CN112876656B - Electron transport type polymer and preparation method thereof, electron transport type film and organic photovoltaic cell device - Google Patents
Electron transport type polymer and preparation method thereof, electron transport type film and organic photovoltaic cell device Download PDFInfo
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Abstract
The invention provides an electron transport type polymer and a preparation method thereof, an electron transport type film and an organic photovoltaic cell device, and relates to the technical field of organic polymer semiconductor materials. The electron-transporting polymer containing the electron-withdrawing side group has a highly planar structure, and is favorable for the transport of carriers; the electron-transport polymer provided by the invention has a plurality of alkyl branched chains, so that the polymer has good solubility, and a polymer solution can form a film on a substrate in a dripping or spin coating manner in the preparation of a device, thereby being beneficial to optimizing the appearance of the film and improving the performance of the device; the electron transport polymer provided by the invention has good thermal stability and good response to sunlight, the optical band gap of the polymer is 1.3-1.4 eV, the absorption of the polymer is more matched with the solar spectrum, wider coverage to the solar spectrum is realized, and the polymer can be used as an electron acceptor material component of an organic photovoltaic cell device.
Description
Technical Field
The invention relates to the technical field of organic polymer semiconductor materials, in particular to an electron transport type polymer, a preparation method thereof, an electron transport type film and an organic photovoltaic cell device.
Background
Polymer Solar Cells (PSCs) have attracted considerable attention due to their simple preparation, light weight and potential for large area roll-to-roll processing (angelw.chem.int.ed.2008, 47,58-77 nat.photon.2012,6,153-161 acc.chem.res.2012,45, 723-733. Recently, huge progress has been made in bulk heterojunction PSCs using conjugated polymers as electron donor (D) materials and small molecule electron acceptors (a) as acceptor materials, with energy conversion efficiencies (PCE) already exceeding 16% (adv. Mater.2019,31,1902210 energy environ.sci.2019,12,3328-3337 j.am. Chem. Soc.2020,142, 1465-1474).
All-polymer solar cells (All-PSCs) have unique advantages such as good morphological stability and mechanical stability due to the use of polymers as both electron donor and acceptor materials (acc, chem, res, 2016,49,2424-2434, chem, rev, 2019,119, 8028-8086). However, the development of All-PSCs is still far behind compared to PSCs using small-molecule non-fullerenes as electron acceptors, mainly because the limited chemical structure limits the energy conversion efficiency of All-polymer solar cells.
Currently, the energy conversion efficiency of All-PSCs, which use only a small fraction of non-fullerene polymer electron acceptors, can reach 8%, and their vast majority are based on PDI, NDI, or B-N hybridized polymer materials (chem.commun.2011, 47,5109-5115, adv.mater.2012,24,613-636, chem.rev.2014,114,8943-9021, chem.rev.2016,116, 11685-11796. The main factors limiting the improvement of the energy conversion efficiency of the All-PSCs are the narrow absorption spectrum, the low molar absorption coefficient and the like of the existing polymer system.
Disclosure of Invention
The invention aims to provide an electron transport type polymer, a preparation method thereof, an electron transport type film and an organic photovoltaic cell device. The electron transport polymer provided by the invention can effectively match with the spectrum of sunlight and can be used as an electron acceptor material in an all-polymer solar cell device.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an electron-transporting polymer containing an electron-withdrawing side group, which has a structure shown in a formula I:
in the formula I, R 1 An alkyl group having 1 to 60 carbon atoms; n is 2 to 2000；π 1 And pi 2 Independently an aromatic conjugated unit; a is
X is hydrogen, fluorine or chlorine.
Preferably, R 1 Including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, or 2-dodecyloctadecyl.
Preferably, n 1 Is composed of
The pi 1 In, R 2 Including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, or 2-dodecyloctadecyl.
Preferably, n 2 Is composed of
The pi 2 In, R 3 Including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, or 2-dodecyloctadecyl.
Preferably, the electron transporting polymer having electron withdrawing side groups comprises:
the invention provides a preparation method of an electron-transporting polymer containing an electron-withdrawing side group, which comprises the following steps:
benzo [1,2-b:4,5-b']Dithiophene-4,8-diones with
Mixing, and carrying out substitution reaction to obtain an intermediate a with a structure shown in a formula II;
mixing the intermediate a with the structure shown in the formula II, n-butyl lithium and tributyl tin chloride, and carrying out a stannization reaction to obtain an intermediate b with the structure shown in the formula III;
the intermediate b with the structure shown in the formula III and Br-pi 1 -CHO mixing, and carrying out Stille coupling reaction under the catalysis of a palladium catalyst to obtain an intermediate c with a structure shown in a formula IV;
carrying out bromination reaction on the intermediate c with the structure shown in the formula IV and N-bromosuccinimide in a tetrahydrofuran solvent to obtain an intermediate d with the structure shown in the formula V;
performing a clairvol reaction on the intermediate d with the structure shown in the formula V and H-A-H under the catalysis of pyridine to obtain an intermediate e with the structure shown in the formula VI;
the intermediate e and H-pi with the structure shown as the formula VI 2 Mixing H and performing Stille polymerization reaction under the catalysis of a palladium catalyst to obtain an electron-withdrawing side group-containing electron-transporting polymer with a structure shown in a formula I;
the invention provides an electron transport type film, which is formed by the solution of the electron transport type polymer containing the electron-withdrawing side group prepared by the preparation method of the technical scheme or the electron transport type polymer containing the electron-withdrawing side group prepared by the preparation method of the technical scheme.
The invention provides an organic photovoltaic cell device which comprises an electron donor material and an electron acceptor material, wherein the electron acceptor material comprises the electron-withdrawing side group-containing electron-transporting polymer in the technical scheme or the electron-withdrawing side group-containing electron-transporting polymer prepared by the preparation method in the technical scheme.
Preferably, the electron donor material comprises PBDB-T.
The invention provides an electron-withdrawing side group-containing electron-transporting polymer with a structure shown in formula I, a main chain of a BDT (building block) forming structural unit has high planarity, and meanwhile, the side group is modified by containing an electron-withdrawing unit, so that the energy level can be adjusted, the transport of charge carriers can be promoted, and the polymer is novel in structure and has originality; the electron-transport polymer provided by the invention has a plurality of alkyl branched chains, so that the polymer has good solubility, and a polymer solution can form a film on a substrate in a dripping or spin coating mode in the preparation of a device, thereby being beneficial to optimizing the appearance of the film and improving the performance of the device; the electron-transporting polymer containing the electron-withdrawing side group has good thermal stability, can be prepared in a laboratory by a high-efficiency and economic route, and the prepared polymer semiconductor material containing the electron-withdrawing side group has good response to sunlight, so that the absorption of the polymer is more matched with the solar spectrum, wider coverage of the solar spectrum is realized, and the polymer can be used as an electron acceptor material component in an active layer of an organic photovoltaic cell device.
Drawings
FIG. 1 is a thermogravimetric and differential scanning calorimetry plots of polymer A1 in example 1 of the present invention;
FIG. 2 is a cyclic voltammogram and an absorption spectrum of polymer A1 in example 1 of the present invention;
FIG. 3 is a thermogravimetric and differential scanning calorimetry plots of polymer A2 in example 2 of the present invention;
FIG. 4 is a cyclic voltammogram and an absorption spectrum of polymer A2 in example 2 of the present invention;
FIG. 5 is a thermogravimetric and differential scanning calorimetry plots of polymer A3 in example 3 of the present invention;
FIG. 6 is a cyclic voltammogram and an absorption spectrum of polymer A3 in example 3 of the present invention;
FIG. 7 is a current-voltage curve diagram of organic solar cell devices prepared by using polymers A1, A2 and A3 as electron acceptor materials in examples 1-3 of the present invention.
