, carrying out reflux reaction, and purifying to obtain 4, 7-di (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer; the reaction route is as follows:
the organic solvent is used for dissolving the raw materials; the catalyst is used for promoting the reflux reaction; in the step S2, br reacts with metallic tin to obtain 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer.
Under anhydrous and anaerobic conditions, as oxygen and water can cause the reaction to cease; the purification treatment may result in higher purity of the resulting monomer.
Preferably, the organic solvent is anhydrous tetrahydrofuran, and the organic solvent has good dissolution effect and is a common solvent; the catalyst is a palladium catalyst, the catalytic effect is obvious, other catalysts with better effects, such as palladium acetate and the like, can be selected, the addition amount of the selected catalysts is required to be adjusted, and the catalyst is particularly required to be obtained according to the test result.
The addition amount of the organic solvent is related to the amount of the 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer and the thiophene tributyltin, and the organic solvent can completely dissolve the 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer and the thiophene tributyltin.
The palladium catalyst may be tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, or the like.
Preferably, the amount of the substances of the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer, the tributyltin thiophene and the catalyst is 1: (2.2-3.5): (0.06-0.12), the product yield is higher and the reactant is not wasted; 20-40 mL of the organic solvent is added per millimole of the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer, preferably 25mL,30mL and 35mL, so as to ensure that the raw materials are dissolved completely to facilitate the reflux reaction, and the solvent is not wasted.
Preferably, the reflux reaction time is 24-48 h, preferably 24h, the reflux temperature is above the boiling point temperature of the organic solvent, the proper reaction time ensures that the reaction is complete, and the proper temperature is used for improving the reaction efficiency without causing too much increase of the production cost; when the organic solvent is anhydrous tetrahydrofuran, namely, the reflux temperature is above 70 ℃, the reflux temperature can be 75 ℃, 80 ℃, 100 ℃, 110 ℃ and the like, but the temperature is not required to be too high, so that the increase of the preparation cost is avoided.
S3: in inert atmosphere and in the absence of illumination, placing 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer and N-bromosuccinimide into an organic solvent for bromination reaction and purifying to obtain 4, 7-bis (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer; the reaction route is as follows:
the purpose of the bromination reaction is to introduce Br into the 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer, wherein the Br is introduced for the next polymerization reaction; n-bromosuccinimide is used to provide Br; chloroform is used as an organic solvent to dissolve the 4, 7-bis (4-hexyl-dithienyl) -2,1, 3-benzothiadiazole monomer and the N-bromosuccinimide, so that the bromination reaction of the 4, 7-bis (4-hexyl-dithienyl) -2,1, 3-benzothiadiazole monomer and the N-bromosuccinimide is facilitated.
The bromination reaction is carried out under the condition of no illumination, so that Br (bromine) visible light decomposition is avoided.
The inert atmosphere is preferably nitrogen or argon.
The purification treatment may result in higher purity of the resulting monomer.
Preferably, the organic solvent is chloroform, which has good dissolution effect and is a common solvent.
Preferably, the mass ratio of the N-bromosuccinimide to the 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer is 2.2 to 3.5, the product yield to this ratio is higher and no reactant is wasted; 10-20 mL of the organic solvent is added into each millimole of the 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer so as to ensure that the raw materials are dissolved completely to facilitate bromination reaction, and meanwhile, the solvent is not wasted.
Preferably, the bromination reaction is carried out for 24 to 48 hours at a temperature of 20 to 30 ℃. Proper reaction time ensures that the reaction is completely carried out, and proper temperature can improve the reaction efficiency without causing too much increase of the production cost.
