CN104031245A - Polymer photovoltaic material, preparation method and use thereof - Google Patents
Polymer photovoltaic material, preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a polymer photovoltaic material, a preparation method and use thereof. The molecule of the polymer material takes two-dimensional conjugate dibenzothiophene or naphtho-bithiophene as a donor, and takes thiophene and pyrrole diketone and derivatives thereof as receptors, and the polymer material has a structure shown in a formula (I) or a formula (II). The polymer material is simple in preparation and easy to purify, and has good solubleness in common organic solvents (for example, dichloromethane, trichloromethane, tetrahydrofuran, chlorobenzene or o-dichlorobenzene and the like). The film with high quality can be prepared by using a liquid method. The macromolecule is applied to a donor material of a solar battery, the energy conversion efficiency exceeds 7.5%, and the open-circuit voltage exceeds 1V.
Description
Technical field
The present invention relates to class photovoltaic material and preparation method thereof, particularly a class solution processable has Polymer photovoltaic materials of high open circuit voltage and preparation method thereof and an application.
Background technology
1986, it was to be that acceptor (A) has been prepared and had the double-deck organic photovoltaic devices of D/A heterojunction (C.W.Tang, Appl.Phys.Lett., 1986,48 to body (D), perylene that doctor Deng Qingyun of Kodak uses CuPc; 183-185.), under simulated solar irradiation, effciency of energy transfer approaches 1%.Nineteen ninety-five, the Yu Gang etc. of black square study group invented the derivative blended type of conjugated polymers/solubility C60 " body heterojunction " (bulk heterojunction) polymer solar battery (G.Yu of solution processable, J.Gao, J.C.Hummelen, F.Wudl, A.J.Heeger, Science, 1995,270:1789-1791).Body heterojunction type solar cell simplified preparation technology, by expanding to acceptor interfacial area and shortening exciton transmission range and improved effciency of energy transfer, thereby organic polymer solar cell research is afterwards all mainly to adopt body heterojunction structure.
In recent years, the polymer solar battery of solution processable is because preparation technology is simple, cost is low, quality is light, can be prepared into the advantages such as flexible device and be subject to extensive concern ((a) J.Chen and Y.Cao, Acc.Chem.Res.2009,42,1709-1718. (b) Y.Li, Acc.Chem.Res.2012,45,723-733.).Lot of domestic and foreign investigator has reported that the effciency of energy transfer of the solar device based on polymer materials reaches or exceedes 8% ((a) Z.He in succession, C.Zhong, S.Su, M.Xu, H.Wu and Y.Cao, Nat.Photonics2012, 6, 591-596. (b) M.Zhang, X.Guo, S.Zhang and J.Hou, Adv.Mater.2014, 26, 1118-1123. (c) Y.Deng, J.Liu, J.Wang, L.Liu, W.Li, H.Tian, X.Zhang, Z.Xie, Y.Geng, and F.Wang, Adv.Mater.2014, 26, 471-476. (d) L.Dou, J.You, J.Yang, C.Chen, Y.He, S.Murase, T.Moriarty, K.Emery, G.Li, Y.Yang, Nat.Photonics2012, 6, 180-185.).But up to the present, the open circuit voltage of high efficiency polymer solar battery is not very high, only have 0.8V left and right, and low open circuit voltage limits the development and futures application of polymer solar battery.
Thienopyrroles diketone is proved to be to form the important structural unit of high-level efficiency polymeric donor photovoltaic material.Itself has lot of advantages, such as: simple in structure, compactness, symmetry and planarity are good, easily synthetic, and there is interaction etc. in carbonylic oxygen atom and adjacent thiophenic sulfur atom.Therefore in the last few years, had been a great concern and obtained good device efficiency ((a) Y.Zou, A.Najari, P.Berrouard, S.Beaupre, B.
y.Tao and M.Leclerc, J.Am.Chem.Soc.2010,132,5330-5331. (b) J.Yuan, Z.Zhai, H.Dong, J.Li, Z.Jiang, Y.Li and W.L.Ma, Adv.Funct.Mater.2013,23,885 – 892. (c) K.Lu, J.Fang, Z.Yu, H.Yan, X.Zhu, Y.Zhang, C.He, and Z.Wei, Org.Electron.2012,13,3234-3242.).But the preparation of Polymer photovoltaic materials solution processable and that have high open circuit voltage is still one and needs the further problem of research.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide a kind of Polymer photovoltaic materials with high open circuit voltage of solution processable, and it is the soluble polymeric material containing Thienopyrroles diketone and derivative, benzene 1,4-Dithiapentalene or naphtho-two thiophene units.The molecule of this polymer materials is taking two-dimensional conjugated benzene 1,4-Dithiapentalene or naphthalene 1,4-Dithiapentalene as to body, Thienopyrroles diketone or derivatives thereof is acceptor, there is good solubility common are in machine solvent (as methylene dichloride, trichloromethane, tetrahydrofuran (THF), chlorobenzene or orthodichlorobenzene etc.), can prepare high-quality film by solution method.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
There is the Polymer photovoltaic materials of high open circuit voltage, have suc as formula the structure shown in (I) or formula (II):
Wherein, R
1and R
2all, independently selected from the straight chained alkyl or the branched-chain alkyl that replace or unsubstituted carbonatoms is 6～12, what D represented is to divide to body, and what A represented is acceptor portion, R
3and R
4all, independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted carbonatoms is 6～12, n is 20～100.