Detailed Description
The invention provides an electron-transporting polymer containing an electron-withdrawing side group, which has a structure shown in formula I:
in the formula I, R 1 An alkyl group having 1 to 60 carbon atoms, preferably 20 to 30 carbon atoms; the R is 1 Is a straight chain or branched alkyl group. In the present invention, said R 1 Preferably methyl, ethyl, propyl, butyl pentyl, hexyl, heptyl, nonyl,Decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl or 2-dodecyloctadecyl.
In formula I, n is 2 to 2000, preferably 2 to 1000, more preferably 2 to 200, still more preferably 2 to 100, still more preferably 2 to 10, and specifically may be 2,4, 6, 8 or 10.
In the formula I,. Pi 1 And pi 2 Independently an aromatic conjugated unit. In the present invention, the pi 1 Preferably, it is
The pi 1 In, R 2 Preferably, it includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl or 2-dodecyloctadecyl.
In the present invention, the pi 2 Preferably pi 2 Is composed of
The pi 2 In, R 3 Preferably, it includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl or 2-dodecyloctadecyl.
In the formula I, A is
In the A, X is hydrogen, fluorine or chlorine.
In the present invention, the dotted lines in the above structural formulae each represent the attachment position of the group.
According to the invention, the electron-transport polymer containing the electron-withdrawing side group takes benzodithiophene as a core electron-donating unit, contains the electron-withdrawing side group and can transport electrons, the two-dimensional conjugated polymer containing the electron-withdrawing side group can regulate the energy level (HOMO: -5.0 to-6.0 eV) and the absorption range (covering 300-900 nm) of the polymer by adopting the electron-donating units with different electronegativities and the electron-withdrawing units with different electroabsorptivities for copolymerization, and the polymer provided by the invention has better matching to the solar spectrum and can be used as an electron-transport material of an all-polymer solar cell.
In a specific embodiment of the present invention, the electron transport polymer having electron withdrawing side groups preferably comprises:
the invention also provides a preparation method of the electron-withdrawing side group-containing electron-transporting polymer, which comprises the following steps:
benzo [1,2-b:4,5-b']Dithiophene-4,8-diones with
Mixing, and carrying out substitution reaction to obtain an intermediate a with a structure shown in a formula II;
mixing the intermediate a with the structure shown in the formula II, n-butyl lithium and tributyl tin chloride, and carrying out a stannization reaction to obtain an intermediate b with the structure shown in the formula III;
the intermediate b with the structure shown in the formula III and Br-pi 1 -CHO mixing, and carrying out Stille coupling reaction under the catalysis of a palladium catalyst to obtain an intermediate c with a structure shown in a formula IV;
carrying out bromination reaction on the intermediate c with the structure shown in the formula IV and N-bromosuccinimide in a tetrahydrofuran solvent to obtain an intermediate d with the structure shown in the formula V;
performing a clairvol reaction on the intermediate d with the structure shown in the formula V and H-A-H under the catalysis of pyridine to obtain an intermediate e with the structure shown in the formula VI;
the intermediate e and H-pi with the structure shown as the formula VI are reacted 2 Mixing H and performing Stille polymerization reaction under the catalysis of a palladium catalyst to obtain an electron-withdrawing side group-containing electron-transporting polymer with a structure shown in a formula I;
the invention relates to benzo [1,2-b:4,5-b']Dithiophene-4,8-diones with
Mixing, and performing substitution reactionTo obtain an intermediate a with a structure shown in a formula II. In the present invention, the benzo [1,2-b:4,5-b']Dithiophene-4,8-diones with
Is preferably 1:2.3 to 2.7, more preferably 1:2.5. in the present invention, the substitution reaction is preferably performed in n-butyllithium or SnCl 2 The hydrochloric acid solution and an organic solvent are carried out in the presence, the organic solvent is preferably anhydrous Tetrahydrofuran (THF), the substitution reaction comprises a first stage reaction, a second stage reaction and a third stage reaction which are carried out in sequence, and specifically, the THF solution of n-butyl lithium is dropwise added to the solution at 0 DEG C
In the THF solution, a first-stage reaction is carried out to obtain a first mixture solution; mixing the first mixture solution with benzo [1,2-b:4,5-b']Mixing dithiophene-4,8-diketone to perform a second-stage reaction to obtain a second mixture solution; adding SnCl dropwise into the second mixture solution 2 Hydrochloric acid solution, and carrying out the third-stage reaction. In the invention, in the first-stage reaction process, the H on the 5-position of the thiophene alkyl chain is extracted by utilizing the strong alkaline action of n-butyl lithium, so that the thiophene alkyl chain is conveniently connected with other units through covalent bonds; in the reaction process of the second stage,
and benzo [1,2-b:4,5-b']Coupling dithiophene-4,8-diketone to obtain an intermediate containing hydroxyl; during the third stage of reaction, in SnCl 2 Removing 1 unit of H from each hydroxyl-containing intermediate obtained in the second stage under the catalysis of hydrochloric acid solution 2 O to obtain the intermediate a with the structure shown in the formula II.
In the present invention, the n-butyllithium is reacted with benzo [1,2-b:4,5-b']The molar ratio of dithiophene-4,8-dione is preferably from 2.4 to 2.8:1, more preferably 2.6:1; the concentration of the n-butyllithium THF solution is preferably 1.4 to 1.8mol/L, more preferably 1.6mol/L; the addition rate of the n-butyllithium solution in THF is preferably 0.3 to 0.5 mL/mLmin, more preferably 0.45mL/min. In the present invention, the
The concentration of the THF solution (2) is preferably 0.24 to 0.28mol/L, more preferably 0.26mol/L. In the present invention, the temperature of the first-stage reaction is preferably 0 ℃; the reaction time in the first stage is preferably from 0.6 to 1.2 hours, more preferably 1 hour, and specifically, it is started after the addition of n-butyllithium in THF is completed.
In the present invention, the temperature of the second stage reaction is preferably 40 to 70 ℃, more preferably 50 ℃; the time is preferably 1.5 to 3 hours, more preferably 2 hours.
In the invention, the second mixture solution obtained after the second-stage reaction is preferably cooled to room temperature, and then SnCl is dropwise added 2 Hydrochloric acid solution, and carrying out the third-stage reaction. In the present invention, the SnCl 2 SnCl in hydrochloric acid solution 2 And benzo [1,2-b:4,5-b']The molar ratio of dithiophene-4,8-dione is preferably from 4.8 to 5.2:1, more preferably 5:1; the SnCl 2 The hydrochloric acid solution is specifically SnCl 2 Is mixed with hydrochloric acid to obtain, wherein, snCl 2 The concentration of (b) is preferably 0.6 to 0.7mol/L, more preferably 0.65mol/L, and the mass content of HCl in hydrochloric acid is preferably 5 to 15%, more preferably 10%; the SnCl 2 The dropping rate of the hydrochloric acid solution is preferably 0.5 to 1mL/min, more preferably 0.8mL/min. In the present invention, the temperature of the third-stage reaction is preferably room temperature, and the time is preferably 0.5 to 2.5 hours, and more preferably 2 hours.
In the present invention, the substitution reaction is preferably carried out in a nitrogen atmosphere.
