CN104031245B - A kind of Polymer photovoltaic materials, preparation method and its usage - Google Patents

A kind of Polymer photovoltaic materials, preparation method and its usage Download PDF

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CN104031245B
CN104031245B CN201410285894.3A CN201410285894A CN104031245B CN 104031245 B CN104031245 B CN 104031245B CN 201410285894 A CN201410285894 A CN 201410285894A CN 104031245 B CN104031245 B CN 104031245B
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CN104031245A (en
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魏志祥
吕琨
夏本正
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National Center for Nanosccience and Technology China
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of Polymer photovoltaic materials, preparation method and its usage. The molecule of this polymeric material is taking two-dimensional conjugated benzene 1,4-Dithiapentalene or naphthalene 1,4-Dithiapentalene as to body, and Thienopyrroles diketone and derivative thereof are acceptor, and it has the structure shown in formula (I) or formula (II). This type of polymeric material preparation method for material is simple, easily purifying, they have good dissolubility common are in machine solvent (as carrene, chloroform, oxolane, chlorobenzene or o-dichlorohenzene etc.), can prepare high-quality film by solwution method. This family macromolecule is for the donor material of solar cell, and energy conversion efficiency exceedes 7.5%, and open-circuit voltage exceedes 1V.

Description

A kind of Polymer photovoltaic materials, preparation method and its usage
Technical field
The present invention relates to class photovoltaic material and preparation method thereof, particularly a class solution processable hasPolymer photovoltaic materials of high open circuit voltage and preparation method thereof and application.
Background technology
1986, it was to be acceptor (A) system to body (D), perylene that doctor Deng Qingyun of Kodak uses CuPcStandby have the double-deck organic photovoltaic devices of D/A hetero-junctions (C.W.Tang, Appl.Phys.Lett.,1986,48; 183-185.), under simulated solar irradiation, energy conversion efficiency approaches 1%. Nineteen ninety-five black square seminarYu Gang etc. invented the derivative blended type of conjugated polymer/solubility C60 of solution processable " body be heterogeneousKnot " (bulkheterojunction) polymer solar battery (G.Yu, J.Gao, J.C.Hummelen, F.Wudl, A.J.Heeger, Science, 1995,270:1789-1791). The letter of body heterojunction type solar cellChange preparation technology, improved power conversion by expanding to acceptor interfacial area and shortening exciton transmission rangeEfficiency, thereby the research of organic polymer solar cell is afterwards all mainly to adopt body heterojunction structure.
In recent years, the polymer solar battery of solution processable was simple because of preparation technology, cost is low,Quality is light, can be prepared into the advantages such as flexible device and be subject to extensive concern ((a) J.ChenandY.Cao, Acc.Chem.Res.2009,42,1709-1718.(b)Y.Li,Acc.Chem.Res.2012,45,723-733.)。Lot of domestic and foreign researcher has reported that the energy conversion efficiency of the solar device based on polymeric material reaches in successionTo or exceed 8% ((a) Z.He, C.Zhong, S.Su, M.Xu, H.WuandY.Cao, Nat.Photonics2012,6,591-596.(b)M.Zhang,X.Guo,S.ZhangandJ.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,andF.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, high efficiency polymer solar batteryOpen-circuit voltage is not very high, only have 0.8V left and right, and low open-circuit voltage has limited polymer solarThe development and futures application of battery.
Thienopyrroles diketone is proved to be to form the important structure list of high efficiency polymeric donor photovoltaic materialUnit. Itself has lot of advantages, such as: simple in structure, compactness, symmetry and flatness are good, easily closeBecoming, there is interaction etc. in carbonylic oxygen atom and adjacent thiophenic sulfur atom. Therefore be subject in the last few years,Pay close attention to greatly and obtained good device efficiency ((a) Y.Zou, A.Najari, P.Berrouard, S.Beaupre,B.Y.TaoandM.Leclerc,J.Am.Chem.Soc.2010,132,5330-5331.(b)J.Yuan,Z.Zhai,H.Dong,J.Li,Z.Jiang,Y.LiandW.L.Ma,Adv.Funct.Mater.2013,23,885–892.(c)K.Lu,J.Fang,Z.Yu,H.Yan,X.Zhu,Y.Zhang,C.He, andZ.Wei, Org.Electron.2012,13,3234-3242.). But solution processable and haveThe preparation of the Polymer photovoltaic materials of 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 having of a kind of solution processableThe Polymer photovoltaic materials of high open circuit voltage, it is for containing Thienopyrroles diketone and derivative thereof, benzo two thiophenesThe soluble polymeric material of fen or naphtho-two thiophene units. The molecule of this polymeric material is with two-dimensional conjugatedBenzene 1,4-Dithiapentalene or naphthalene 1,4-Dithiapentalene are to body, and Thienopyrroles diketone or derivatives thereof is acceptor, oftenIn the organic solvent (as carrene, chloroform, oxolane, chlorobenzene or o-dichlorohenzene etc.) of seeing, haveGood dissolubility, can prepare high-quality film by solwution 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, R1And R2All independently selected from the straight chained alkyl replacing or unsubstituted carbon number is 6～12Or branched alkyl, what D represented is to divide to body, what A represented is acceptor portion, R3And R4All independentlyBe selected from direct-connected alkyl or alkoxyl that replacement or unsubstituted carbon number are 6～12, n is 20～100.