Exemplary Polymer photovoltaic materials has following structure:
R
1be selected from straight chained alkyl or branched-chain alkyl that replacement or unsubstituted carbonatoms are 6～12.
Thienopyrroles diketone has strong electron-withdrawing power, therefore can drag down under normal circumstances the highest occupied molecular orbital (HOMO energy level) of polymer materials, thereby can increase the open circuit voltage of polymer solar battery.The present invention is incorporated into Thienopyrroles diketone and derivative thereof in the Polymer photovoltaic materials of solution processable, carries out copolymerization with benzene 1,4-Dithiapentalene or the naphthalene 1,4-Dithiapentalene with two-dimentional conjugated structure, has prepared the Polymer photovoltaic materials of efficient solution processable.
Two of object of the present invention is to provide a kind of preparation method of the Polymer photovoltaic materials with high open circuit voltage, and described method comprises the steps:
Under inert atmosphere, under the katalysis of palladium catalyst, compound shown in compound shown in formula (III) and formula (IV) a or formula (IV) b is reacted, obtain the Polymer photovoltaic materials shown in formula (I) or formula (II);
Wherein, R
1and R
2all independently selected from replacing or unsubstituted carbonatoms be 6～12 straight chained alkyl or branched-chain alkyl, R
3and R
4all independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted carbonatoms is 6～12.
In the present invention, under inert atmosphere, under the katalysis of palladium catalyst, in the time making shown in compound shown in formula (III) and formula (IV) a that compound reacts, obtain compound shown in formula (I), when compound shown in compound shown in formula (III) and formula (IV) b is reacted, obtain compound shown in formula (II).
Preferably, described palladium catalyst is at tetrakis triphenylphosphine palladium.
Preferably, shown in compound shown in formula (III) and formula (IV) a, the molar ratio of compound is 1:1～1.5:1, for example 1.03:1,1.06:1,1.09:1,1.12:1,1.15:1,1.18:1,1.21:1,1.24:1,1.27:1,1.3:1,1.33:1,1.36:1,1.39:1,1.42:1,1.45:1 or 1.48:1, preferably 1:1.
Preferably, shown in compound shown in formula (III) and formula (IV) b, the molar ratio of compound is 1:1～1.5:1, for example 1.03:1,1.06:1,1.09:1,1.12:1,1.15:1,1.18:1,1.21:1,1.24:1,1.27:1,1.3:1,1.33:1,1.36:1,1.39:1,1.42:1,1.45:1 or 1.48:1, preferably 1:1.
Preferably, shown in described palladium catalyst and formula (III), the molar ratio of compound is 0.02～0.05:1, for example 0.022:1,0.024:1,0.026:1,0.028:1,0.03:1,0.032:1,0.034:1,0.036:1,0.038:1,0.04:1,0.042:1,0.044:1,0.046:1 or 0.048:1, preferably 0.02:1.
Preferably, the temperature of reaction of described reaction is 100～120 DEG C, for example 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, 110 DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C, 115 DEG C, 116 DEG C, 117 DEG C, 118 DEG C or 119 DEG C, preferably 120 DEG C.
Preferably, the reaction times of described reaction is 12～48 hours, for example 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours or 46 hours, preferably 24 hours.
Preferably, described reaction is carried out in organic solvent, and described organic solvent is specially the mixture of any one or at least two kinds in toluene, chlorobenzene or orthodichlorobenzene.The mixture of for example toluene of described mixture and chlorobenzene, the mixture of toluene and orthodichlorobenzene, the mixture of chlorobenzene and orthodichlorobenzene, the mixture of toluene, chlorobenzene and orthodichlorobenzene.
Preferably, described method also comprises following purification step: will be containing the solution cool to room temperature of the Polymer photovoltaic materials shown in formula (I) or formula (II), then add methanol extraction, throw out is filtered and collected, then pass through apparatus,Soxhlet's, with methyl alcohol, acetone and normal hexane etc., the composition of small molecules amount is removed respectively, then with trichloromethane, the composition of macromolecule is extracted, vacuum-evaporation is fallen after partial solvent, add methyl alcohol postprecipitation, throw out is filtered and collected, obtain the Polymer photovoltaic materials shown in formula (I) or formula (II).
Preferably, described method also comprises following purification step: will be dissolved in methylene dichloride containing the one in compound shown in formula (IV) a or formula (IV) b, wash and extract with the saturated aqueous solution of sodium-chlor subsequently, anhydrous magnesium sulfate drying, vacuum-evaporation is fallen after solvent, adopts methylene dichloride and the sherwood oil mixed solvent that volume ratio is 3:1～5:1 to cross the purification of chromatography silica gel post.