After the substitution reaction (i.e., the third reaction stage is completed), the present invention preferably quenches the reaction with water, and uses water and CH 2 Cl 2 Extracting, then taking a lower organic phase, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent by using a rotary evaporator to obtain a crude product; and purifying the crude product by column chromatography to obtain an intermediate a with a structure shown in a formula II. In the invention, the intermediate a with the structure shown in the formula II is a yellow-green oily liquid.
In a specific embodiment of the present invention, the substitution reaction is represented by the formula:
after the intermediate a with the structure shown in the formula II is obtained, the intermediate a with the structure shown in the formula II, n-butyl lithium and tributyl tin chloride are mixed for stannization reaction to obtain the intermediate b with the structure shown in the formula III.
In the present invention, the molar ratio of the intermediate a having the structure represented by formula II, n-butyllithium and tributyltin chloride is preferably 1:2.0 to 2.4:2.1 to 2.5, more preferably 1:2.2:2.3. in the present invention, the stannation reaction is carried out in the presence of an organic solvent, preferably THF. In the invention, specifically, a THF solution of n-butyl lithium is dropwise added into a THF solution of the intermediate a at-78 ℃, and is stirred and mixed at-78 ℃ to obtain a mixture solution; tributylchlorobutyltin is then added dropwise to the mixture solution. The mixing sequence is favorable for ensuring that reactants are fully reacted. In the present invention, the concentration of the THF solution of n-butyllithium is preferably 1.4 to 1.8mol/L, more preferably 1.6mol/L; the dropwise addition rate of the n-butyllithium THF solution is preferably 0.3 to 0.5mL/min, more preferably 0.45mL/min. In the present invention, the concentration of the THF solution of the intermediate a is preferably 0.060 to 0.075mol/L, more preferably 0.068mol/L. In the present invention, the stirring and mixing time is preferably 0.5 to 1.5 hours, and more preferably 1 hour. In the present invention, the dropping rate of the tributylchlorobutyltin is preferably 0.3 to 0.5mL/min, and more preferably 0.45mL/min.
In the present invention, the stannation reaction is preferably performed at room temperature, and the time of the stannation reaction is preferably 8 to 16 hours, and more preferably 12 hours; the stannation reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 450rpm; the stannation reaction is preferably carried out in a nitrogen atmosphere.
After the stannation reaction, the invention is superiorQuenching with water, and adding water and CH 2 Cl 2 Extraction was carried out, then the lower organic phase was taken, dried using anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporator to give the crude product which was used in the next reaction without further purification.
In a specific embodiment of the present invention, the reaction formula of the stannation reaction is as follows:
after obtaining the intermediate b with the structure shown in the formula III, the invention combines the intermediate b with the structure shown in the formula III and Br-pi 1 And (4) mixing the intermediate C and the intermediate C, and performing a Stille coupling reaction under the catalysis of a palladium catalyst to obtain an intermediate c with a structure shown in a formula IV. In the invention, the intermediate a and Br-pi with the structure shown in formula II 1 The molar ratio of — CHO is preferably 1:2 to 2.8, more preferably 1:2.5. in the present invention, the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium, and the molar ratio of the intermediate a having a structure represented by formula II to the palladium catalyst is preferably 1:0.03 to 0.05, more preferably 1:0.05. in the present invention, the Stille coupling reaction is preferably performed in the presence of an organic solvent, the organic solvent is preferably THF, and the ratio of the amount of the intermediate a having the structure shown in formula II to the amount of anhydrous THF is preferably 1mmol:10 to 20mL, more preferably 1mmol:14 to 15mL.
In the invention, the temperature of the Stille coupling reaction is preferably 120-140 ℃, and more preferably 130 ℃; the time of the Stille coupling reaction is preferably 8 to 16 hours, and more preferably 12 hours; the Stille coupling reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 450rpm; the Stille coupling reaction is preferably carried out in a nitrogen atmosphere.
After the Stille coupling reaction, the reaction is preferably quenched with water, water and CH in the reaction mixture 2 Cl 2 Extracting, then taking a lower organic phase, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent by using a rotary evaporator to obtain a crude product; subjecting the crude product toAnd (5) purifying by column chromatography to obtain an intermediate c with a structure shown in a formula IV. In the invention, the intermediate c with the structure shown in the formula IV is yellow oily liquid.
In a specific embodiment of the present invention, the reaction formula of the Stille coupling reaction is as follows:
after obtaining the intermediate c with the structure shown in the formula IV, the intermediate c with the structure shown in the formula IV and N-bromosuccinimide (NBS) are subjected to bromination reaction in a tetrahydrofuran solvent to obtain the intermediate d with the structure shown in the formula V. In the present invention, the molar ratio of the intermediate c having the structure represented by formula IV to NBS is preferably 1:2.0 to 2.5, more preferably 1:2.3. in the present invention, the ratio of the intermediate c having the structure shown in formula IV to tetrahydrofuran is preferably 1mmol:100 to 200mL, more preferably 1mmol:150 to 160mL. In the present invention, the tetrahydrofuran is preferably anhydrous tetrahydrofuran. In the present invention, the intermediate c having the structure shown in formula IV, NBS and tetrahydrofuran solvent are preferably mixed at 0 ℃, which is advantageous to reduce the generation of impurities by mixing at a low temperature.
In the invention, the bromination reaction is preferably carried out at room temperature, and the time of the bromination reaction is preferably 8 to 16 hours, and more preferably 12 hours; the bromination reaction is preferably carried out in the absence of light, so as to avoid side reactions of NBS under illumination. In the present invention, the bromination reaction is preferably carried out under a nitrogen atmosphere.
After the bromination reaction, the reaction is preferably quenched with water, and with water and CH in accordance with the present invention 2 Cl 2 Extracting, taking a lower organic phase, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent by using a rotary evaporator to obtain a crude product; and purifying the crude product by column chromatography to obtain an intermediate d with a structure shown in a formula V. In the invention, the intermediate d with the structure shown in the formula V is yellow oily liquid.
In a specific embodiment of the invention, the bromination reaction is of the formula:
after the intermediate d with the structure shown in the formula V is obtained, the intermediate d with the structure shown in the formula V and H-A-H are subjected to a Cleveland reaction under the catalysis of pyridine to obtain an intermediate e with the structure shown in the formula VI. In the present invention, the molar ratio of the intermediate d having the structure represented by formula V to H-a-H is preferably 1:2 to 4, more preferably 1:3; the dosage ratio of the intermediate d with the structure shown in the formula V to pyridine is preferably 1mmol:10 to 30 drops, more preferably 1mmol:26 drops. In the present invention, the clairver reaction is preferably carried out in the presence of an organic solvent, preferably anhydrous chloroform or anhydrous THF, and the intermediate d having the structure represented by formula V and the organic solvent are preferably used in a ratio of 1mmol:50 to 300mL, more preferably 1mmol:85 to 170mL. In the invention, the intermediate d with the structure shown in the formula V and H-A-H are dissolved in an organic solvent to obtain a mixed solution; pyridine is then added dropwise to the mixed solution. In the present invention, the dropping rate of the pyridine is preferably 30 drops/min.
In the present invention, the temperature of the clairvoyer reaction is preferably 60 to 100 ℃, more preferably 80 ℃; the time of the clairvoyer reaction is preferably 8 to 16 hours, and more preferably 12 hours; the clairver reaction is preferably carried out under stirring conditions, preferably at a speed of 380rpm. In the present invention, the clairver reaction is preferably carried out under nitrogen atmosphere conditions.