S4: mixing 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer and carbazole boride in inert atmosphere under anhydrous and anaerobic condition, adding Pd 2 (dba) 3 、P(o-tolyl) 3 、K 2 CO 3 And an organic solvent, performing Suzuki coupling polymerization and purification treatment to obtain an electrochromic polymer, namely P (Cz-Tz);
mixing 4, 7-di (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer and carbazole boride in inert atmosphere under anhydrous and anaerobic condition, adding Pd 2 (dba) 3 、P(o-tolyl) 3 、K 2 CO 3 And an organic solvent, performing Suzuki coupling polymerization and purification treatment to obtain an electrochromic polymer, namely P (Cz-Th-Tz);
mixing 4, 7-di (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer and carbazole boride in inert atmosphere under anhydrous and anaerobic condition, adding Pd 2 (dba) 3 、P(o-tolyl) 3 、K 2 CO 3 And an organic solvent, performing Suzuki coupling polymerization and purification treatment to obtain an electrochromic polymer called P (Cz-BTh-Tz);
the reaction route of step S4 is as follows:
the Suzuki coupling polymerization mode has few side reactions, and the product is easy to purify; the reaction monomer used in the invention has the best effect of Suzuki coupling polymerization.
The inert atmosphere is preferably nitrogen or argon.
Under anhydrous and anaerobic conditions, as oxygen and water can cause the reaction to cease; the purification treatment may result in higher purity of the resulting monomer.
Preferably, the organic solvent is toluene, the dissolution effect is good, the solvent is a common solvent, the addition amount is determined according to the amount of the reactants, the reactants can be dissolved, and 10-20 mL of the organic solvent is generally added for every millimole of the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer or the 4, 7-bis (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer or the 4, 7-bis (5' -bromo-4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer.
Preferably, the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer or the 4, 7-bis (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer or the 4, 7-bis (5' -bromo-4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer is mixed with carbazole boride, pd 2 (dba) 3 、P(o-tolyl) 3 The amount of the substance is 1:1: (0.03-0.07): (0.06-0.14), the raw materials are saved under the proportion relationship, and the yield of the product is high.
Preferably Pd 2 (dba) 3 And P (o-tolyl) 3 The mass ratio of the substances is (3-6): (6-12), pd 2 (dba) 3 And P (o-tolyl) 3 The catalyst is a catalyst, and the catalytic effect is better in a proper proportion; the K is 2 CO 3 The concentration of (C) is 0.5-4 mol/L, and is used as a solvent for dissolving Pd 2 (dba) 3 、P(o-tolyl) 3 Addition amount and Pd 2 (dba) 3 、P(o-tolyl) 3 In relation, just the whole Pd can be dissolved 2 (dba) 3 、P(o-tolyl) 3 The preparation method is finished;
preferably, the time of the Suzuki coupling polymerization is 36-96 hours, and the reflux temperature of the Suzuki coupling polymerization is above the boiling point of the organic solvent. Proper reaction time ensures that the reaction is completely carried out, and proper temperature can improve the reaction efficiency without causing too much increase of the production cost.
The invention also provides a polymer film which is formed by spraying the electrochromic polymer containing the carbazole structure or the electrochromic polymer containing the carbazole structure prepared by the preparation method; the thickness of the polymer film is 100-800 nm.
Preferably, the film forming method of the polymer film comprises the following steps: and dissolving the electrochromic polymer containing the carbazole structure in an organic solvent to prepare a polymer solution, and then coating the polymer solution on the surface of the conductive material to form the polymer film.
Preferably, the organic solvent includes chloroform, tetrahydrofuran, toluene, etc.; the concentration of the polymer solution is 2 to 10mg/ml, and too low or too high a concentration results in poor properties of the resulting copolymer film.
The polymer film provided by the invention can be used for carrying out electrochemical and photoelectrochemical property characterization by adopting an electrochemical workstation and a spectrophotometer, adopts a three-electrode system and adopts lithium perchlorate/propylene carbonate solution as electrolyte.
The three-electrode system is characterized in that a polymer film is used as a working electrode, a stainless steel wire or a platinum wire is used as a counter electrode, and a silver wire or Ag/AgCl is used as a reference electrode.
The concentration of the electrolyte lithium perchlorate/propylene carbonate solution is 0.02-2 mol/L.
The invention also provides application of the electrochromic polymer containing the carbazole structure in electrochromic devices, wherein the polymer is the electrochromic polymer containing the carbazole structure or the electrochromic polymer containing the carbazole structure prepared by the preparation method.
The electrochromic device basically comprises an electron source, an ion source, a transparent conductive layer, an electrochromic layer, an electrolyte layer, an electrode layer and the like, and the electrochromic polymer provided by the invention can be used for developing and developing information display devices, electrochromic intelligent dimming windows, non-glare reflectors, electrochromic information memories, color varistors, high-resolution photoelectric camera equipment and other electrochromic devices, and is used as an electrochromic layer of the electrochromic device.