Exemplary Polymer photovoltaic materials has following structure:
R1Be selected from straight chained alkyl or branched alkyl that replacement or unsubstituted carbon number are 6～12.
Thienopyrroles diketone has strong electron-withdrawing power, therefore can drag down under normal circumstances polymeric materialThe highest occupied molecular orbital (HOMO energy level) of material, thus the open circuit electricity of polymer solar battery can be increasedPress. The present invention is incorporated into Thienopyrroles diketone and derivative thereof the Polymer photovoltaic materials of solution processableIn, carry out copolymerization with benzene 1,4-Dithiapentalene or the naphthalene 1,4-Dithiapentalene with two-dimentional conjugated structure, prepare efficientThe Polymer photovoltaic materials of solution processable.
Two of object of the present invention is to provide a kind of preparation of the Polymer photovoltaic materials with high open circuit voltageMethod, described method comprises the steps:
Under inert atmosphere, under the catalytic action of palladium catalyst, make compound shown in formula (III) and formula (IV)Shown in a or formula (IV) b, compound reacts, and obtains the polymer photovoltaic shown in formula (I) or formula (II)Material;
Wherein, R1And R2All independently selected from the straight chained alkyl replacing or unsubstituted carbon number is 6～12Or branched alkyl, R3And R4All independently selected from replace or unsubstituted carbon number to be 6～12 direct-connectedAlkyl or alkoxyl.
In the present invention, under inert atmosphere, under the catalytic action of palladium catalyst, when making shown in formula (III)When compound reacts shown in compound and formula (IV) a, obtain compound shown in formula (I), when making formula(III) shown in compound shown in and formula (IV) b, compound reacts, and obtains chemical combination shown in formula (II)Thing.
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 is1:1～1.5:1, 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 is1:1～1.5:1, 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 reaction temperature of described reaction is 100～120 DEG C, for example 101 DEG C, 102 DEG C, 103 DEG C,104℃、105℃、106℃、107℃、108℃、109℃、110℃、111℃、112℃、113℃、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 time of described reaction is 12～48 hours, for example 14 hours, 16 hours, 18Hour, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34Hour, 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, described organic solvent be specially toluene, chlorobenzene orThe mixture of any one in o-dichlorohenzene or at least two kinds. For example toluene of described mixture and chlorobenzeneMixture, the mixture of toluene and o-dichlorohenzene, the mixture of chlorobenzene and o-dichlorohenzene, toluene, chlorobenzene andThe mixture of o-dichlorohenzene.
Preferably, described method also comprises following purification step: will be containing gathering shown in formula (I) or formula (II)The solution cool to room temperature of compound photovoltaic material, then adds methanol extraction, sediment is filtered and is collected, soBy apparatus,Soxhlet's, with methyl alcohol, acetone and n-hexane etc., the composition of little molecular weight is removed respectively afterwards, soWith chloroform, the composition of macromolecule is extracted afterwards, vacuum evaporation is fallen after partial solvent, adds methyl alcoholPostprecipitation, filters sediment to collect, and obtains the Polymer photovoltaic materials shown in formula (I) or formula (II).
Preferably, described method also comprises following purification step: will be containing shown in formula (IV) a or formula (IV) bOne in compound is dissolved in carrene, washes and extracts subsequently with the saturated aqueous solution of sodium chloride, anhydrousDried over mgso, vacuum evaporation is fallen after solvent, adopts carrene and benzinum that volume ratio is 3:1～5:1 mixedBonding solvent is crossed chromatography silica gel post and is purified.
Preferably, described carrene and benzinum volume ratio are 3:1～5:1, for example 3.5:1,4:1,4.5:1Or 5:1, preferably 3:1.
Preferably, shown in formula (IV) b, compound is prepared by the following method:
Under inert atmosphere, under the catalytic action of palladium catalyst, make compound shown in formula (V) and formula (VI)Shown in compound react, then its product is reacted with N-bromo-succinimide, obtainCompound shown in formula (IV) b.