Preferably, described methylene dichloride and sherwood oil volume ratio are 3:1～5:1, for example 3.5:1,4:1,4.5:1 or 5:1, preferably 3:1.
Preferably, shown in formula (IV) b, compound is prepared by the following method:
Under inert atmosphere, under the katalysis of palladium catalyst, compound shown in compound shown in formula (V) and formula (VI) is reacted, then its reaction product is reacted with N-bromo-succinimide, obtain compound shown in formula (IV) b.
Wherein, R
2be selected from straight chained alkyl or branched-chain alkyl that replacement or unsubstituted carbonatoms are 6～12, R
3and R
4all independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted the total number of carbon atoms is 6～12.
Exemplary inert atmosphere is as nitrogen.
Preferably, described palladium catalyst is tetrakis triphenylphosphine palladium.
Preferably, shown in compound shown in formula (V) and formula (VI), the molar ratio of compound is 2:1～3:1, for example 2.05:1,2.1:1,2.15:1,2.2:1,2.25:1,2.3:1,2.35:1,2.4:1,2.45:1,2.5:1: 2.55:1,2.6:1,2.65:1,2.7:1,2.75:1,2.8:1,2.85:1,2.9:1,2.95:1 or 3.0:1, preferably 2:1.
Preferably, shown in described palladium catalyst and formula (V), the molar ratio of compound is 0.02～0.05:1, for example 0.022:1,0.024:1,0.026:1,0.028:1,0.03:1,0.032:1,0.034:1,0.036:1,0.038:1,0.04:1,0.042:1,0.044:1,0.046:1 or 0.048:1, preferably 0.02:1.
Preferably, the temperature of reaction of the reaction of compound shown in compound shown in formula (V) and formula (VI) is 100～120 DEG C, for example 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, 110 DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C, 115 DEG C, 116 DEG C, 117 DEG C, 118 DEG C or 119 DEG C, preferably 120 DEG C.
Preferably, the reaction times of the reaction of compound shown in compound shown in formula (V) and formula (VI) is 24～48 hours, for example 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours or 46 hours, preferably 24 hours.
Preferably, described reaction is carried out in organic solvent, and described organic solvent is specially the mixture of any one or at least two kinds in toluene, chlorobenzene or orthodichlorobenzene.The mixture of for example toluene of described mixture and chlorobenzene, the mixture of toluene and orthodichlorobenzene, the mixture of chlorobenzene and orthodichlorobenzene, the mixture of toluene, chlorobenzene and orthodichlorobenzene.
Preferably, by the reaction mixture cool to room temperature of compound shown in compound shown in formula (V) and formula (VI), then be dissolved in methylene dichloride, wash with sodium chloride aqueous solution subsequently, anhydrous magnesium sulfate drying, vacuum-evaporation is fallen after solvent, adopt methylene dichloride and the sherwood oil mixed solvent that volume ratio is 6:1 to cross the purification of chromatography silica gel post, obtain yellow solid (being the reaction product of the compound shown in the compound shown in formula (V) and formula (VI)), then it is reacted with N-bromo-succinimide.
Preferably, the detailed process that the reaction product of the compound shown in the compound shown in formula (V) and formula (VI) is reacted with N-bromo-succinimide is:
It is in the trichloromethane and trifluoroacetic acid mixing solutions of 10:1～10:3 that the reaction product of compound shown in compound shown in formula (V) and formula (VI) is added to volume ratio, and preferably 10:1, then adds N-bromo-succinimide to react.
The temperature of reaction of preferably, reacting with N-bromo-succinimide is room temperature.Described room temperature is 25 DEG C.
Preferably, the reaction times of reacting with N-bromo-succinimide is 5～24 hours, for example 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours or 23 hours, preferably 5 hours.
Preferably, to carry out reacted reaction product sodium chloride aqueous solution with N-bromo-succinimide washes, anhydrous magnesium sulfate drying, solvent is fallen in vacuum-evaporation, the methylene dichloride that employing volume ratio is 3:1 and the mixed solvent of sherwood oil are crossed chromatography silica gel post and are purified, obtain yellow solid, obtain compound shown in formula (IV) b.
The preparation method of compound shown in exemplary formula (IV) b; comprise that step is as follows: under the katalysis of tetrakis triphenylphosphine palladium; compound shown in compound shown in formula V and formula VI is reacted, 24～48 hours (preferably 48 hours) of 100～120 DEG C (preferably 120 DEG C) backflow under nitrogen protection.By reaction mixture cool to room temperature, be then dissolved in methylene dichloride, wash with sodium chloride aqueous solution subsequently, anhydrous magnesium sulfate drying, vacuum-evaporation is fallen after solvent, adopts methylene dichloride/sherwood oil (6/1, V/V) cross chromatography silica gel post and purify, obtain yellow solid; Then yellow solid is mixed with trichloromethane, add a small amount of trifluoroacetic acid, then add N-bromo-succinimide, under room temperature, react 5～24 hours (preferably 5 hours), wash with sodium chloride aqueous solution subsequently, anhydrous magnesium sulfate drying, vacuum-evaporation is fallen after solvent, adopts methylene dichloride/sherwood oil (3/1, V/V) to cross chromatography silica gel post and purifies, obtain yellow solid, obtain the compound shown in formula (IV) b.