Example 1
The embodiment provides a preparation method of an electrochromic polymer containing a carbazole structure and having a P (Cz-BTh-Tz) structure, which comprises the following steps:
s1: 4, 7-bis (4-hexylthienyl) -2,1 under nitrogen protectionBromination of 3-benzothiadiazole (2 mmol) and NBS (4.6 mmol) was carried out in 30ml of chloroform at room temperature in the absence of light for 48 hours, the reaction mixture was poured into 200ml of water for washing, the organic phase and the aqueous phase were separated, the organic phase was collected, the aqueous phase was extracted with 20ml of methylene chloride (this extraction process was carried out three times) and the obtained extract was combined with the organic phase, dried over anhydrous magnesium sulfate, concentrated, followed by column chromatography and washing with methanol to give intermediate product 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer in a yield of 72% (general yield of 40% in the prior art). 1 H-NMR(400MHz,CDCl 3 ):δ7.77(s,2H),7.76(s,2H),2.64(m,4H),1.66(s,4H),1.32(s,12H),0.89(s,6H)。
S2: in a 100mL three-port flask, 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer (2 mmol), thiothidiazine tributyltin (5 mmol) and bis (triphenylphosphine) palladium dichloride (0.12 mmol) were added to 60mL of anhydrous tetrahydrofuran, the gas was pumped with a vacuum pump and nitrogen bottle and refluxed under nitrogen protection for 24h, the solvent was dried after cooling, 40mL of dichloromethane dissolution product was added, then rotary evaporation was performed to obtain the initial product, washing with deionized water, separating the organic and aqueous phases, collecting the organic phase, extracting the aqueous phase with 15mL of dichloromethane (this extraction process was performed three times) and combining the obtained extract with the organic phase, drying with anhydrous magnesium sulfate, concentrating, and further column chromatography with n-hexane/dichloromethane as the mobile phase (volume ratio 2/1) to obtain the intermediate product 4, 7-bis (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer as a dark red solid, which is a general yield of 38% (yield of the existing technology). 1 H-NMR(400MHz,CDCl 3 ):δ7.99(s,2H),7.83(s,2H),7.35(d,2H),7.24(d,2H),7.11(d,2H),2.84(s,4H),1.74(s,4H),1.43(s,4H),1.35(s,8H),0.88(s,6H)。
S3: the bromination reaction in step 1 was repeated except that the original reaction monomer 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole was replaced with the product 4, 7-bis (4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer in step S2 to give 4, 7-bis (5' -bromo-4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer in 73% yield (prior art)The general yield of the technique was 50%). 1 H-NMR(400MHz,CDCl 3 ) Delta 7.96 (s, 2H), 7.83 (s, 2H), 7.06 (d, 2H), 6.98 (d, 2H), 2.79 (d, 4H), 1.71 (s, 4H), 1.43 (s, 4H), 1.34 (s, 8H), 0.91 (s, 6H), as shown in FIG. 2.