Wherein, R2Be selected from straight chained alkyl or branched alkane that replacement or unsubstituted carbon number are 6～12Base, R3And R4All independently selected from replace or unsubstituted the total number of carbon atoms direct-connected alkyl that is 6～12 orAlkoxyl.
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 reaction temperature of the reaction of compound shown in compound shown in formula (V) and formula (VI) is100～120 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 or119 DEG C, preferably 120 DEG C.
Preferably, the reaction time of the reaction of compound shown in compound shown in formula (V) and formula (VI) is 24～48Hour, 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, described organic solvent be specially toluene, chlorobenzene orThe mixture of any one in o-dichlorohenzene or at least two kinds. For example toluene of described mixture and chlorobenzeneMixture, the mixture of toluene and o-dichlorohenzene, the mixture of chlorobenzene and o-dichlorohenzene, toluene, chlorobenzene andThe mixture of o-dichlorohenzene.
Preferably, by cold the reaction mixture of compound shown in compound shown in formula (V) and formula (VI)But arrive room temperature, be then dissolved in carrene, wash with sodium-chloride water solution subsequently, anhydrous magnesium sulfate drying,Vacuum evaporation is fallen after solvent, adopts carrene and the benzinum mixed solvent that volume ratio is 6:1 to cross chromatogram siliconGlue post is purified, and obtaining yellow solid (is the compound shown in the compound shown in formula (V) and formula (VI)Product), then it is reacted with N-bromo-succinimide.
Preferably, product and the N-of the compound shown in the compound shown in formula (V) and formula (VI)The detailed process of bromo-succinimide reaction is:
Add volume ratio to be the product of compound shown in compound shown in formula (V) and formula (VI)In the chloroform of 10:1～10:3 and trifluoroacetic acid mixed solution, preferably 10:1, then adds N-bromo fourth twoAcid imide reacts.
The reaction temperature of preferably, reacting with N-bromo-succinimide is room temperature. Described room temperature is25℃。
Preferably, the reaction time of reacting with N-bromo-succinimide is 5～24 hours, for example 6Hour, 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 or23 hours, preferably 5 hours.
Preferably, will carry out reacted product sodium-chloride water solution with N-bromo-succinimide and wash,Anhydrous magnesium sulfate drying, solvent is fallen in vacuum evaporation, the carrene that employing volume ratio is 3:1 and benzinumMixed solvent is crossed chromatography silica gel post and is purified, and obtains yellow solid, obtains compound shown in formula (IV) b.
Shown in exemplary formula (IV) b, the preparation method of compound, comprises that step is as follows: at four (triphensBase phosphine) under the catalytic action of palladium, the compound shown in the 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. WillReaction mixture cool to room temperature, is then dissolved in carrene, washes subsequently nothing with sodium-chloride water solutionWater magnesium sulfate is dry, and vacuum evaporation is fallen after solvent, adopts carrene/benzinum (6/1, V/V) to cross chromatogramSilicagel column is purified, and obtains yellow solid; Then yellow solid is mixed with chloroform, add a small amount of trifluoroAcetic acid, then adds N-bromo-succinimide, and (preferably 5 is little under room temperature, to react 5～24 hoursTime), wash with sodium-chloride water solution subsequently, anhydrous magnesium sulfate drying, vacuum evaporation is fallen after solvent, adopts twoChloromethanes/benzinum (3/1, V/V) is crossed chromatography silica gel post and is purified, and obtains yellow solid, obtains formula (IV)Compound shown in b.
Three of object of the present invention is to provide a kind of polymer photovoltaic with high open circuit voltage as aboveThe purposes of material, 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 is applied to Thienopyrroles diketone and the derivative thereof with strong electron-withdrawing power can add by solutionThe design of the Polymer photovoltaic materials of work and synthetic in, synthesized with benzene 1,4-Dithiapentalene or naphthalene 1,4-Dithiapentalene and thiopheneThe soluble polymer molecule that fen pyrroles's diketone and its derivative are core. They common are machine solvent (asChloroform, oxolane, toluene) in have good dissolubility, can get rid of with solution the method preparation of paintingHigh-quality film; Meanwhile, these polymer molecules have wide visible region and absorb, lower HOMOEnergy level and relatively narrow band gap. Taking this type of polymer molecule as to body, PC60BM or PC70BM is acceptorPrepared body heterojunction organic solar batteries, the highest energy conversion efficiency after its optimization can exceed7.5%, and open-circuit voltage exceedes 1V. In addition, the preparation method of polymeric material 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:PC70The polymer solar electricity of BM/Ca/AlThe I-V curve of pond device;
Fig. 6 is for having shown that structure is ITO/PEDOT:PSS/P4:PC60The polymer solar electricity of BM/Ca/AlThe I-V curve of pond device.
