CN109880063B - Conjugated polymer based on benzodithiophene unit, preparation method and application - Google Patents
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- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a conjugated polymer based on a benzodithiophene unit, and a preparation method and application thereof. The structure of the conjugated polymer based on benzodithiophene unitThe formula is shown as follows:
wherein n is an integer between 15 and 40. Compared with the traditional organic conjugated polymers such as polyaniline, polypyrrole, polythiophene, polycarbazole and the like, the conjugated polymer based on the benzodithiophene unit provided by the invention has higher carrier mobility due to a large planar pi electron conjugated structure and strong pi-pi interaction, and further has higher Seebeck coefficient and excellent thermoelectric property. Meanwhile, the polymer is easy to dissolve in common organic solvents such as dichloromethane, trichloromethane, chlorobenzene and the like, has good processability and thermal stability, and can be prepared into large-area flexible thermoelectric devices.
Description
Technical Field
The invention relates to the field of organic thermoelectric materials, in particular to a conjugated polymer based on a benzodithiophene unit, and a preparation method and application thereof.
Background
With the increasing shortage of energy supply and the increasing severity of environmental pollution, the importance of using thermoelectric materials to generate electricity from low-grade energy and waste heat for solving energy and environmental problems is gradually appearing. Thermoelectric materials are semiconductor functional materials which utilize the transport and interaction of carriers and phonons in solid to realize the interconversion between heat energy and electric energy, and the performance of the thermoelectric materials is usually expressed by thermoelectric figure of merit ZT ═ S2The characterization is carried out by sigma T/kappa, wherein S is the Seebeck coefficient of the material, sigma is the electric conductivity, T is the thermodynamic temperature, kappa is the thermal conductivity, and S is2σ is called the power factor. The larger the ZT value is, the higher the thermoelectric conversion efficiency is, and a thermoelectric material having excellent performance is required to have a larger Seebeck coefficient, high electrical conductivity, and low thermal conductivity. However, the Seebeck coefficient, the electrical conductivity and the thermal conductivity of the thermoelectric material are not independent of each other, but all depend on the electronic structure of the material and the transport characteristics of carriers.
Compared with inorganic thermoelectric materials (alloy and solid solution thereof, skutterudite, calcium cobaltate-based oxide, boride, high manganese silicide and the like), the organic polymer thermoelectric material has the advantages of rich resources, low cost, easy synthesis, easy processing and forming, environmental friendliness and the like, and is paid much attention to. Particularly, most polymer materials have very low thermal conductivity, about only 0.1-1W/mK, which is 1-2 orders of magnitude lower than that of inorganic semiconductor thermoelectric materials, which is very beneficial for improving the thermoelectric performance of the materials, so that the thermoelectric performance of organic polymers is also characterized by a power factor. However, the conductivity and the Seebeck coefficient of the organic polymer after chemical doping are still at very low levels, so that the power factor of the material is difficult to improve and the application is very difficult.
Improving the carrier mobility of the organic semiconductor is an important way for obtaining high conductivity and high Seebeck coefficient. Generally, the organic polymer has the characteristics of large planar pi electron conjugated structure, strong pi-pi interaction and easy crystallization, so that the introduction of the planar pi electron conjugated structural unit into a molecular chain is a key point of thermoelectric high molecular structure design. The condensed ring thiophene has the characteristics of obvious molecular planarity, conjugation, electron delocalization and the like, so that the polymer containing the condensed ring thiophene unit has higher carrier mobility, and the common condensed ring thiophene unit comprises: di-and tri-benzothiophenes, benzodithiophenes, and indacenodithiophenes, and the like. The literature reports that 4, 8-dialkoxy substituted benzodithiophene unit and ester group substituted thieno [3,4-b ] thiophene are copolymerized, and the obtained polymer shows higher hole mobility and wide-range visible light absorption. Therefore, excellent thermoelectric properties are expected to be obtained by preparing a conjugated polymer based on a benzodithiophene unit.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a conjugated polymer based on a benzodithiophene unit, a preparation method and an application thereof, and aims to solve the problem that the power factor of a material is difficult to improve because the conductivity and the Seebeck coefficient of the conventional conjugated polymer are still at very low levels after chemical doping.