S4: in a 25ml two-port flask, 4, 7-bis (5' -bromo-4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer (1 mmol) and carbazole boride (1 mmol) were added to a flask containing Pd 2 (dba) 3 (0.04mmol)、P(o-tolyl) 3 (0.08 mmol), 1.5mL of 2mol/L K 2 CO 3 Extracting and ventilating the mixed solution of aqueous solution and 20ml of toluene, maintaining nitrogen atmosphere in a double-mouth bottle, heating to 110 ℃ (the boiling point of toluene as an organic solvent is 110 ℃) for Suzuki coupling polymerization for 72 hours, cooling to room temperature to obtain a crude electrochromic polymer product turbid liquid containing carbazole structures, dripping the turbid liquid into 300ml of methanol/water (volume ratio of 1/1) mixed solution for precipitation, filtering and drying the precipitate, sequentially extracting the precipitate by 200ml of methanol, n-hexane, dichloromethane and chloroform to obtain chloroform extract, concentrating the chloroform extract to about 5ml, dripping the 5ml of concentrated solution into 300ml of methanol for precipitation again, and collecting and drying the precipitate to obtain the target polymer P (Cz-BTh-Tz), wherein the target polymer is black yellow solid with the yield of 30% (the general yield of 11% in the prior art). As shown in the figure 3c of the drawings, 1 H-NMR(400MHz,CDCl 3 ):δ8.10(br,d,2H),8.01(br,s,2H),7.79(br,s,2H),7.63(br,s,2H),7.51(br,s,2H),7.39(br,s,2H),7.14(br,s,2H),4.63(br,s,1H),2.90(br,s,4H),2.36(br,s,2H),1.98(br,s,2H),1.79(br,s,2H),1.15-1.47(br,s,36H),0.78(br,s,12H)，Mw(Da):19000，Mn(Da):9200，PDI：2.05。
example 2
The embodiment provides a preparation method of a P (Cz-Tz) electrochromic polymer containing carbazole structure, which comprises the following steps:
s1: under the protection of nitrogen, 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole (2 mmol) and NBS (6.0 mmol) are placed in 20ml of chloroform, bromination reaction is carried out for 36h at room temperature without illumination, reaction mixture is poured into 200ml of water for washing, organic phase and aqueous phase are separated, organic phase is collected, aqueous phase is extracted by 20ml of dichloromethane (the extraction process is carried out three times), obtained extract liquid is combined with the organic phase, after drying by anhydrous magnesium sulfate, concentration is carried out, column chromatography is carried out, methanol is used for washing, and intermediate product 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer is obtained.
S2: in a 100mL three-port flask, 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer (2 mmol), thiofuran tributyltin (4.4 mmol) and bis (triphenylphosphine) palladium dichloride (0.20 mmol) were added to 40mL of anhydrous tetrahydrofuran, the mixture was evacuated with a vacuum pump and a nitrogen bottle and refluxed under the protection of nitrogen for 36 hours, the solvent was dried after cooling, 40mL of dichloromethane dissolved product was added, and then rotary evaporation was performed to obtain the initial product, washing with deionized water, separating the organic phase and the aqueous phase, collecting the organic phase, extracting the aqueous phase with 15mL of dichloromethane (the extraction process was performed three times) and combining the obtained extract with the organic phase, drying with anhydrous magnesium sulfate, concentrating, and further subjecting the obtained solution to column chromatography with n-hexane/dichloromethane as the mobile phase (volume ratio 2/1) to obtain a dark red solid, namely the intermediate product 4, 7-bis (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer
S3: the bromination reaction in step 1 is repeated except that the original reaction monomer 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole is replaced by the product 4, 7-bis (4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer in step S2 to obtain 4, 7-bis (5' -bromo-4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer;
s4: in a 25ml two-necked flask, 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole (1 mmol) and carbazole boride (1 mmol) were added to a flask containing Pd 2 (dba) 3 (0.03mmol)、P(o-tolyl) 3 (0.06 mmol), 1.5mL of 2mol/L K 2 CO 3 Extracting air from the mixed solution of aqueous solution and 20ml toluene, maintaining nitrogen atmosphere in a double-mouth bottle, heating to 110 ℃ (the boiling point of toluene as an organic solvent is 110 ℃) for Suzuki coupling polymerization for 36h, cooling to room temperature to obtain a turbid solution of electrochromic polymer crude product containing carbazole structure, dripping the turbid solution into 300ml of mixed solution of methanol/water (volume ratio is 1/1) for precipitation, filtering and bakingAnd (3) carrying out Soxhlet extraction on the dry precipitate by using 200ml of methanol, normal hexane, dichloromethane and chloroform in sequence to obtain chloroform extract, concentrating the chloroform extract to about 5ml, then dripping the 5ml concentrate into 300ml of methanol for precipitation again, collecting the precipitate and drying to obtain the target polymer P (Cz-Tz) as yellow solid, wherein the yield is 65%. As shown in figure 3a of the drawings, 1 H-NMR(400MHz,CDCl 3 ):δ8.38(br,d,2H),8.17(br,s,2H),7.90(br,s,2H),7.75(br,s,2H),4.76(br,s,1H),2.50(br,s,2H),2.02(br,s,2H),1.15-1.28(br,s,24H),0.80(br,s,6H)，Mw(Da):6800，Mn(Da):4000，PDI：1.71。
in this embodiment, the reaction monomer 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole may be prepared by step S1, or obtained by purchase, and suppliers include aladine (aladin), merck sigma (sigma), and the like.