Detailed description of the invention
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 conventional method; Described reagent andMaterial, if no special instructions, all can obtain from commercial channels.
Embodiment 1BDTT synthetic (in formula (III), R1＝C6H13Compound)
Chemical reaction flow process as follows (concrete reactions steps and reaction condition bibliography LijunHuo,Angew.Chem.Int.Ed.2011,50,9697–9702)：
Embodiment 22BrTPD's is synthetic
Chemical reaction flow process as follows (concrete reactions steps and reaction condition bibliography YingpingZou,J.Am.Chem.Soc.2010,132,5330–5331)：
Synthesizing of embodiment 3 polymer Ps 1
Chemical reaction flow process is as follows, and concrete reactions steps and reaction condition are as follows:
In 50mL there-necked flask, add 162.7mg (0.18mmol) compound 6 and 76.5mg (0.18Mmol) compound 9, then add the super dry toluene of 16mL and the super dry DMF of 4mL, logicalAfter 20 minutes argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium, then take out inflation three times, slowly will afterwardsTemperature rises to 110 DEG C, lucifuge reaction 24 hours under argon shield. Question response finishes, reaction system natureBe cooled to after room temperature, reactant liquor is splashed in 200mL methyl alcohol and carries out precipitating, leach sediment and turnedMove in apparatus,Soxhlet's, carry out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, concentrated finalThe chloroform extract arriving, and be added dropwise in 200mL methyl alcohol and carry out precipitating again, filter out precipitation alsoCarry out vacuum drying, finally obtain 137.0mg polymer P 1, productive rate 85%. By gel exclusion chromatography with fourHydrogen furans is the number-average molecular weight Mn=59.6KDa that mobile phase at room temperature records this polymer, decentralizationPDI＝2.38。
The preparation method of other polymer P 2-P3 is substantially the same, only need by compound 9 with as follows inCompound 16-17 carries out respectively polymerisation.
Synthesizing of embodiment 4 compounds 12
Chemical reaction flow process is as follows, and concrete reactions steps and reaction condition are as follows:
Compound 10 (2.0g, 8.0mmol) is dissolved in to CHCl3/CH3COOH volume ratio 10:1's is moltenIn liquid, add NBS (N-bromo-succinimide) (3.2g, 18mmol) to stir 3 hours. Reaction knotCHCl after bundle3Extract 3 times, organic phase rotary evaporation, except desolventizing, does eluent with n-hexane, uses silica gelChromatographic column separated product, colourless transparent liquid (3.1g, productive rate 95%). MS (MALDI-TOF-MS): m/z ＝410.2。1HNMR(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, and pass into argon gas and take out and fill three times,Be cooled to-78 DEG C and stir 10 minutes, 2.4M butyl lithium (3.2ml/7.8mmol) is complete in 20-30 minutePortion drips, and keeps low-temp reaction 3 hours. The disposable 1M trimethyltin chloride (9.2ml/9.2 that addsMmol), reaction is spent the night. N-hexane extraction three times, rotary evaporation obtains yellow liquid after going out desolventizing, nothingNeed to purify and directly drop into next step reaction.