After the clairvigal reaction, the obtained system is preferably dripped into methanol, solid substances are separated out, and the obtained solid substances are dried after filtration to obtain an intermediate e with a structure shown in a formula VI. In the present invention, the dropping rate is preferably 0.4 to 0.6mL/min, more preferably 0.5mL/min. In the invention, the intermediate e with the structure shown in the formula VI is a blue solid.
In a specific embodiment of the invention, the reaction formula of the clairver reaction is as follows:
after obtaining the intermediate e with the structure shown in the formula VI, the invention combines the intermediate e with the structure shown in the formula VI and H-pi 2 Mixing the materials with hydrogen (OH) and performing Stille polymerization reaction under the catalysis of a palladium catalyst to obtain the electron-withdrawing side group-containing electron-transporting polymer with the structure shown in the formula I. In the invention, the intermediate e and H-pi with the structure shown in the formula VI 2 The molar ratio of-H is preferably 1:2.2 to 2.6, more preferably 1:2.4. in the present invention, the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium, and the molar ratio of the intermediate e having the structure shown in formula VI to the palladium catalyst is preferably 1:0.03 to 0.05, more preferably 1:0.05. in the present invention, the Stille polymerization reaction is preferably carried out in the presence of an organic solvent, preferably toluene; the ratio of the amount of intermediate e having the structure shown in formula VI to toluene is preferably 1mmol:50 to 150mL, more preferably 1mmol:120mL. In the invention, the intermediate e and H-pi with the structure shown in the formula VI are preferably firstly used 2 Mixing H and a palladium catalyst, vacuumizing and replacing nitrogen for three times, and adding toluene to remove the interference of water and oxygen in the air.
In the present invention, the temperature of the Stille polymerization reaction is preferably 120 to 160 ℃, and more preferably 140 ℃; the time of the Stille polymerization reaction is preferably 36 to 72 hours, and more preferably 48 hours; the Stille polymerization reaction is preferably carried out in a nitrogen atmosphere.
After the Stille polymerization reaction, preferably, the obtained reaction system is cooled to room temperature, then is dripped into methanol for precipitation, and the obtained solid material is a crude product after filtration; purifying the crude product by sequentially passing methanol, n-hexane, dichloromethane and chloroform; and (3) dropwise adding the chloroform phase concentrated solution into methanol for secondary precipitation, filtering, and drying the obtained solid material to obtain the electron-withdrawing side group-containing electron-transporting polymer with the structure shown in the formula I. In the present invention, the dropping rate is preferably 0.4 to 0.6mL/min, more preferably 0.5mL/min. In the invention, the electron-transporting polymer containing the electron-withdrawing side group with the structure shown in the formula I is a black solid.
In a specific embodiment of the present invention, the reaction formula of the Stille polymerization reaction is:
the invention also provides an electron transport type film which is formed by the solution of the electron transport type polymer containing the electron-withdrawing side group prepared by the preparation method of the technical scheme or the electron transport type polymer containing the electron-withdrawing side group prepared by the preparation method of the technical scheme. In the present invention, the solvent of the solution of the electron transport polymer having a pendant electron-withdrawing group preferably comprises chlorobenzene, dichlorobenzene, chloroform or dichloromethane; the mass concentration of the solution of the electron transport polymer having electron-withdrawing side groups is preferably 5 to 20mg/mL, more preferably 20mg/mL. In the invention, the electron-transporting polymer has a plurality of alkyl branched chains, so that the polymer has good solubility, and the polymer solution can form a film on a substrate in a dropping coating or spin coating mode in the preparation of a device, thereby being beneficial to optimizing the appearance of the film and improving the performance of the device. In the present invention, the use of the electron transport thin film includes an active layer material for the production of an organic solar cell; the thickness of the electron transport thin film is preferably 150nm.
The invention also provides an organic photovoltaic cell device which comprises an electron donor material and an electron acceptor material, wherein the electron acceptor material comprises the electron transport type polymer containing the electron-withdrawing side group in the technical scheme or the electron transport type polymer containing the electron-withdrawing side group prepared by the preparation method in the technical scheme. In the present invention, the electron donor material of the organic photovoltaic cell device preferably comprises PBDB-T. The electron-transporting polymer containing the electron-withdrawing side group provided by the invention has appropriate HOMO and LUMO energy levels, energy level band gaps and absorption spectra, and is suitable for being applied to organic photovoltaic cells.
As an embodiment of the invention, the invention preferably uses the commercially available PBDB-T as an electron donor material, uses the electron transport polymer containing the electron-withdrawing side group as an electron acceptor material, and adopts a classical sandwich device structure to prepare an organic solar cell device; the classic sandwich device structure is preferably ITO/PEDOT: PSS/PBDB-T: acceptor/PFN-Br/Ag. The invention has no special requirements on the specific preparation process of the organic solar cell device, and the preparation process known by the technical personnel in the field can be adopted.
In a specific embodiment of the present invention, the method for manufacturing an organic solar cell device includes the steps of: carrying out ultrasonic cleaning on Indium Tin Oxide (ITO) by using acetone and isopropanol in sequence, and then treating in ultraviolet ozone for 10 minutes; placing the cleaned and blow-dried ITO substrate on a rotary table of a spin coater, spin-coating a PEDOT/PSSS aqueous solution on the ITO substrate by adopting a solution spin coating method, and then drying the ITO substrate in the air at the temperature of 150 ℃ for 15 minutes to form PEDOT: a PSS film; spin-coating a solution of PBDB-T and the electron transporting polymer containing pendant electron withdrawing groups in chlorobenzene in a glove box under nitrogen atmosphere to deposit the PBDB-T and electron withdrawing groups on PEDOT: forming an active layer film with the thickness of 100-150 nm on the PSS film; and evaporating 20nm Ca and 100nm Al as anode electrodes under a high vacuum condition to obtain the organic solar cell device. In the present invention, the mass ratio of the PBDB-T to the electron transporting polymer having electron withdrawing side groups is preferably 1:1. In the present invention, the process of manufacturing the organic solar cell device is preferably performed in a glove box under a nitrogen atmosphere.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, the chemical reagents are purchased from commercial companies, and if no special description is given, the chemical reagents are not further purified before use; the anhydrous tetrahydrofuran is prepared by distilling metal sodium and benzophenone, and all reactions are carried out in a nitrogen atmosphere in the process of preparing the electron transport polymer containing the electron-withdrawing side group; the hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are obtained by testing a Switzerland Bruk 400MHz nuclear magnetic resonance instrument; the ultraviolet spectrum of the polymer was measured by a PerkiElmer LAMBDA 950 spectrometer; the cyclic voltammetry curve is obtained by testing of an electrochemical workstation of Shanghai Chenghua CHI730 e; thermal analysis was performed by semer femtograph and differential calorimetric scanning system tests.