Example 3
The embodiment provides a preparation method of a P (Cz-Th-Tz) electrochromic polymer containing carbazole structure, which comprises the following steps:
s1: under the protection of nitrogen, 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole (2 mmol) and NBS (7.0 mmol) are placed in 40ml of chloroform, bromination reaction is carried out for 48h at room temperature without illumination, reaction mixture is poured into 200ml of water for washing, organic phase and aqueous phase are separated, organic phase is collected, aqueous phase is extracted by 20ml of dichloromethane (the extraction process is carried out three times), obtained extract liquid is combined with the organic phase, after drying by anhydrous magnesium sulfate, concentration is carried out, column chromatography is carried out, methanol is used for washing, and intermediate product 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer is obtained.
S2: in a 100mL three-port flask, 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer (2 mmol), thiofuran tributyltin (7.0 mmol) and bis (triphenylphosphine) palladium dichloride (0.24 mmol) were added to 80mL of anhydrous tetrahydrofuran, the air was evacuated by a vacuum pump and a nitrogen bottle, and the mixture was refluxed under nitrogen protection for 48 hours, the solvent was dried after cooling, 40mL of dichloromethane dissolved product was added, and then rotary evaporation was performed to obtain the initial product, washing with deionized water, separating the organic phase and the aqueous phase, collecting the organic phase, extracting the aqueous phase with 15mL of dichloromethane (the extraction process was performed three times) and combining the obtained extract with the organic phase, drying with anhydrous magnesium sulfate, concentrating, and further subjecting the obtained extract to column chromatography with n-hexane/dichloromethane as the mobile phase (volume ratio 2/1) to obtain a dark red solid, namely, intermediate product 4, 7-bis (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer
S3: the bromination reaction in step 1 is repeated except that the original reaction monomer 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole is replaced by the product 4, 7-bis (4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer in step S2 to obtain 4, 7-bis (5' -bromo-4-hexyldithiophene) -2,1, 3-benzothiadiazole monomer;
s4: in a 25ml two-necked flask, 4, 7-bis (4-hexyl-bisthienyl) -2,1, 3-benzothiadiazole monomer (1 mmol) and carbazole boride (1 mmol) were added to a flask containing Pd 2 (dba) 3 (0.07mmol)、P(o-tolyl) 3 (0.14 mmol), 1.5mL of 2mol/L K 2 CO 3 Extracting and ventilating the mixed solution of aqueous solution and 20ml of toluene, maintaining nitrogen atmosphere in a double-mouth bottle, heating to 110 ℃ (the boiling point of toluene as an organic solvent is 110 ℃) for Suzuki coupling polymerization for 96 hours, cooling to room temperature to obtain a crude electrochromic polymer product turbid liquid containing carbazole structures, dripping the turbid liquid into 300ml of methanol/water (volume ratio of 1/1) mixed solution for precipitation, filtering and drying the precipitate, sequentially extracting the precipitate by 200ml of methanol, n-hexane, dichloromethane and chloroform to obtain chloroform extract, concentrating the chloroform extract to about 5ml, dripping the 5ml of concentrated solution into 300ml of methanol for precipitation again, collecting and drying the precipitate to finally obtain the target polymer P (Cz-Th-Tz) as yellow solid with the yield of 80 percent. As shown in figure 3b of the drawings, 1 H-NMR(400MHz,CDCl 3 ):δ8.24(br,d,2H),8.14(br,s,2H),7.76(br,s,2H),7.70(br,s,2H),7.05(br,s,2H),4.70(br,s,1H),2.65(br,s,4H),2.33(br,s,2H),1.92(br,s,2H),1.67(br,s,4H),1.14-1.38(br,s,36H),0.87(br,s,12H)，Mw(Da):13400，Mn(Da):7200，PDI：1.86。
example 4
The electrochromic polymers P (Cz-BTh-Tz), P (Cz-Tz) and P (Cz-Th-Tz) prepared in examples 1 to 3 were formed into polymer films, respectively:
dissolving electrochromic polymer in chloroform to prepare polymer solution of 4mg/ml, filtering to eliminate insoluble matter, spraying in a spray gun with air pressure of 2MPa, vacuum drying in a vacuum drier at 40 deg.c to form polymer film of 420nm thickness.