Embodiment 5TPD-Br (compound 13)
Chemical reaction flow process figure is as shown in the flow chart in embodiment 4, and (5g/18.8mmol) is molten for compound 8In 50ml trifluoroacetic acid, drip the 5ml concentrated sulfuric acid, add NBS (1.7g/9mmol) to stir after 5 minutesPour into and in intermediate water, use CHCl3Extract 3 times. Organic phase rotary evaporation is used CH except after desolventizing2Cl2/ n-hexaneVolume ratio 1:1 mixed solution does eluent, uses silica gel column chromatography separated product, obtains white solid product(2.6g, productive rate 40%). MS (MALDI-TOF-MS): m/z=408.0.1HNMR(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 62BrTPD-C6-TPD (compound 15)
Chemical reaction flow process figure as shown in the flow chart in embodiment 4, compound 12 (660mg/1.5mmol)Be dissolved in and heavily steam toluene with compound 13 (1g/2.9mmol), logical argon gas, after 10 minutes, adds catalyst four(triphenyl phosphorus) palladium, logical argon gas is taken out and is filled 3 times. Under argon shield, 110 DEG C are reacted 24 hours. Reaction knotAfter bundle, use a dry method on a sample CH2Cl2/ n-hexane volume ratio 6:1 mixed solution does eluent, uses silica gel layerAnalyse post separated product, obtain yellow solid (740mg, productive rate 80%). MS (MALDI-TOF-MS):m/z＝636.8。1HNMR(400MHz，CDCl3，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 concentrated sulfuric acid 3ml,Add NBS (276.2mg/1.56mmol) room temperature reaction 5 hours, use CHCl3Extract organic phase 3 timesRotary evaporation is except desolventizing, CH2Cl2/ n-hexane 3:1 does eluent, uses silica gel column chromatography separated product,Obtain yellow solid (186.7mg, productive rate 30%). MS (MALDI-TOF-MS): m/z=796.7.1HNMR(400MHz，CDCl3，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 condition are as follows:
In 50mL there-necked flask, add 90.4mg (0.1mmol) compound 6 and 93.7mg (0.1mmol)Compound 15, then add the super dry toluene of 12mL and the super dry DMF of 2mL, logical 20 pointsAfter clock argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium, then take out inflation three times, afterwards slowly by temperatureRise to 110 DEG C, lucifuge reaction 24 hours under argon shield. Question response finishes, and reaction system is naturally coolingTo room temperature, reactant liquor is splashed in 200mL methyl alcohol and carries out precipitating, leach sediment and transfer them toIn apparatus,Soxhlet's, carry out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, concentrated finally obtainChloroform extract, and be added dropwise in 200mL methyl alcohol and carry out precipitating again, filter out and precipitate and carry outVacuum drying, finally obtains 87.8mg polymer P 2, productive rate 65%. By gel exclusion chromatography with tetrahydrochysene furanMutter and at room temperature record the number-average molecular weight M of this polymer for mobile phasen=15.6KDa, decentralization 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 condition are as follows:
By 7.2g (50mmol) compound 23,17.6g (200mmol) n-amyl alcohol, 25mL toluene and0.6g (5mmol) anhydrous Na HSO4, adding in 100mL there-necked flask, high pure nitrogen protection, stirsBe warming up to 110 DEG C, react 5 hours. After finishing, reaction is cooled to room temperature, after steaming desolventizes, and use benzinum/Ethyl acetate volume ratio 100:1 mixed solution does eluent, uses silica gel column chromatography separated product, obtains nothingLook liquid, (11.05g, productive rate 65%),1HNMR(400MHz，CDCl3，ppm)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 CHCl3/CH3COOH volume ratio 10:1's is moltenIn liquid, add NBS (N-bromo-succinimide) (3.2g, 18mmol) to stir 3 hours. Reaction knotCHCl after bundle3Extract 3 times, organic phase rotary evaporation, except desolventizing, does eluent with n-hexane, uses silica gelChromatographic column separated product, transparency liquid (3.1g, productive rate 95%). MS (MALDI-TOF-MS): m/z=414.2。1HNMR(400MHz,CDCl3，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, and pass into argon gas and take out and fill three times,Be cooled to-78 DEG C and stir 10 minutes, 2.4M butyl lithium (2.5ml/6mmol) is whole in 20-30 minuteDrip, keep low-temp reaction 3 hours. The disposable 1M trimethyltin chloride (7.2ml/7.2 that addsMmol), reaction is spent the night. N-hexane extraction three times, rotary evaporation obtains yellow liquid after going out desolventizing, nothingNeed to purify and directly drop into next step reaction.
Synthesizing of embodiment 9 compounds 28
As described in Example 8, concrete reactions steps and reaction condition 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,Logical argon gas, after 10 minutes, adds catalyst tetrakis triphenylphosphine palladium, and logical argon gas is taken out and filled 3 times. Protect at argon gasProtect lower 110 DEG C of reactions 24 hours. After finishing, reaction uses a dry method on a sample CH2Cl2/ n-hexane volume ratio 6:1Mixed solution does eluent, uses silica gel column chromatography separated product, obtains yellow solid (938.0mg, productive rate80％)。MS(MALDI-TOF-MS)：m/z＝782.3。1HNMR(400MHz，CDCl3，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 CHCl3Extract 3 times, organic phase rotary evaporation removes desolventizing,CH2Cl2/ n-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=940.1.1HNMR(400MHz，CDCl3，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 condition are as follows:
In 50mL there-necked flask, add 90.4mg (0.1mmol) compound 6 and 94.0mg (0.1mmol)Compound 28, then add the super dry o-dichlorohenzene of 12mL and the super dry DMF of 2mL, logical 20After minute argon gas, add rapidly 15mg tetrakis triphenylphosphine palladium, then take out inflation three times, afterwards slowly by temperatureDegree rises to 120 DEG C, lucifuge reaction 24 hours under argon shield. Question response finishes, and reaction system is naturally coldBut to room temperature, reactant liquor is splashed in 200mL methyl alcohol and carries out precipitating, leach sediment and by its transferTo apparatus,Soxhlet's, carry out extracting with methyl alcohol, acetone, n-hexane and chloroform successively, concentrate and finally obtainChloroform extract, and be added dropwise in 200mL methyl alcohol and carried out precipitating again, filter out precipitation and go forward side by sideRow vacuum drying, finally obtains 88.2mg polymer P 10, productive rate 65%. By gel exclusion chromatography with tetrahydrochyseneFurans is the number-average molecular weight Mn=31.9KDa that mobile phase at room temperature records this polymer, decentralizationPDI＝1.52。
Embodiment 11 measures the ultraviolet-visible absorption spectroscopy of polymer under chloroformic solution neutralized film state alsoUtilize empirical equation to calculate the optical band gap of polymer.