Three of object of the present invention is to provide a kind of purposes of the Polymer photovoltaic materials with high open circuit voltage as above, and it is for the preparation of photovoltaic device.
Preferably, described photovoltaic device is organic solar batteries.
Preferably, it is for the preparation of the donor material of organic solar batteries.
Compared with the prior art, the present invention has following beneficial effect:
The present invention by have the Thienopyrroles diketone of strong electron-withdrawing power and derivative thereof be applied to solution processable Polymer photovoltaic materials design and synthetic in, synthesized the soluble polymer molecule taking benzene 1,4-Dithiapentalene or naphthalene 1,4-Dithiapentalene and Thienopyrroles diketone and its derivative as core.They have good solubility common are in machine solvent (as trichloromethane, tetrahydrofuran (THF), toluene), can prepare high-quality film by the method that solution gets rid of painting; Meanwhile, these polymer molecules have wide visible region and absorb, lower HOMO energy level and relatively narrow band gap.Taking this type of polymer molecule as to body, PC
60bM or PC
70bM is that acceptor has been prepared body heterojunction organic solar batteries, and the highest energy efficiency of conversion after its optimization can exceed 7.5%, and open circuit voltage exceedes 1V.In addition, the preparation method of polymer materials provided by the invention is simple, easily purifying.
Brief description of the drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of polymer P 1 under chloroformic solution neutralized film state;
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of polymer P 4 under chloroformic solution neutralized film state;
Fig. 3 is the oxidizing potential that polymer P 1 electrochemical method is measured;
Fig. 4 is the cyclic voltammetry curve that polymer P 4 electrochemical methods are measured;
Fig. 5 is for having shown that structure is ITO/PEDOT:PSS/P1:PC
70the I-V curve of the polymer solar cell device of BM/Ca/Al;
Fig. 6 is for having shown that structure is ITO/PEDOT:PSS/P4:PC
60the I-V curve of the polymer solar cell device of BM/Ca/Al.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1 BDTT synthetic (in formula (III), R
1=C
6h
13compound)
Chemical reaction flow process (concrete reactions steps and reaction conditions reference Lijun Huo, Angew.Chem.Int.Ed.2011,50,9697 – 9702) as follows:
Embodiment 2 2BrTPD's is synthetic
Chemical reaction flow process (concrete reactions steps and reaction conditions reference Yingping Zou, J.Am.Chem.Soc.2010,132,5330 – 5331) as follows:
Synthesizing of embodiment 3 polymer Ps 1
Chemical reaction flow process is as follows, and concrete reactions steps and reaction conditions are as follows:
In 50mL there-necked flask; add 162.7mg (0.18mmol) compound 6 and 76.5mg (0.18mmol) compound 9; add again the super dry toluene of 16mL and the super dry N of 4mL; dinethylformamide; lead to and after argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium in 20 minutes; take out again inflation three times, slowly temperature is risen to 110 DEG C afterwards, lucifuge reaction 24 hours under argon shield.Question response finishes, reaction system naturally cools to after room temperature, reaction solution is splashed into and in 200mL methyl alcohol, carries out precipitating, leach throw out and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, normal hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum-drying, finally obtain 137.0mg polymer P 1, productive rate 85%.At room temperature record the number-average molecular weight Mn=59.6KDa of this polymkeric substance taking tetrahydrofuran (THF) as moving phase by gel exclusion chromatography, dispersity PDI=2.38.
The preparation method of other polymer P 2-P3 is substantially the same, only needs compound 9 to carry out respectively polyreaction with the compound 16-17 in as follows.
Synthesizing of embodiment 4 compounds 12
Chemical reaction flow process is as follows, and concrete reactions steps and reaction conditions are as follows:
Compound 10 (2.0g, 8.0mmol) is dissolved in to CHCl
3/ CH
3in the solution of COOH volume ratio 10:1, add NBS (N-bromo-succinimide) (3.2g, 18mmol) to stir 3 hours.Reaction finishes rear CHCl
3extract 3 times, organic phase rotary evaporation, except desolventizing, does eluent with normal hexane, uses silica gel column chromatography separated product, colourless transparent liquid (3.1g, productive rate 95%).MS(MALDI-TOF-MS):m/z＝410.2。
1H?NMR(400MHz,CDCl3,ppm)δ:2.53(t，4H)，1.65(t，4H)，1.38(m，12H)，0.92(t，6H)。
Compound 11 (1g/3.7mmol) is dissolved in 15ml dry tetrahydrofuran, passing into argon gas takes out and fills three times, be cooled to-78 DEG C and stir 10 minutes, 2.4M butyllithium (3.2ml/7.8mmol) all dripped in 20-30 minute, kept low-temp reaction 3 hours.The disposable 1M trimethyltin chloride (9.2ml/9.2mmol) that adds, reaction is spent the night.N-hexane extraction three times, rotary evaporation obtains yellow liquid after going out desolventizing, directly drops into next step reaction without purifying.