Example 1
The polymer A1 was prepared by the following synthetic route:
(1) Synthesis of Compound 3: a solution of n-butyllithium (22.1mmol, 2.6 equiv) in THF (13.8 mL) was added dropwise at 0 ℃ to a solution of 3- (2-octyldodecyl) thiophene (compound 2,7.7g,21.1mmol,2.5 equiv) in anhydrous THF (80 mL) at a rate of 0.45 mL/min; stirring the obtained mixture solution at 0 ℃ to react for 1 hour; then benzo [1,2-b:4,5-b']Dithiophene-4,8-dione (Compound 1,1.8g,8.44mmol, 1equiv) was added to the mixture solution, and stirred at 50 ℃ for reaction for 2 hours, after cooling to room temperature, snCl was added dropwise at a rate of 0.8mL/min to the reaction system 2 (8.0 g,42.2mmol, 5equiv) by weight of HCl (65 mL); the mixture solution was reacted at room temperature for 2 hours under a nitrogen atmosphere; after the reaction was completed, the reaction was quenched with distilled water, and water (70 mL) and CH were added 2 Cl 2 (70 mL. Times.3) and then the lower organic phase was taken, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporator to give the crude product; the crude product was purified by column chromatography to give compound 3 (4.7g, 61%) as a yellowish green oily liquid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.63(d,J＝5.7Hz,2H),7.45(d,J＝5.7Hz,2H),7.29(d,J＝1.4Hz,2H),7.08(s,2H),2.67(d,J＝6.7Hz,4H),1.69(br,2H),1.34-1.26(m,64H),0.87(m,12H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):142.46,139.26,139.20,136.67,130.13,127.71,124.30,123.46,122.03,39.25,35.18,33.67,32.08,30.22,29.86,29.82,29.53,26.91,22.84,14.27。
(2) Synthesis of Compound 4: a solution of n-butyllithium (6 mmol, 2.2equiv) in THF (3.8 mL) was added dropwise at-78 deg.C to a solution of compound 3 (2.5g, 2.73mmol, 1equiv) in anhydrous THF (40 mL) at a rate of 0.45 mL/min; the mixture solution was stirred at this temperature for 1 hour, and then tributylchlorobutyltin (2g, 6.28mmol,2.3 equiv) was added dropwise to the mixture solution at a rate of 0.45 mL/min; heating the mixture solution to room temperature, stirring at 450rpm overnight, and carrying out the reaction under the nitrogen atmosphere; after the reaction was completed, the reaction was quenched with distilled water, and water (70 mL) and CH were added 2 Cl 2 (70 mL. Times.3) and then the lower organic phase was taken, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporator; the crude product obtained was a yellowish green oily liquid, compound 4, which was used directly in the next step without column chromatography purification.
(3) Synthesis of Compound 6: compound 4, compound 5 (1.88g, 6.8mmol,2.5 equiv) and 40mL of anhydrous THF were added to a dry two-necked bottle; tetrakis (triphenylphosphine) palladium (159mg, 0.14mmol, 0.05equiv) was added to the mixture solution, and the mixture solution was heated to 130 ℃, stirred overnight at 450rpm, and the reaction was performed under a nitrogen atmosphere; after the reaction was completed, the reaction was quenched with distilled water, and water (70 mL) and CH were added 2 Cl 2 (70 mL. Times.3) and then the lower organic phase was taken, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporator; the crude product was purified by column chromatography to give compound 6 (1.41g, 62%) as a yellow oily liquid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):9.85(s,2H),7.81(s,2H),7.61(s,2H),7.34(d,J＝1.4Hz,2H),7.12(d,J＝1.4Hz,2H),2.85(t,J＝7.8Hz,4H),2.67(d,J＝6.7Hz,4H),1.78-1.60(br,4H),1.40-1.17(m,42H),0.91-0.82(m,18H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):182.63,142.78,142.13,141.80,140.93,139.82,138.82,138.29,137.14,136.69,130.32,124.32,123.73,122.57,39.22,35.15,33.63,32.06,31.74,30.56,30.24,29.87,29.84,29.80,29.65,29.50,29.31,27.06,26.89,22.83,22.81,22.75,14.26,14.24。
(4) Synthesis of compound 7: compound 6 (250mg, 0.19mmol, 1.0equiv), NBS (78mg, 0.44mmol, 2.3equiv) and anhydrous THF (30 mL) were added to a dry round-bottomed flask at 0 deg.C; the mixture is stirred at room temperature overnight, and is reacted in a dark place, and the reaction is carried out in a nitrogen atmosphere; after the reaction was completed, the reaction was quenched with distilled water, and water (70 mL) and CH were added 2 Cl 2 (70 mL. Times.3) and then the lower organic phase was taken, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by rotary evaporator; the crude product was purified by column chromatography to give compound 7 (2458g, 88%) as a yellow oily liquid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):9.86(s,2H),7.77(s,2H),7.62(s,2H),7.20(s,2H),2.86(t,J＝7.7Hz,4H),2.63(d,J＝7.2Hz,4H),1.78-1.60(br,4H),1.40-1.17(m,42H),0.91-0.81(m,18H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):182.59,142.40,142.21,142.07,140.40,139.79,138.71,138.01,137.16,137.08,130.16,123.56,123.26,111.50,38.77,33.68,32.06,31.75,30.60,30.22,29.83,29.80,29.68,29.50,29.48,29.33,27.07,26.79,22.82,22.75,20.85,14.26,14.24。
(5) Synthesis of monomer M1: adding compound 7 (460mg, 0.31mmol,1.0 equiv), compound 8 (183mg, 0.94mmol,3.0 equiv) and anhydrous chloroform (50 mL) to a round-bottomed flask containing magnetons; dropwise adding 8 drops of pyridine into the mixture solution at the rate of 30 drops/min, heating to 80 ℃, stirring at 380rpm for reacting overnight, and carrying out the reaction under the nitrogen atmosphere; after completion of the reaction, the mixture solution was added dropwise at a rate of 0.5mL/min to 300mL of methanol, and the precipitated solid was filtered and dried to obtain a blue solid, i.e., monomer M1 (380mg, 67%). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):8.81(s,2H),8.70(d,J＝8.0Hz,2H),7.94(m,2H),7.87(s,2H),7.82-7.83(m,4H),7.70(s,2H),7.22(s,2H),7.20(s,2H),2.88(t,J＝8.0Hz,4H),2.67(d,J＝7.0Hz,4H),1.85-1.77(br,2H),1.70-1.65(m,4H),1.47-1.12(m,84),0.92-0.79(m,18H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):188.25,160.27,147.61,147.06,142.76,142.30,140.16,137.88,137.48,137.42,137.06,136.15,135.48,134.83,130.34,125.57,124.09,123.81,123.62,114.52,114.46,111.75,70.43,38.74,34.54,33.66,32.06,31.75,30.40,30.25,29.87,29.84,29.81,29.61,29.50,26.76,22.82,22.77,14.26,14.25。
(6) Synthesis of Polymer A1: a dry two-necked flask was charged with monomer M1 (95.1mg, 0.05mmol), monomer M2 (53.4mg, 0.12mmol) and the catalyst tetrakis (triphenylphosphine) palladium (2.9 mg), and the flask was purged with nitrogen by vacuum three times and charged with the solvent toluene (6 mL) by syringe; stirring the mixture solution at 140 ℃ to react for 48 hours, and carrying out the reaction under the nitrogen atmosphere; after the mixture solution is recovered to room temperature, the obtained polymer solution is dripped into 200mL of methanol at the speed of 0.5mL/min, and polymer precipitate is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a Soxhlet extractor sequentially using methanol, n-hexane, dichloromethane and chloroform as solvents, the concentrated solution of the chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration through filter paper and dried to obtain a black solid, i.e., polymer A1 (110mg, 70%).