Appropriate polymer P 1 is dissolved in chloroform, to be made into certain density solution and to get part solution and is spin-coated toOn quartz plate, make the film of polymer.
The ultraviolet-visible absorption spectroscopy that polymer P 1 records under chloroformic solution neutralized film state is as Fig. 1 instituteShow. The optical band gap of polymer uses formula (Eg=1240/ λ absorbs limit) calculate, wherein P1 existsMaximum absorption band in chloroformic solution is 530nm, and film has wide absorption at 300-650nm, maximum suctionReceipts peak is 606nm, absorbs limit at 655nm, and optical band gap is 1.89eV, shows that this is an arrowbandThe semiconducting organic polymer of gap.
The method of testing of other polymer Ps 2-P13 is substantially the same. Fig. 2 is that polymer P 4 is in chloroformic solutionWith the ultraviolet-visible absorption spectroscopy figure under filminess. Absorbing boundary in P4 chloroformic solution is 654nm,Large absworption peak is in 625nm left and right. Show the chloroform of two kinds of polymer in dilution at the acromion of 620nm left and rightIn solution, still have certain accumulation. Accumulation under filminess add force thin polymer film absorbing boundary all thanSolution has obvious red shift, and P4 is from 654nm to 655nm. By formula Eg=1240/ λ, can calculateThe optical band gap of 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 1For 0.83eV. According to formula EHOMO＝-e(Eox onset+ 4.71) (eV) calculate the HOMO of polymer P 1Energy level is-5.54eV, and lower HOMO energy level contributes to improve the V of solar celloc, increase simultaneouslyThe aerial stability of polymer.
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 hexafluorophosphoric acid 4-butyl amine and surveyAmount. The initial oxidation current potential obtaining from figure and initial reduction potential, then calculate E by formulaHOMO＝-e(Eox onset+4.71)(eV)＝-5.62eV，ELUMO＝-e(Ered onset+4.71)(eV)＝-3.43eV。
The method of testing of other polymer Ps 1-P13 is substantially the same.
The Photovoltaic Properties test of embodiment 13P1
Taking P1 as to body, PC70BM is that acceptor has been prepared organic solar batteries device by solution spin coating.
Device architecture is ITO/PEDOT:PSS/P1:PC70BM/Ca/Al. Preparation method is as follows:
By the PC of P1 and homogenous quantities70BM blend (P1:PC70BM mass ratio is 1:1), be dissolved in trichlorineIn methane to make the solution of 10mg/mL. In the glass substrate of transparent silver oxide tin (ITO) coating, makeMake organic solar batteries. Transparent conducting glass with ITO is used to deionized water, acetone, isopropyl successivelyThe each ultrasonic cleaning of alcohol 15 minutes, then uses ozone treatment substrate surface, and PEDOT:PSS is spin-coated on to ITOUpper, the rotating speed of spin coating is 2000-6000 rev/min, and is dried 15 minutes at 150 DEG C, and obtaining thickness is 30The anode modification layer of nm. In glove box by polymer and [6,6]-phenyl C70Methyl butyrate (PC70BM)Chloroformic solution with the rotating speed of 600-4000 rev/min, this solution is evenly spin-coated on anode modification layer, obtainThickness is the active material layer of 100-300nm. Finally 2 × 10-6Under the vacuum of holder, Ca evaporation is extremely livedProperty material layer on, to form thickness be 20nm cathodic modification layer; And 2 × 10-6Holder vacuum under by AlEvaporation to negative electrode decorative layer, to form thickness be 100nm negative electrode, thus obtain polymer solar electricityPond device. The white light source that the filter set cooperation that uses 500W xenon lamp and AM1.5 is simulated solar irradiation,Regulate the light intensity of device measured place to 100mW/cm-2, use Keithley to the prepared polymer sunOpen-circuit voltage, short circuit current and three parameters of fill factor, curve factor of energy battery device are tested. Fig. 5 is for aobviousShow that structure is ITO/PEDOT:PSS/P1:PC70The I-V of the polymer solar cell device of BM/Ca/AlCurve, the wherein open-circuit voltage (V of polymer P 1oc)=0.99V, short circuit current (Jsc)＝8.69mA/cm2，Fill factor, curve factor (FF)=45%. Fig. 6 is for having shown that structure is ITO/PEDOT:PSS/P4:PC60BM/Ca/AlThe I-V curve of polymer solar cell device. Wherein open-circuit voltage (the V of polymer P 4oc)＝1.01V，Short circuit current (Jsc)＝13.07mA/cm2, fill factor, curve factor (FF)=47%.