Embodiment 5 TPD-Br (compound 13)
Chemical reaction flow process figure is as shown in the schema in embodiment 4, and compound 8 (5g/18.8mmol) is dissolved in 50ml trifluoroacetic acid, drips the 5ml vitriol oil, adds NBS (1.7g/9mmol) to stir to pour into after 5 minutes in intermediate water, to use CHCl
3extract 3 times.Organic phase rotary evaporation is used CH except after desolventizing
2cl
2/ normal hexane volume ratio 1:1 mixing solutions does eluent, uses silica gel column chromatography separated product, obtains white solid product (2.6g, productive rate 40%).MS(MALDI-TOF-MS)：m/z＝408.0。
1H?NMR(400MHz，CDCl3，ppm)δ：7.8(s，1H)，3.61(t，2H)，1.64(m，2H)，1.26(m，10H)，0.87(t，3H)。
Embodiment 6 2BrTPD-C6-TPD (compound 15)
Chemical reaction flow process figure is as shown in the schema in embodiment 4, compound 12 (660mg/1.5mmol) is dissolved in and heavily steams toluene with compound 13 (1g/2.9mmol), logical argon gas, after 10 minutes, adds catalyzer four (triphenyl phosphorus) palladium, and logical argon gas is taken out and filled 3 times.Under argon shield, 110 DEG C are reacted 24 hours.After finishing, reaction uses a dry method on a sample CH
2cl
2/ normal hexane volume ratio 6:1 mixing solutions does eluent, uses silica gel column chromatography separated product, obtains yellow solid (740mg, productive rate 80%).MS(MALDI-TOF-MS)：m/z＝636.8。
1H?NMR(400MHz，CDCl
3，ppm)δ：7.79(s，2H)，3.61(t，4H)，2.31(s，6H),1.64(m，4H)，1.26(m，20H)，0.87(t，6H)。
Compound 14 (500mg/0.78mmol) is dissolved in 150ml trifluoroacetic acid, drips vitriol oil 3ml, adds NBS (276.2mg/1.56mmol) room temperature reaction 5 hours, uses CHCl
3extract 3 times, organic phase rotary evaporation is except desolventizing, CH
2cl
2/ normal hexane 3:1 does eluent, uses silica gel column chromatography separated product, obtains yellow solid (186.7mg, productive rate 30%).MS(MALDI-TOF-MS)：m/z＝796.7。
1H?NMR(400MHz，CDCl
3，ppm)δ：3.61(t，4H)，2.31(s，6H)，1.64(m，4H)，1.26(m，20H)，0.87(t，6H)。
Synthesizing of embodiment 7 polymer Ps 4
Figure is as follows for chemical reaction flow process, and concrete reactions steps and reaction conditions are as follows:
In 50mL there-necked flask; add 90.4mg (0.1mmol) compound 6 and 93.7mg (0.1mmol) compound 15; add again the super dry toluene of 12mL and the super dry N of 2mL; dinethylformamide; lead to and after argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium in 20 minutes; take out again inflation three times, slowly temperature is risen to 110 DEG C afterwards, lucifuge reaction 24 hours under argon shield.Question response finishes, reaction system naturally cools to after room temperature, reaction solution is splashed into and in 200mL methyl alcohol, carries out precipitating, leach throw out and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, normal hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum-drying, finally obtain 87.8mg polymer P 2, productive rate 65%.At room temperature record the number-average molecular weight M of this polymkeric substance taking tetrahydrofuran (THF) as moving phase by gel exclusion chromatography
n=15.6KDa, dispersity PDI=2.32.
The preparation method of other polymer P 5-P12 is substantially the same, and concrete reacting flow chart is as follows:
Synthesizing of embodiment 8 compounds 26
Chemical reaction flow process is as follows, and concrete reactions steps and reaction conditions are as follows:
By 7.2g (50mmol) compound 23,17.6g (200mmol) Pentyl alcohol, 25mL toluene and 0.6g (5mmol) anhydrous Na HSO
4, adding in 100mL there-necked flask, high pure nitrogen protection, stirs and is warming up to 110 DEG C, reacts 5 hours.Reaction is cooled to room temperature after finishing, and after steaming and desolventizing, does eluent with petrol ether/ethyl acetate volume ratio 100:1 mixing solutions, uses silica gel column chromatography separated product, obtains colourless liquid, and (11.05g, productive rate 65%),
1h NMR (400MHz, CDCl
3, ppm) and δ: 0.91 (t, 6H), 1.34-1.47 (m, 8H) 1.80-1.86 (m, 4H), 3.97 (t, 4H), 6.18 (s, 2H).