The polymer A1 is subjected to a thermodynamic performance test, and thermogravimetry and differential scanning calorimetry curves of the polymer A1 are shown in figure 1, wherein a in figure 1 is a thermogravimetry curve, the experiment is carried out under the protection of nitrogen, the temperature rise rate is in the range of 30-600 ℃ at 10 ℃/min, the polymer A1 has 5% mass loss, and the temperature is 335 ℃, which indicates that the polymer A1 has good thermal stability and is enough to deal with the thermal treatment of various organic photoelectric devices. As shown in B in FIG. 1, when the differential scanning calorimetry curve was measured at an increasing/decreasing rate of 5 ℃/min for the polymer A1, it was found that the polymer A1 did not have a significant endothermic or exothermic peak in the range of 30 to 315 ℃.
The polymer A1 is subjected to electrochemical performance test, and the test instrument is CHI730e electrochemical workstation of Shanghai Chenghua. The working electrode is a glassy carbon electrode, the counter electrode is a platinum wire, the reference electrode is silver/silver chloride, and the electrolyte is 0.1M acetonitrile solution of tetrabutylammonium hexafluorophosphate. The cyclic voltammogram of polymer A1 is shown as a in figure 2, using ferrocene calibration. The cyclic voltammogram shows that the highest occupied orbital (HOMO) energy level of the polymer A1 is-5.45 eV, and the lowest unoccupied orbital (LUMO) energy level is-3.83 eV, which proves that the polymer can be used for preparing a polymer solar cell.
The film absorption spectrum of the polymer A1 is shown as b in FIG. 2, with a film absorption coverage of 300nm to 900nm; the maximum absorption wavelength is positioned at 600nm, and the film absorption sideband of the polymer is 863nm; the optical bandgap of the polymer was calculated to be 1.44eV, indicating that the polymer has a lower bandgap, making the absorption of the polymer more matched to the solar spectrum.
Example 2
Polymer A2 was prepared according to the following synthetic route:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 4 was prepared according to the procedure of example 1.
(3) Compound 6 was prepared according to the procedure of example 1.
(4) Compound 7 was prepared according to the procedure of example 1.
(5) Synthesis of monomer M3: compound 7 (1.4g, 1.07mmol, 1.0equiv), compound 8 (741mg, 3.22mmol, 3.0equiv), and anhydrous chloroform (80 mL) were added to a round-bottomed flask containing magnetons; adding 28 drops of pyridine into the mixture solution at the rate of 30 drops/min, heating to 80 ℃, stirring at 380rpm for reacting overnight, and reacting under the nitrogen atmosphere; after completion of the reaction, the mixture solution was added dropwise at a rate of 0.5mL/min to 300mL of methanol, and the precipitated solid was filtered and dried to obtain a blue solid, monomer M3 (820 mg, 46%). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):8.79(s,2H),8.54(dd,J＝6.5Hz,9.9Hz,2H),7.88(s,2H),7.73-7.65(m,4H),7.23(s,2H),2.88(t,J＝8.0Hz,4H),2.67(d,J＝7.0Hz,4H),1.85-1.76(br,2H),1.75-1.65(m,4H),1.47-1.12(m,84),0.93-0.77(m,18H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):185.93,158.15,156.17,156.01,153.56,153.42,148.23,147.92,143.05,142.36,140.23,137.75,137.61,137.55,137.34,136.73,136.62,135.90,134.79,133.42,130.40,124.10,123.92,122.69,115.33,115.12,114.09,113.98,113.04,112.85,111.85,38.76,34.53,33.66,32.06,31.74,30.36,30.25,29.87,29.84,29.81,29.62,29.50,26.76,22.82,22.77,14.24。
(6) Synthesis of Polymer A2: a dry two-necked flask was charged with monomer M3 (96.7mg, 0.05mmol), monomer M4 (49.1mg, 0.12mmol) and the catalyst tetrakis (triphenylphosphine) palladium (2.9 mg), and the reaction was carried out three times by changing nitrogen through vacuum, and solvent toluene (6 mL) was added by syringe; stirring the mixture solution at 140 ℃ to react for 48 hours, and carrying out the reaction under the nitrogen atmosphere; after the mixture solution is recovered to room temperature, the obtained polymer solution is dripped into 200mL of methanol at the speed of 0.5mL/min, and polymer precipitate is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a Soxhlet extractor sequentially using methanol, n-hexane, dichloromethane and chloroform as solvents, a concentrated solution of a chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration through a filter paper and dried to obtain a black solid, i.e., polymer A2 (98mg, 67%).
The thermo-mechanical property test of the polymer A2 is carried out, and the thermogravimetric and differential scanning calorimetry curve chart of the polymer A2 is shown in figure 3, wherein a in figure 3 is a thermogravimetric curve, the experiment is carried out under the protection of nitrogen, the heating rate of 10 ℃/min is in the range of 30-600 ℃, the mass loss of the polymer A2 is relative to 5%, and the temperature is 335 ℃, which indicates that the polymer A2 has good thermal stability and is enough to cope with the heat treatment of various organic photoelectric devices. As shown in b of fig. 3, when the differential thermal scanning curve of polymer A2 is measured at an increasing/decreasing rate of 5 ℃/min, it can be found that polymer A2 does not have an obvious endothermic or exothermic peak in the range of 30 to 315 ℃.
And (3) carrying out electrochemical performance test on the polymer A2, wherein the test instrument is CHI730e electrochemical workstation of Shanghai Chenghua. The working electrode is a glassy carbon electrode, the counter electrode is a platinum wire, the reference electrode is silver/silver chloride, and the electrolyte is 0.1M acetonitrile solution of tetrabutylammonium hexafluorophosphate. The cyclic voltammogram of polymer A2 is shown as a in figure 4, using ferrocene calibration. The cyclic voltammogram shows that the highest occupied orbital (HOMO) energy level of the polymer A2 is-5.78 eV, and the lowest unoccupied orbital (LUMO) energy level of the polymer A2 is-3.87 eV, so that the polymer can be used for preparing a polymer solar cell.
The film absorption spectrum of polymer A2 is shown as b in fig. 4, with a film absorption coverage of 300nm to 900nm; the maximum absorption wavelength is positioned at 601nm, and the film absorption sideband of the polymer is 857nm; the optical bandgap of the polymer was calculated to be 1.45eV, indicating that the polymer has a lower bandgap, making the absorption of the polymer more matched to the solar spectrum.
Example 3
Polymer A3 was prepared according to the following synthetic route:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 4 was prepared according to the procedure of example 1.
(3) Compound 6 was prepared according to the procedure of example 1.
(4) Compound 7 was prepared according to the procedure of example 1.