The technical scheme of the invention is as follows:
a conjugated polymer based on benzodithiophene units, wherein the formula is shown in the following formula:
A preparation method of the conjugated polymer based on the benzodithiophene unit comprises the following steps:
the following monomers were provided:
a monomer I:
monomer II:
and adding the monomer I and the monomer II into an organic solvent, adding a catalyst and a ligand, and carrying out a Stille coupling reaction to prepare the conjugated polymer based on the benzodithiophene unit.
Further, the catalyst is tris (dibenzylideneacetone) dipalladium or tetrakis (triphenylphosphine) palladium.
Further, the ligand is tri (o-tolyl) phosphine.
Further, the organic solvent is anhydrous deoxygenated toluene or chlorobenzene.
Further, the molar ratio of the monomer I to the monomer II is 1: 1.
Further, the temperature of the Stille coupling reaction is 105-115 ℃.
Further, the time of the Stille coupling reaction is 70-75 hours.
The invention also relates to the application of the conjugated polymer based on the benzodithiophene unit in serving as a thermoelectric material.
Has the advantages that: compared with the traditional organic conjugated polymers such as polyaniline, polypyrrole, polythiophene, polycarbazole and the like, the conjugated polymer based on the benzodithiophene unit provided by the invention has higher carrier mobility due to a large planar pi electron conjugated structure and strong pi-pi interaction, and further has higher Seebeck coefficient and excellent thermoelectric property. Meanwhile, the polymer is easy to dissolve in common organic solvents such as dichloromethane, trichloromethane, chlorobenzene and the like, has good processability and thermal stability, and can be prepared into large-area flexible thermoelectric devices.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of a conjugated polymer based on benzodithiophene units in the examples.
FIG. 2 is a thermogravimetric plot of a conjugated polymer based on benzodithiophene units in the examples.
FIG. 3 shows SEM pictures of the conjugated polymer film based on benzodithiophene unit before and after doping (a is the film before doping and b is the film after doping) in the example.
FIG. 4 is a diagram showing UV-VIS-NIR absorption spectra of the conjugated polymer film based on benzodithiophene units of the example before and after doping.
FIG. 5 is a graph of thermoelectric performance of films of conjugated polymers based on benzodithiophene units in examples after doping.
FIG. 6 is a graph showing the variation of conductivity of a benzodithiophene unit-based conjugated polymer film in an exemplary embodiment at a temperature range of 100-300K (a is the natural logarithm of the conductivity ln (σ) and the reciprocal T of the temperature T-1B is the natural logarithm of the conductivity ln (σ) and the temperature T-1/2Schematic diagram of the relationship (c).
FIG. 7 is a graph of XPS S2 p signals for films of conjugated polymers based on benzodithiophene units in examples.
Detailed Description
The invention provides a conjugated polymer based on a benzodithiophene unit, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a conjugated polymer based on a benzodithiophene unit, wherein the structural formula of the conjugated polymer is shown as the following formula:
Compared with the traditional organic conjugated polymers such as polyaniline, polypyrrole, polythiophene, polycarbazole and the like, the conjugated polymer based on the benzodithiophene unit provided by the invention has higher carrier mobility due to a large planar pi electron conjugated structure and strong pi-pi interaction, and further has higher Seebeck coefficient and excellent thermoelectric property. Meanwhile, the polymer is easy to dissolve in common organic solvents such as dichloromethane, trichloromethane, chlorobenzene and the like, has good processability and thermal stability, and can be prepared into large-area flexible thermoelectric devices.
The embodiment of the invention provides a preparation method of a conjugated polymer based on a benzodithiophene unit, which comprises the following steps:
the following monomers were provided:
a monomer I:
monomer II:
and adding the monomer I and the monomer II into an organic solvent, adding a catalyst and a ligand, and carrying out a Stille coupling reaction to prepare the conjugated polymer based on the benzodithiophene unit.
In one embodiment, the catalyst is tris (dibenzylideneacetone) dipalladium or tetrakis (triphenylphosphine) palladium.
In one embodiment, the ligand is tri (o-tolyl) phosphine, which is used to facilitate the Stille coupling reaction.
In one embodiment, the organic solvent is toluene or chlorobenzene that is anhydrous and oxygen-scavenging.
In one embodiment, the molar ratio of monomer I to monomer ii is 1: 1.