Compound 24 (2.0g, 8.0mmol) is dissolved in to CHCl
3/ CH
3in the solution of COOH volume ratio 10:1, add NBS (N-bromo-succinimide) (3.2g, 18mmol) to stir 3 hours.Reaction finishes rear CHCl
3extract 3 times, organic phase rotary evaporation, except desolventizing, does eluent with normal hexane, uses silica gel column chromatography separated product, transparent liquid (3.1g, productive rate 95%).MS(MALDI-TOF-MS):m/z＝414.2。
1H?NMR(400MHz,CDCl
3，ppm)δ：0.91(t，6H)，1.34-1.47(m，8H)1.80-1.86(m，4H)，3.97(t，4H)。
Compound 25 (1g/2.4mmol) is dissolved in 15ml dry tetrahydrofuran, passing into argon gas takes out and fills three times, be cooled to-78 DEG C and stir 10 minutes, 2.4M butyllithium (2.5ml/6mmol) all dripped in 20-30 minute, kept low-temp reaction 3 hours.The disposable 1M trimethyltin chloride (7.2ml/7.2mmol) that adds, reaction is spent the night.N-hexane extraction three times, rotary evaporation obtains yellow liquid after going out desolventizing, directly drops into next step reaction without purifying.
Synthesizing of embodiment 9 compounds 28
As described in Example 8, concrete reactions steps and reaction conditions are as follows for chemical reaction flow process:
Compound 26 (873mg/1.5mmol) and compound 8 (1.0g/3mmol) are dissolved in and heavily steam toluene, and logical argon gas, after 10 minutes, adds catalyzer tetrakis triphenylphosphine palladium, and logical argon gas is taken out and filled 3 times.Under argon shield, 110 DEG C are reacted 24 hours.After finishing, reaction uses a dry method on a sample CH
2cl
2/ normal hexane volume ratio 6:1 mixing solutions does eluent, uses silica gel column chromatography separated product, obtains yellow solid (938.0mg, productive rate 80%).MS(MALDI-TOF-MS)：m/z＝782.3。
1H?NMR(400MHz，CDCl
3，ppm)δ：7.73(s，2H)，4.18(t，4H)，3.66(t，4H)，1.85-1.94(m，4H)，1.64-1.71(m，4H)，1.39-1.51(m，8H),1.19-1.37(m，20H)，0.96(t，6H)，0.87(t，6H)。
Compound 27 (1g/1.3mmol) is dissolved in 150ml trifluoroacetic acid, adds NBS (513.3mg/2.9mmol) room temperature reaction 5 hours, uses CHCl
3extract 3 times, organic phase rotary evaporation is except desolventizing, CH
2cl
2/ normal hexane 3:1 does eluent, uses silica gel column chromatography separated product, obtains yellow solid (1.1g, productive rate 90%).MS(MALDI-TOF-MS)：m/z＝940.1。
1H?NMR(400MHz，CDCl
3，ppm)δ：4.18(t，4H)，3.66(t，4H)，1.85-1.94(m，4H)，1.64-1.71(m，4H)，1.39-1.51(m，8H),1.19-1.37(m，20H)，0.96(t，6H)，0.87(t，6H)。
Synthesizing of embodiment 10 polymer Ps 13
Figure is as follows for chemical reaction flow process, and concrete reactions steps and reaction conditions are as follows:
In 50mL there-necked flask; add 90.4mg (0.1mmol) compound 6 and 94.0mg (0.1mmol) compound 28; add again the super dry orthodichlorobenzene of 12mL and the super dry N of 2mL; dinethylformamide; lead to and after argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium in 20 minutes; take out again inflation three times, slowly temperature is risen to 120 DEG C afterwards, lucifuge reaction 24 hours under argon shield.Question response finishes, reaction system naturally cools to after room temperature, reaction solution is splashed into and in 200mL methyl alcohol, carries out precipitating, leach throw out and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, normal hexane and chloroform successively, the concentrated chloroform extract finally obtaining, and be added dropwise to and in 200mL methyl alcohol, carried out precipitating again, filter out and precipitate and carry out vacuum-drying, finally obtain 88.2mg polymer P 10, productive rate 65%.At room temperature record the number-average molecular weight Mn=31.9KDa of this polymkeric substance taking tetrahydrofuran (THF) as moving phase by gel exclusion chromatography, dispersity PDI=1.52.
Embodiment 11 measures the ultraviolet-visible absorption spectroscopy of polymkeric substance under chloroformic solution neutralized film state and utilizes experimental formula to calculate the optical band gap of polymkeric substance.
Appropriate polymer P 1 is dissolved in chloroform, to be made into certain density solution and to get part solution and is spin-coated to the film of making polymkeric substance on quartz plate.
The ultraviolet-visible absorption spectroscopy that polymer P 1 records under chloroformic solution neutralized film state as shown in Figure 1.The optical band gap of polymkeric substance uses formula (E
g=1240/ λ absorbs limit) calculate, wherein the maximum absorption band of P1 in chloroformic solution is 530nm, film has wide absorption at 300-650nm, maximum absorption band is 606nm, absorb limit at 655nm, optical band gap is 1.89eV, shows that this is the semiconducting organic polymer of a narrow band gap.
The testing method of other polymer Ps 2-P13 is substantially the same.Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of polymer P 4 under chloroformic solution neutralized film state.Absorbing boundary in P4 chloroformic solution is 654nm, and maximum absorption band is in 625nm left and right.Show that at the acromion of 620nm left and right two kinds of polymkeric substance still have certain accumulation in the chloroformic solution of dilution.Accumulation under filminess adds forces the absorbing boundary of polymeric film all to have obvious red shift than solution, and P4 is from 654nm to 655nm.By formula E
g=1240/ λ, the optical band gap that can calculate P4 is 1.89eV.