(5) Synthesis of monomer M3: compound 7 (1.4g, 1.07mmol, 1.0equiv), compound 8 (741mg, 3.22mmol, 3.0equiv), and anhydrous chloroform (80 mL) were added to a round-bottomed flask containing magnetons; adding 28 drops of pyridine into the mixture solution at the rate of 30 drops/min, heating to 80 ℃, stirring at 380rpm for reacting overnight, and reacting under the nitrogen atmosphere; after the reaction was completed, the mixture solution was added dropwise to 300mL of methanol at a rate of 0.5mL/min, and the precipitated solid was filtered and dried to obtain a blue solid, monomer M3 (820 mg, 46%). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):8.79(s,2H),8.54(dd,J＝6.5Hz,9.9Hz,2H),7.88(s,2H),7.73-7.65(m,4H),7.23(s,2H),2.88(t,J＝8.0Hz,4H),2.67(d,J＝7.0Hz,4H),1.85-1.76(br,2H),1.75-1.65(m,4H),1.47-1.12(m,84),0.93-0.77(m,18H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):185.93,158.15,156.17,156.01,153.56,153.42,148.23,147.92,143.05,142.36,140.23,137.75,137.61,137.55,137.34,136.73,136.62,135.90,134.79,133.42,130.40,124.10,123.92,122.69,115.33,115.12,114.09,113.98,113.04,112.85,111.85,38.76,34.53,33.66,32.06,31.74,30.36,30.25,29.87,29.84,29.81,29.62,29.50,26.76,22.82,22.77,14.24。
(6) Polymer A3 Synthesis: a dry two-necked flask was charged with monomer M3 (96.7mg, 0.05mmol), monomer M2 (53.5mg, 0.12mmol) and tetrakis (triphenylphosphine) palladium (2.9 mg) as a catalyst, and the flask was evacuated under nitrogen for three times, and then charged with toluene (6 mL) as a solvent by syringe; stirring the mixture solution at 140 ℃ to react for 48 hours, and carrying out the reaction under the nitrogen atmosphere; after the mixture solution is recovered to room temperature, the obtained polymer solution is dripped into 200mL of methanol at the speed of 0.5mL/min, and polymer precipitate is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a Soxhlet extractor sequentially using methanol, n-hexane, dichloromethane and chloroform as solvents, a concentrated solution of a chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration through a filter paper and dried to obtain a black solid, i.e., polymer A3 (120mg, 80%).
The polymer A3 is subjected to a thermodynamic performance test, thermogravimetry and differential scanning calorimetry curves of the polymer A3 are shown in figure 5, wherein a in figure 5 is a thermogravimetry curve, the experiment is carried out under the protection of nitrogen, the temperature rise rate is 10 ℃/min and is in a range from 30 to 600 ℃, the polymer A3 has 5% mass loss, and the temperature is 322 ℃, which indicates that the polymer has good thermal stability and is enough to deal with the heat treatment of various organic photoelectric devices. As shown in b of FIG. 5, the differential scanning calorimetry curve of the polymer A3 at an increasing/decreasing rate of 5 ℃/min shows that the polymer A3 has no significant endothermic or exothermic peak in the range of 30 to 275 ℃.
And (3) carrying out an electrochemical performance test on the polymer A3, wherein the test instrument is CHI730e electrochemical workstation of Shanghai Chenghua. The working electrode is a glassy carbon electrode, the counter electrode is a platinum wire, the reference electrode is silver/silver chloride, and the electrolyte is 0.1M acetonitrile solution of tetrabutylammonium hexafluorophosphate. The cyclic voltammogram of polymer A3 is shown as a in fig. 6, using ferrocene for calibration. The cyclic voltammogram shows that the highest occupied orbital (HOMO) energy level of the polymer A3 is-5.39 eV, and the lowest unoccupied orbital (LUMO) is-3.61 eV, so that the polymer can be used for preparing a polymer solar cell.
The film absorption spectrum of polymer A3 is shown as b in fig. 6, with a film absorption coverage of 300nm to 900nm; the maximum absorption wavelength is at 645nm, and the film absorption sideband of the polymer is 876nm; the optical bandgap of the polymer was calculated to be 1.41eV, indicating that the polymer has a lower bandgap, making the absorption of the polymer more matched to the solar spectrum.
Example 4
Polymer A4 was prepared according to the following synthetic route:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 4 was prepared according to the procedure of example 1.
(3) Compound 6 was prepared according to the procedure of example 1.
(4) Compound 7 was prepared according to the procedure of example 1.
(5) Synthesis of monomer M5: compound 7 (1.4g, 1.07mmol, 1.0equiv), compound 8 (530mg, 3.22mmol, 3.0equiv) and anhydrous THF (80 mL) were added to a round-bottomed flask containing magnetons; adding 28 drops of pyridine into the mixture solution at the rate of 30 drops/min, heating to 80 ℃, stirring at 380rpm for reacting overnight, and reacting under the nitrogen atmosphere; after completion of the reaction, the mixture solution was dropwise added at a rate of 0.5mL/min to 300mL of methanol, and the precipitated solid was filtered and dried to obtain monomer M5 (750mg, 70%). 1 HNMR(chloroform-d,298K,400MHz,δ/ppm):8.01(s,2H),7.76(s,2H),7.39-7.42(m,4H),7.16(s,2H),4.3-4.36(m,4H),2.62-2.68(dd,J＝7.2Hz,4H),1.85-1.75(s,2H),1.60-1.51(m,14H),1.45-0.17(m,56H),0.87-0.81(m,16H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):165.74,165.03,145.13,142.26,139.75,137.64,137.39,137.33,136.98,135.70,130.26,127.98,127.36,123.75,121.10,114.83,112.98,112.06,111.70,77.34,77.22,77.13,77.02,76.70,56.38,40.80,38.52,34.36,33.58,31.93,30.16,29.76,29.74,29.72,29.69,29.40,29.38,26.69,22.70,14.20,14.13。
(6) Synthesis of Polymer A4: a dry two-necked flask was charged with monomer M5 (100.7 mg, 0.05mmol), monomer M4 (49.1mg, 0.12mmol) and the catalyst tetrakis (triphenylphosphine) palladium (2.9 mg), and the flask was evacuated under nitrogen for three times, and then charged with the solvent toluene (6 mL) by syringe; stirring the mixture solution at 140 ℃ to react for 48 hours, and carrying out the reaction under the nitrogen atmosphere; after the mixture solution is recovered to room temperature, the obtained polymer solution is dripped into 200mL of methanol at the speed of 0.5mL/min, and polymer precipitate is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer thus obtained was collected, sequentially separated and purified by a Soxhlet extractor using methanol, n-hexane, dichloromethane and chloroform as solvents, the chloroform phase was collected as a concentrated solution and precipitated in methanol, and the precipitate was collected by filtration through filter paper and dried to obtain a black solid, i.e., polymer A4 (118mg, 79%).
Example 5
Polymer A5 was prepared according to the following synthetic route:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 4 was prepared according to the procedure of example 1.
(3) Compound 6 was prepared according to the procedure of example 1.
(4) Compound 7 was prepared according to the procedure for example 1.
(5) Synthesis of monomer M5: compound 7 (1.4g, 1.07mmol, 1.0equiv), compound 8 (622mg, 3.22mmol, 3.0equiv), and anhydrous THF (80 mL) were added to a round-bottomed flask containing magnetons; adding 28 drops of pyridine into the mixture solution at the rate of 30 drops/min, heating to 80 ℃, stirring at 380rpm for reacting overnight, and reacting under the nitrogen atmosphere; after completion of the reaction, the mixture solution was dropwise added at a rate of 0.5mL/min to 300mL of methanol, and the precipitated solid was filtered and dried to obtain monomer M5 (820 mg, 70%). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):8.01(s,2H),7.76(s,2H),7.39-7.42(m,4H),7.16(s,2H),4.3-4.36(m,4H),2.62-2.68(dd,J＝7.2Hz,4H),1.85-1.75(s,2H),1.60-1.51(m,14H),1.45-0.17(m,56H),0.87-0.81(m,16H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):165.74,165.03,145.13,142.26,139.75,137.64,137.39,137.33,136.98,135.70,130.26,127.98,127.36,123.75,121.10,114.83,112.98,112.06,111.70,77.34,77.22,77.13,77.02,76.70,56.38,40.80,38.52,34.36,33.58,31.93,30.16,29.76,29.74,29.72,29.69,29.40,29.38,26.69,22.70,14.20,14.13。
(6) Synthesis of Polymer A5: in a dry two-necked flask, monomer M5 (100.7mg, 0.05mmol), monomer M2 (53.4mg, 0.12mmol) and the catalyst tetrakis (triphenylphosphine) palladium (2.9 mg) were charged, and the reaction was carried out three times by changing nitrogen through vacuum, and solvent toluene (6 mL) was added by syringe; stirring the mixture solution at 140 ℃ to react for 48 hours, and carrying out the reaction under the nitrogen atmosphere; after the mixture solution is recovered to room temperature, the obtained polymer solution is dripped into 200mL of methanol at the speed of 0.5mL/min, and polymer precipitate is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a Soxhlet extractor sequentially using methanol, n-hexane, dichloromethane and chloroform as solvents, the concentrated solution of the chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration through filter paper and dried to obtain a black solid, i.e., polymer A5 (86mg, 56%).