In one embodiment, the temperature of the Stille coupling reaction is 105-115 ℃.
In one embodiment, the time for the Stille coupling reaction is 70 to 75 hours.
The invention also relates to the application of the conjugated polymer based on the benzodithiophene unit in serving as a thermoelectric material.
The present invention will be described in further detail with reference to specific examples.
1. Synthesis of conjugated polymers based on benzodithiophene units
(1) To a dry three-necked flask was quickly added 131.57mg of monomer I:
38.85mg of monomer II:
5.92mg of tris (dibenzylideneacetone) dipalladium and 7.88mg of tris (o-tolyl) phosphine, the flask was purged with argon after connecting to a reflux unit and sealed, and 6ml of oxygen-removed anhydrous toluene was added to the flask via a syringe.
(2) The flask containing the reaction raw materials is placed in an oil bath kettle on a magnetic stirrer, the temperature is slowly raised to 110 ℃, and the reaction is carried out for 72 hours under constant temperature and reflux.
(3) The mixed solution obtained by cooling to room temperature was diluted with chloroform and washed with deionized water, and the organic layer obtained by separation was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain a solid.
(4) And dissolving the solid in a mixed solvent of tetrahydrofuran/acetone, centrifuging at the rotating speed of 7000rpm for 30 minutes, purifying and drying to obtain the target product.
2. Preparation and chemical doping of conjugated polymer film based on benzodithiophene unit
(1) 40mg of the synthesized polymer was weighed out and dissolved in 4ml of anhydrous chlorobenzene, and the solution was dissolved completely by sonication for 1 hour.
(2) Cutting the purchased glass slide into 15 x 15mm2The small pieces are sequentially washed by deionized water, acetone and isopropanol and dried by nitrogen. Dripping the polymer solution prepared in the step (1) on the surface of a clean glass slide at room temperature until the solvent is volatilized to form a film.
(3) Dissolving anhydrous ferric chloride in nitromethane to obtain a bright yellow solution of 20mg/ml, soaking the polymer film in the solution for chemical doping, taking out after 1 minute, fully cleaning with the nitromethane, and airing.
3. Results and analysis
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of the resulting conjugated polymer based on a benzodithiophene unit dissolved in deuterated chloroform at 600MHz, from which the information of the polymer is shown below:1H NMR(600MHz，CDCl3δ ppm) 7.71(s,2H),7.44(s,2H),6.92(s,2H),4.39(s,4H),3.74(s,4H),1.33-2.18 (broad peak, 18H),0.78-1.12 (broad peak, 12H). Wherein the peak a corresponds to a benzodithiophene unit, the peak b and the peak c correspond to a bithiophene unit, and the peak d corresponds to an ethylenedioxythiophene unit.
FIG. 2 is a thermogravimetric curve of a conjugated polymer based on benzodithiophene units under a nitrogen atmosphere (airflow rate of 40mL/min, heating rate of 10 ℃/min), wherein weight loss occurs only when the temperature rises to over 230 ℃, and the decomposition temperature is about 395 ℃ when the weight loss reaches 95%, and the polymer shows good thermal stability.
FIG. 3 shows SEM pictures of a conjugated polymer film based on benzodithiophene units before and after doping (a is the film before doping, and b is the film after doping). The surface of the film before doping is compact and flat, only a small amount of particles are available, and the surface appearance of the film after doping with ferric chloride is not obviously changed, which shows that the doping has little influence on the appearance of the polymer film.
FIG. 4 is a UV-VIS-NIR absorption spectrum of a film of a conjugated polymer based on benzodithiophene units, with the undoped polymer having a maximum absorption peak at 567nm and an apparent shoulder indicating a strong π - π interaction between molecules. The optical bandgap of the polymer, calculated from the initial absorption wavelength of 632nm, is about 1.96eV, and is a narrower bandgap polymer. After chemical doping, the absorption at 567nm is reduced, and a broad absorption occurs in the long wavelength direction, which is related to the formation of carriers such as polarons.