Fig. 3 is the oxidizing potential that polymer P 1 electrochemical method is measured.The oxidation take-off potential of polymer P 1 is 0.83eV.According to formula E
hOMO=-e (E
ox onset+ 4.71) (eV) calculate, the HOMO energy level of polymer P 1 is-5.54eV, and lower HOMO energy level contributes to improve the V of solar cell
oc, increased the aerial stability of polymkeric substance simultaneously.
Embodiment 12 measures the cyclic voltammetry curve under polymer thin membrane stage
Fig. 4 is the cyclic voltammogram based on P4 film.The chloroform soln of P4 is coated on platinum electrode, with Ag/Ag
+for reference electrode, wait to dry in the acetonitrile solution that film forming is placed on phosphofluoric acid 4-butyl amine and measure.The initial oxidation current potential obtaining from figure and initial reduction potential, then calculate E by formula
hOMO=-e (E
ox onset+ 4.71) (eV)=-5.62eV, E
lUMO=-e (E
red onset+ 4.71) (eV)=-3.43eV.
The testing method of other polymer Ps 1-P13 is substantially the same.
The Photovoltaic Properties test of embodiment 13 P1
Taking P1 as to body, PC
70bM is that acceptor has been prepared organic solar batteries device by solution spin coating.
Device architecture is ITO/PEDOT:PSS/P1:PC
70bM/Ca/Al.Preparation method is as follows:
By the PC of P1 and homogenous quantities
70bM blend (P1:PC
70bM mass ratio is 1:1), be dissolved in trichloromethane to make the solution of 10mg/mL.In the glass substrate of transparent silver suboxide tin (ITO) coating, manufacture organic solar batteries.Transparent conducting glass with ITO is used to deionized water, acetone, the each ultrasonic cleaning of Virahol 15 minutes successively, then use ozonize substrate surface, PEDOT:PSS is spin-coated on ITO, the rotating speed of spin coating is 2000-6000 rev/min, and be dried 15 minutes at 150 DEG C, obtaining thickness is the anode modification layer of 30nm.In glove box by polymkeric substance and [6,6]-phenyl C
70methyl-butyrate (PC
70bM) chloroformic solution is evenly spin-coated on this solution on anode modification layer with the rotating speed of 600-4000 rev/min, obtains the active material layer that thickness is 100-300nm.Finally 2 × 10
-6under the vacuum tightness of holder by Ca evaporation to active material layer, to form thickness be 20nm cathodic modification layer; And 2 × 10
-6under the vacuum tightness of holder by Al evaporation to negative electrode decorative layer, to form thickness be 100nm negative electrode, thus obtain polymer solar cell device.The white light source that the filter set cooperation that uses 500W xenon lamp and AM1.5 is simulated solar irradiation, regulates the light intensity of device measured place to 100mW/cm
-2, use Keithley open circuit voltage, short-circuit current and three parameters of packing factor to prepared polymer solar cell device to test.Fig. 5 is for having shown that structure is ITO/PEDOT:PSS/P1:PC
70the I-V curve of the polymer solar cell device of BM/Ca/Al, the wherein open circuit voltage (V of polymer P 1
oc)=0.99V, short-circuit current (J
sc)=8.69mA/cm
2, packing factor (FF)=45%.Fig. 6 is for having shown that structure is ITO/PEDOT:PSS/P4:PC
60the I-V curve of the polymer solar cell device of BM/Ca/Al.Wherein open circuit voltage (the V of polymer P 4
oc)=1.01V, short-circuit current (J
sc)=13.07mA/cm
2, packing factor (FF)=47%.
The testing method of other polymer Ps 2-P13 is substantially the same, and acceptor material is PC
70bM or PC
60bM.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a Polymer photovoltaic materials, is characterized in that, it has the structure shown in formula (I) or formula (II):
Wherein, R
1and R
2all independently selected from replacing or unsubstituted carbonatoms be 6～12 straight chained alkyl or branched-chain alkyl, R
3and R
4all, independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted carbonatoms is 6～12, n is 20～100.
2. a preparation method for Polymer photovoltaic materials as claimed in claim 1, is characterized in that, described method comprises the steps:
Under inert atmosphere, under the katalysis of palladium catalyst, compound shown in compound shown in formula (III) and formula (IV) a or formula (IV) b is reacted, obtain the Polymer photovoltaic materials shown in formula (I) or formula (II);
Wherein, R
1and R
2all independently selected from replacing or unsubstituted carbonatoms be 6～12 straight chained alkyl or branched-chain alkyl, R
3and R
4all independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted carbonatoms is 6～12.