(1) Electrochemical performance and solution spectroscopic testing of electrochromic polymers and polymer films:
three electrode system and electrolyte system: the three-electrode system is adopted, a stainless steel sheet is used as a counter electrode, a calibrated silver wire is used as a reference electrode, a polymer film is used as a working electrode, and a supporting electrolyte is as follows: 0.2mol/L of lithium perchlorate propylene carbonate solution.
The cyclic voltammogram of the polymer film is shown in FIG. 4, and the scanning voltage ranges from-1.8V to 1.2V. As can be seen from the figure, the polymer film can complete oxidation doping in the range of 0.3V-1.1V, and can complete reduction doping in the range of-0.7V-1.8V.
The spectrum electrochemical spectrogram of the polymer film under different applied voltages is shown in figure 6, the color conversion photo is shown in figure 7, the single absorption peak of the neutral state P (Cz-Tz) polymer film is at 446nm, the polymer film presents yellow, the polymer film is transparent yellow after being completely oxidized, and the absorption peak at 446nm is weakened; the single absorption peak of the P (Cz-Th-Tz) polymer film is positioned at 502nm, and is golden yellow, the absorption peak at 502nm is weakened after complete oxidation, the absorption peak at 680nm is strengthened, and the trough exists at 562nm, so that the film is dark green; the double absorption peaks of the P (Cz-BTh-Tz) polymer film are positioned at 398nm and 533nm, and the P (Cz-BTh-Tz) polymer film presents pink color, and presents light blue color after complete oxidation, and the absorption in the visible light region is obviously reduced.
The electrochromic polymer was dissolved in chloroform to form a polymer solution at a concentration of 2 x 10 -4 The color photograph and spectral absorption curve of the solution at mg/mL are shown in FIG. 5. The P (Cz-Tz) single absorption peak is at 433nm and shows yellow color, the P (Cz-Th-Tz) single absorption peak is at 483nm and shows orange color, and the P (Cz-BTh-Tz) single absorption peak is at 512nm, appear dark red.
(2) Voltage step timing electric quantity/timing absorbance test is carried out on a polymer film made of a P (Cz-Th-Tz) polymer:
the step potential was-0.4V and 1.15V, and the voltage residence time was 5s, using the three electrode system and the electrolyte system described above.
As shown in FIG. 8, the polymer film has a reversible color change process, a transmittance contrast ratio of 15% at 502nm, and response times for the oxidation process and the reduction process to reach 90% transmittance difference of 1.8s and 3.6s, respectively, and a transmittance contrast ratio of 5% is lost 1000 times of cyclic color change.
The embodiment shows that the polymer film prepared by the invention has rich color conversion, is embedded and regulated by a thiophene structure, has the characteristics of obvious color change, high color change rate, good stability and the like, and can be applied to the fields of preparation of double-color electrochromic devices, electrochromic display, self-adaptive camouflage and the like.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the description of the present invention and the accompanying drawings or direct/indirect application in other related technical fields are included in the scope of the invention.