FIG. 5 shows the thermoelectric properties of a conjugated polymer film based on benzodithiophene units after doping with temperature. The film conductivity is about 1.64S cm at room temperature-1The Seebeck coefficient is 115.58 mu V.K-1Calculated power factor of 2.19 μ W m-1·K-2. With the increase of the environmental temperature, the conductivity of the film is gradually reduced, and the Seebeck coefficient is obviously increased. When the temperature reaches 350K, the Seebeck coefficient is as high as 882.4 mu V.K-1. The power factor shows the same change trend with the temperature rise as the Seebeck coefficient, and the power factor at 350K is about 101.3 mu W.m-1·K-2。
FIG. 6 shows the relationship between the conductivity and the temperature of the conjugated polymer film based on benzodithiophene units in the low temperature range (100-300K). From FIG. 6(a), the natural logarithm of the conductivity ln (σ) and the reciprocal T of the temperature T are found-1The linear relation is formed, the activation energy of the carrier is calculated to be about 40.5meV according to an Arrhenius equation, and the carrier distribution is easier to be delocalized due to low activation energy. Further, ln (. sigma.) and T are found in FIG. 6(b)-1/2And also linearly, indicating that the conduction of carriers among polymer molecular chains conforms to a one-dimensional transition mode in this temperature range.
Fig. 7 is a graph of XPS S2 p signals of a conjugated polymer film based on benzodithiophene units, and the S peak is significantly shifted toward a low binding energy direction after doping with anhydrous ferric chloride, confirming that chemical doping occurs, and the electron cloud density around the S atom is changed. However, after heating, the S peak moves to the direction of high binding energy, and probably the Seebeck coefficient of the polymer film is increased because the doping degree is slightly reduced by increasing the temperature.
In conclusion, compared with the traditional organic conjugated polymers such as polyaniline, polypyrrole, polythiophene and polycarbazole, the conjugated polymer based on the benzodithiophene unit provided by the invention has higher carrier mobility due to a large planar pi electron conjugated structure and strong pi-pi interaction, and further has higher Seebeck coefficient and excellent thermoelectric property. Meanwhile, the polymer is easy to dissolve in common organic solvents such as dichloromethane, trichloromethane, chlorobenzene and the like, has good processability and thermal stability, and can be prepared into large-area flexible thermoelectric devices.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. Conjugated polymer based on benzodithiophene units, characterized in that it has the formula:
2. A method for preparing a benzodithiophene unit-based conjugated polymer according to claim 1, comprising the steps of:
the following monomers were provided:
a monomer I:
monomer II:
and adding the monomer I and the monomer II into an organic solvent, adding a catalyst and a ligand, and carrying out a Stille coupling reaction to prepare the conjugated polymer based on the benzodithiophene unit.
3. The method according to claim 2, wherein the catalyst is tris (dibenzylideneacetone) dipalladium or tetrakis (triphenylphosphine) palladium.
4. The method of claim 2, wherein the ligand is tri (o-tolyl) phosphine.
5. The method for preparing a conjugated polymer based on benzodithiophene unit according to claim 2, wherein said organic solvent is toluene or chlorobenzene which is anhydrous and oxygen-scavenging.
6. The method of claim 2, wherein the molar ratio of monomer I to monomer II is 1: 1.
7. The method for preparing a benzodithiophene unit-based conjugated polymer according to claim 2, wherein the temperature of the Stille coupling reaction is 105-115 ℃.
8. The process for the preparation of conjugated polymers based on benzodithiophene units according to claim 2, wherein the time of the Stille coupling reaction is 70-75 hours.
9. Use of a conjugated polymer based on benzodithiophene units according to claim 1 as a thermoelectric material.
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| CN108395556A (en) * | 2018-03-27 | 2018-08-14 | 中国科学院化学研究所 | A kind of high regularity polythiophene film and preparation method thereof with excellent thermoelectricity capability |
| CN108623791A (en) * | 2018-05-21 | 2018-10-09 | 深圳大学 | A kind of organic thermoelectric film material of D-A type conjugated polymer and preparation method thereof |
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| CN108395556A (en) * | 2018-03-27 | 2018-08-14 | 中国科学院化学研究所 | A kind of high regularity polythiophene film and preparation method thereof with excellent thermoelectricity capability |
| CN108623791A (en) * | 2018-05-21 | 2018-10-09 | 深圳大学 | A kind of organic thermoelectric film material of D-A type conjugated polymer and preparation method thereof |
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