3. method as claimed in claim 2, is characterized in that, described palladium catalyst is at tetrakis triphenylphosphine palladium;
Preferably, shown in compound shown in formula (III) and formula (IV) a, the molar ratio of compound is 1:1～1.5:1, preferably 1:1;
Preferably, shown in compound shown in formula (III) and formula (IV) b, the molar ratio of compound is 1:1～1.5:1, preferably 1:1;
Preferably, shown in described palladium catalyst and formula (III), the molar ratio of compound is 0.02～0.05:1, preferably 0.02:1;
Preferably, the temperature of reaction of described reaction is 100～120 DEG C, preferably 120 DEG C;
Preferably, the reaction times of described reaction is 12～48 hours, preferably 24 hours;
Preferably, described reaction is carried out in organic solvent, and described organic solvent is the mixture of any one or at least two kinds in toluene, chlorobenzene or orthodichlorobenzene.
4. method as claimed in claim 2 or claim 3, is characterized in that, described method also comprises following purification step:
Will be containing the solution cool to room temperature of the Polymer photovoltaic materials shown in formula (I) or formula (II), then add methanol extraction, throw out is filtered and collected, then pass through apparatus,Soxhlet's, adopt respectively methyl alcohol, acetone, normal hexane and chloroform extraction, vacuum-evaporation is fallen after partial solvent, adds methyl alcohol postprecipitation, throw out is filtered and collected, obtain the Polymer photovoltaic materials shown in formula (I) or formula (II);
Preferably, described method also comprises following purification step: will be dissolved in methylene dichloride containing the one in compound shown in formula (IV) a or formula (IV) b, wash and extract with the saturated aqueous solution of sodium-chlor subsequently, anhydrous magnesium sulfate drying, vacuum-evaporation is fallen after solvent, adopt methylene dichloride and sherwood oil mixed solvent that volume ratio is 3:1～5:1, preferably 3:1, crosses chromatography silica gel post and purifies.
5. the method as described in one of claim 2-4, is characterized in that, shown in formula (IV) b, compound is prepared by the following method:
Under inert atmosphere, under the katalysis of palladium catalyst, compound shown in compound shown in formula (V) and formula (VI) is reacted, then its reaction product is reacted with N-bromo-succinimide, obtain compound shown in formula (IV) b;
Wherein, R
2be selected from straight chained alkyl or branched-chain alkyl that replacement or unsubstituted carbonatoms are 6～12, R
3and R
4all independently selected from the direct-connected alkyl or the alkoxyl group that replace or unsubstituted carbonatoms is 6～12.
6. method as claimed in claim 5, is characterized in that, described palladium catalyst is tetrakis triphenylphosphine palladium;
Preferably, shown in compound shown in formula (V) and formula (VI), the molar ratio of compound is, 2:1～3:1, preferably 2:1;
Preferably, shown in described palladium catalyst and formula (V), the molar ratio of compound is 0.02～0.05:1, preferably 0.02:1;
Preferably, the temperature of reaction of the reaction of compound shown in compound shown in formula (V) and formula (VI) is 100～120 DEG C, preferably 120 DEG C;
Preferably, the reaction times of the reaction of compound shown in compound shown in formula (V) and formula (VI) is 24～48 hours, preferably 24 hours;
Preferably, described reaction is carried out in organic solvent, and described organic solvent is the mixture of any one or at least two kinds in toluene, chlorobenzene or orthodichlorobenzene;
Preferably, by the reaction mixture cool to room temperature of compound shown in compound shown in formula (V) and formula (VI), then be dissolved in methylene dichloride, wash subsequently anhydrous magnesium sulfate drying with sodium chloride aqueous solution, vacuum-evaporation is fallen after solvent, adopt methylene dichloride and sherwood oil mixed solvent that volume ratio is 4:1～6:1, preferably 6:1, crosses chromatography silica gel post and purifies, obtain yellow solid, then it is reacted with N-bromo-succinimide.
7. the method as described in one of claim 2-6, is characterized in that, the detailed process that shown in compound shown in formula (V) and formula (VI), the reaction product of compound is reacted with N-bromo-succinimide is:
It is in the trichloromethane and trifluoroacetic acid mixing solutions of 10:1～10:3 that the reaction product of compound shown in compound shown in formula (V) and formula (VI) is added to volume ratio, and preferably 10:1, then adds N-bromo-succinimide to react.
8. the method as described in one of claim 2-7, is characterized in that, the temperature of reaction of reacting with N-bromo-succinimide is room temperature;
Preferably, the reaction times of reacting with N-bromo-succinimide is 5～24 hours, preferably 5 hours;
Preferably, to carry out reacted reaction product sodium chloride aqueous solution with N-bromo-succinimide washes, anhydrous magnesium sulfate drying, solvent is fallen in vacuum-evaporation, the methylene dichloride that employing volume ratio is 3:1 and the mixed solvent of sherwood oil are crossed chromatography silica gel post and are purified, obtain yellow solid, obtain compound shown in formula (IV) b.
9. a purposes for Polymer photovoltaic materials as claimed in claim 1, is characterized in that, it is for the preparation of photovoltaic device.
10. purposes as claimed in claim 9, is characterized in that, described photovoltaic device is organic solar batteries;
Preferably, it is for the preparation of the donor material of organic solar batteries.
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