The method of testing of other polymer Ps 2-P13 is substantially the same, and acceptor material is PC70BM orPC60BM。
Applicant's statement, the present invention illustrates detailed process equipment and process of the present invention by above-described embodimentFlow process, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that the present inventionMust rely on above-mentioned detailed process equipment and process flow process could implement. Person of ordinary skill in the field shouldThis understands, any improvement in the present invention, the equivalence replacement to the each raw material of product of the present invention and auxiliary elementThe selections of interpolation, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (37)

1. a Polymer photovoltaic materials, is characterized in that, it has the structure shown in formula (II):
Wherein, R1And R2All independently selected from the straight chained alkyl replacing or unsubstituted carbon number is 6～12Or branched alkyl, R3And R4All independently selected from the straight chain replacing or unsubstituted carbon number is 6～12Alkyl or alkoxyl, n is 20～100.
2. a preparation method for Polymer photovoltaic materials as claimed in claim 1, is characterized in that, instituteThe method of stating comprises the steps:
Under inert atmosphere, under the catalytic action of palladium catalyst, make compound shown in formula (III) and formula (IV)Shown in b, compound reacts, and obtains the Polymer photovoltaic materials shown in formula (II);
Wherein, R1And R2All independently selected from the straight chained alkyl replacing or unsubstituted carbon number is 6～12Or branched alkyl, R3And R4All independently selected from the straight chain replacing or unsubstituted carbon number is 6～12Alkyl or alkoxyl.
3. method as claimed in claim 2, is characterized in that, described palladium catalyst is at four (triphenylsPhosphine) palladium.
4. method as claimed in claim 2, is characterized in that, compound shown in formula (III) and formula (IV)The molar ratio of compound shown in b is 1:1～1.5:1.
5. method as claimed in claim 3, is characterized in that, compound shown in formula (III) and formula (IV)The molar ratio of compound shown in b is 1:1.
6. method as claimed in claim 2, is characterized in that, shown in described palladium catalyst and formula (III)The molar ratio of compound is 0.02～0.05:1.
7. method as claimed in claim 6, is characterized in that, shown in described palladium catalyst and formula (III)The molar ratio of compound is 0.02:1.
8. method as claimed in claim 2, is characterized in that, the reaction temperature of described reaction is100～120℃。
9. method as claimed in claim 8, is characterized in that, the reaction temperature of described reaction is 120 DEG C.
10. method as claimed in claim 2, is characterized in that, the reaction time of described reaction is 12～48Hour.
11. methods as claimed in claim 10, is characterized in that, the reaction time of described reaction is 24Hour.
12. methods as claimed in claim 2, is characterized in that, described reaction is carried out in organic solvent,Described organic solvent is the mixture of any one or at least two kinds in toluene, chlorobenzene or o-dichlorohenzene.
13. methods as claimed in claim 2, is characterized in that, described method also comprises following purifying stepRapid:
Will be containing the solution cool to room temperature of the Polymer photovoltaic materials shown in formula (II), then add methyl alcohol heavyForm sediment, sediment is filtered and collected, then, by apparatus,Soxhlet's, adopt respectively methyl alcohol, acetone, n-hexaneExtract with chloroform, vacuum evaporation is fallen after partial solvent, adds methyl alcohol postprecipitation, and sediment is filtered and receivedCollection, obtains the Polymer photovoltaic materials shown in formula (II).
14. methods as claimed in claim 2, is characterized in that, described method also comprises following purifying stepRapid: will to be dissolved in carrene containing the one in compound shown in formula (IV) b, subsequently satisfying with sodium chlorideWash and extract with the aqueous solution, anhydrous magnesium sulfate drying, vacuum evaporation is fallen after solvent, adopts volume ratio to beThe carrene of 3:1～5:1 and benzinum mixed solvent, cross chromatography silica gel post and purify.