Example 6
Polymer A6 was prepared according to the following synthetic route:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 4 was prepared according to the procedure of example 1.
(3) Compound 6 was prepared according to the procedure of example 1.
(4) Compound 7 was prepared according to the procedure of example 1.
(5) Monomer M1 was prepared according to the procedure of example 1.
(6) Synthesis of Polymer A6: adding monomer M1 (95.1mg, 0.05mmol), monomer M4 (49.1mg, 0.12mmol) and catalyst tetrakis (triphenylphosphine) palladium (2.9 mg) into a dry two-necked bottle, vacuumizing and changing nitrogen for three times, adding solvent toluene (6 mL) by using a syringe, stirring the mixture solution at 140 ℃ for reaction for 48 hours, and carrying out the reaction under the nitrogen atmosphere; and (3) after the mixture solution is returned to room temperature, dropwise adding the obtained polymer solution into 200mL of methanol at the speed of 0.5mL/min, filtering by using filter paper to obtain a polymer precipitate, namely a crude polymer product, collecting the crude polymer product, sequentially using methanol, n-hexane, dichloromethane and chloroform as solvents, separating and purifying by using a Soxhlet extractor, collecting a chloroform phase concentrated solution, precipitating in the methanol, filtering by using the filter paper to collect a precipitate, and drying to obtain a black solid, namely the polymer A6 (98mg, 68%).
Test example
Representative polymers A1, A2 and A3 synthesized in examples 1 to 3 were used as electron acceptor materials in organic solar cell devices (ITO anode/anode interface layer/active layer/cathode interface layer/cathode).
Table 1 shows device performance parameters of organic solar cells prepared based on the polymers A1, A2 and A3 as electron acceptor materials and PBDB-T as electron donor materials;
the device structure is as follows: ITO/PEDOT PSS/PBDB-T: acceptor/PFN-Br/Ag.
Table 1 device performance parameters of organic solar cells prepared based on examples 1 to 3
Table 2 shows physical characterization data including HOMO, LUMO, eg, egopt, td and the location of the crystalline peaks based on the polymers A1, A2 and A3.
TABLE 2 physical characterization data for examples 1-3 electron transport polymers
As can be seen from Table 2, the polymers A1, A2 and A3 all have high thermal stability and the thermal decomposition temperature is above 300 ℃; simultaneous optical bandgap Eg opt 1.44eV, 1.45eV and 1.41eV respectively, and the optical band gaps are lower; the HOMO's are all higher at-5.45 eV, -5.78eV, and-5.39eV, and the LUMO's are all lower at-3.83 eV, -3.87eV, and-3.61 eV, respectively, such that Eg = HOMO-LUMO, all give lower band gaps Eg of 1.62eV, 1.92eV, and 1.78eV, respectively. This indicates that the three polymers have better thermal stability and excellent electrochemical properties.
Preparing an organic solar cell device by using a commercially available PBDB-T as a donor of an organic solar cell and polymers A1, A2 and A3 as electron acceptor materials respectively; ultrasonically cleaning the purchased ITO substrate by acetone and isopropanol in sequence, and then treating in ultraviolet ozone for 10 minutes; placing the cleaned and blow-dried ITO substrate on a rotary table of a spin coater, spin-coating a PEDOT/PSSS aqueous solution on ITO conductive glass by adopting a solution spin coating method, and then drying the ITO conductive glass in the air at 150 ℃ for 15 minutes to form PEDOT: a PSS film; PBDB-T: a solution of A1/A2/A3 (w/w = 1:1) in chlorobenzene was spin-deposited on PEDOT: forming an active layer film with the thickness of 100-150 nm on the PSS film; evaporating 20nm Ca and 100nm Al as anode electrodes under high vacuum condition, and the prepared solar cell has effective working area of 4mm 2 . All preparation processes were carried out in a nitrogen atmosphere glove box. The device test is carried out under the irradiation of an Orie191192 AM1.5 sunlight simulation lamp, and the radiation degree is 1kW/m 2 J-V curves were tested using a Keithley model 2400 digital Source Meter. The current-voltage curves of the prepared positive battery devices are shown in fig. 7, and the relevant data are listed in table 1. As can be seen from FIG. 7 and Table 1, the electron transport polymer containing electron-withdrawing side groups provided by the present invention as an acceptor for an active layer can obtain a higher openingAnd the circuit voltage obtains certain battery device performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. An electron-transporting polymer having a pendant electron-withdrawing group, characterized by having a structure represented by any one of formulas A1 to A6:
n is 2 to 2000;
the R is 1 Is 2-octyl dodecyl;
the R is 2 Is hexyl.
2. A method of making an electron transporting polymer having electron withdrawing pendant groups according to claim 1 comprising the steps of:
benzo [1,2-b:4,5-b']Dithiophene-4,8-diones with
Mixing, and carrying out substitution reaction to obtain an intermediate a with a structure shown in a formula II;
mixing the intermediate a with the structure shown in the formula II, n-butyl lithium and tributyl tin chloride, and carrying out a stannization reaction to obtain an intermediate b with the structure shown in the formula III;
the intermediate b with the structure shown in the formula III and Br-pi 1 -CHO mixing, and performing Stille coupling reaction under the catalysis of a palladium catalyst to obtain a catalyst withAn intermediate c having a structure represented by formula IV;
carrying out bromination reaction on the intermediate c with the structure shown in the formula IV and N-bromosuccinimide in a tetrahydrofuran solvent to obtain an intermediate d with the structure shown in the formula V;
performing a clairvoyer reaction on the intermediate d with the structure shown in the formula V and H-A-H under the catalysis of pyridine to obtain an intermediate e with the structure shown in the formula VI;
the intermediate e and H-pi with the structure shown as the formula VI are reacted 2 Mixing H and performing Stille polymerization reaction under the catalysis of a palladium catalyst to obtain an electron-withdrawing side group-containing electron-transporting polymer with a structure shown in a formula I;
the R is 1 Is 2-octyl dodecyl;
π 1 is composed of
The R is 2 Is hexyl;
H-π 2 -H is
H-A-H is
3. An electron transport film comprising a solution of the electron transport polymer having an electron-withdrawing side group according to claim 1 or the electron transport polymer having an electron-withdrawing side group prepared by the method according to claim 2.
4. An organic photovoltaic cell device comprising an electron donor material and an electron acceptor material, wherein the electron acceptor material comprises the electron transport polymer having a pendant electron-withdrawing group of claim 1 or the electron transport polymer having a pendant electron-withdrawing group prepared by the preparation method of claim 2.
5. The organic photovoltaic cell device of claim 4, wherein the electron donor material comprises PBDB-T.
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