Claims (5)
1. Use of an electrochromic polymer containing carbazole structures in the preparation of a yellow, golden or pink to transparent reversible change polymer film, characterized in that the polymer film is spray coated with an electrochromic polymer containing carbazole structures selected from the group consisting of P (Cz-Tz), P (Cz-Th-Tz) and P (Cz-BTh-Tz); the preparation method of the electrochromic polymer containing the carbazole structure comprises the following steps:
s1: in inert atmosphere and in the absence of illumination, 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole and N-bromosuccinimide are placed in an organic solvent for bromination reaction, and purification treatment is carried out to obtain 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer; the mass ratio of the N-bromosuccinimide to the 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole is 2.2-3.5; adding 10-20 mL of the organic solvent into every millimole of the 4, 7-bis (4-hexylthienyl) -2,1, 3-benzothiadiazole;
s2: mixing 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer with thiophene tributyltin in an inert atmosphere under anhydrous and anaerobic conditions, adding a catalyst and an organic solvent, carrying out reflux reaction, and purifying to obtain 4, 7-di (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer; the mass ratio of the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer to the thiophene tributyltin to the catalyst is 1: (2.2-3.5): (0.06-0.12); adding 20-40 mL of the organic solvent per millimole of the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer;
s3: in inert atmosphere and in the absence of illumination, placing 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer and N-bromosuccinimide into an organic solvent for bromination reaction and purifying to obtain 4, 7-bis (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer; the mass ratio of the N-bromosuccinimide to the 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer is 2.2-3.5; adding 10-20 mL of the organic solvent into every millimole of the 4, 7-bis (4-hexyl-dithienyl) -2,1, 3-benzothiadiazole monomer;
s4: mixing 4, 7-di (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer or 4, 7-di (4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer or 4, 7-di (5' -bromo-4-hexyl-dithiophene) -2,1, 3-benzothiadiazole monomer with carbazole boride in inert atmosphere under anhydrous and anaerobic condition, adding Pd 2 (dba) 3 、P(o-tolyl) 3 、K 2 CO 3 Carrying out Suzuki coupling polymerization and purification treatment on the solution and an organic solvent to obtain an electrochromic polymer containing carbazole structure, wherein the electrochromic polymer is called P (Cz-Tz) or P (Cz-Th-Tz) or P (Cz-BTh-Tz); the 4, 7-bis (4-hexyl-5-bromo-thienyl) -2,1, 3-benzothiadiazole monomer or the 4, 7-bis (4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomerOr the 4, 7-di (5' -bromo-4-hexyl-bithiophene) -2,1, 3-benzothiadiazole monomer and carbazole boride, pd 2 (dba) 3 、P(o-tolyl) 3 The mass ratio of the substances is 1:1: (0.03 to 0.07): (0.06-0.14);
the structural formulas of P (Cz-Tz), P (Cz-Th-Tz) and P (Cz-BTh-Tz) are respectively as follows:
wherein, -C 8 H 17 Is n-octyl, -C 6 H 13 Is a positive hexyl group; n represents a natural number, and the polymerization degree is 8-100;
the electrochromic polymer is a donor-acceptor type soluble electrochromic polymer, wherein a carbazole unit is a donor unit, 2,1, 3-benzothiadiazole is an acceptor unit, and a thiophene unit is a bridging unit and a donor unit.
2. The use according to claim 1, wherein,
in the step S1, the organic solvent is chloroform;
in the step S2, the organic solvent is anhydrous tetrahydrofuran, and the catalyst is a palladium catalyst;
in the step S3, the organic solvent is chloroform;
in the step S4, the organic solvent is toluene.
3. The use according to claim 1, wherein,
in the S1 and the S3, the bromination reaction time is 24-48 hours, and the temperature is 20-30 ℃;
in the step S2, the time of the reflux reaction is 24-48 hours, and the reflux temperature is above the boiling point temperature of the organic solvent;
in the step S4, the time of the Suzuki coupling polymerization is 36-96 h, and the reflux temperature of the Suzuki coupling polymerization is above the boiling point of the organic solvent.
4. The use according to claim 1, wherein the polymer film has a thickness of 100 to 800nm.
5. The use according to claim 4, wherein the film forming method of the polymer film comprises: and dissolving the electrochromic polymer containing the carbazole structure in an organic solvent to prepare a polymer solution, and then coating the polymer solution on the surface of the conductive material to form the polymer film.
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| " Simple Synthesis of P(Cbz- alt -TBT) and PCDTBT by Combining Direct Arylation with Suzuki Polycondensation of Heteroaryl Chlorides";Florian Lombeck et al.;《Macromol. Rapid Commun.》;20151231;第231-237页 * |
| "A Spectroscopic and DFT Study of the Electronic Properties of Carbazole-Based D−A Type Copolymers";Matthew E. Reish et al.;《 J. Phys. Chem. C》;20120918;第21255-21266页 * |
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