15. methods as claimed in claim 14, is characterized in that, adopt the dichloromethane that volume ratio is 3:1Alkane and benzinum mixed solvent, cross chromatography silica gel post and purify.
16. methods as claimed in claim 2, is characterized in that, shown in formula (IV) b, compound passes throughFollowing methods preparation:
Under inert atmosphere, under the catalytic action of palladium catalyst, make compound shown in formula (V) and formula (VI)Shown in compound react, then its product is reacted with N-bromo-succinimide, obtainCompound shown in formula (IV) b;
Wherein, R2Be selected from straight chained alkyl or branched alkane that replacement or unsubstituted carbon number are 6～12Base, R3And R4All independently selected from the straight chained alkyl or the alkane that replace or unsubstituted carbon number is 6～12Oxygen base.
17. methods as claimed in claim 16, is characterized in that, described palladium catalyst is four (triphenylsPhosphine) palladium.
18. methods as claimed in claim 16, is characterized in that, compound shown in formula (V) and formula (VI)Shown in the molar ratio of compound be 2:1～3:1.
19. methods as claimed in claim 18, is characterized in that, compound shown in formula (V) and formula (VI)Shown in the molar ratio of compound be 2:1.
20. methods as claimed in claim 16, is characterized in that, described palladium catalyst and formula (V) instituteThe molar ratio that shows compound is 0.02～0.05:1.
21. methods as claimed in claim 20, is characterized in that, described palladium catalyst and formula (V) instituteThe molar ratio that shows compound is 0.02:1.
22. methods as claimed in claim 16, is characterized in that, compound shown in formula (V) and formula (VI)Shown in the reaction temperature of compound reaction be 100～120 DEG C.
23. methods as claimed in claim 22, is characterized in that, compound shown in formula (V) and formula (VI)Shown in the reaction temperature of compound reaction be 120 DEG C.
24. methods as claimed in claim 16, is characterized in that, compound shown in formula (V) and formula (VI)Shown in reaction time of compound reaction be 24～48 hours.
25. methods as claimed in claim 24, is characterized in that, compound shown in formula (V) and formula (VI)Shown in reaction time of compound reaction be 24 hours.
26. methods as claimed in claim 16, is characterized in that, described reaction is carried out in organic solvent,Described organic solvent is the mixture of any one or at least two kinds in toluene, chlorobenzene or o-dichlorohenzene.
27. methods as claimed in claim 16, is characterized in that, by compound and formula shown in formula (V)(VI) the reaction mixture cool to room temperature of compound shown in, is then dissolved in carrene, uses subsequentlySodium-chloride water solution is washed, anhydrous magnesium sulfate drying, and vacuum evaporation is fallen after solvent, and employing volume ratio is 4:1～6:1Carrene and benzinum mixed solvent, cross chromatography silica gel post and purify, obtain yellow solid, then by itReact with N-bromo-succinimide.
28. methods as claimed in claim 27, is characterized in that, adopt the dichloromethane that volume ratio is 6:1Alkane and benzinum mixed solvent, cross chromatography silica gel post and purify.
29. methods as claimed in claim 16, is characterized in that, compound shown in formula (V) and formula (VI)Shown in the product of the compound detailed process of reacting with N-bromo-succinimide be:
Add volume ratio to be the product of compound shown in compound shown in formula (V) and formula (VI)In the chloroform of 10:1～10:3 and trifluoroacetic acid mixed solution, then add N-bromo-succinimide to carry outReaction.
30. methods as claimed in claim 29, is characterized in that, by compound and formula shown in formula (V)(VI) it is that the chloroform of 10:1 mixes molten with trifluoroacetic acid that the product of compound shown in adds volume ratioIn liquid, then add N-bromo-succinimide to react.
31. methods as claimed in claim 16, is characterized in that, carry out with N-bromo-succinimideThe reaction temperature of reaction is room temperature.
32. methods as claimed in claim 16, is characterized in that, carry out with N-bromo-succinimideThe reaction time of reaction is 5～24 hours.
33. methods as claimed in claim 32, is characterized in that, carry out with N-bromo-succinimideThe reaction time of reaction is 5 hours.
34. methods as claimed in claim 16, is characterized in that, will enter with N-bromo-succinimideThe reacted product of row is washed with sodium-chloride water solution, anhydrous magnesium sulfate drying, and solvent is fallen in vacuum evaporation,The carrene that employing volume ratio is 3:1 and the mixed solvent of benzinum are crossed chromatography silica gel post and are purified, and obtain HuangLook solid, obtains compound shown in formula (IV) b.
The purposes of 35. 1 kinds of Polymer photovoltaic materials as claimed in claim 1, is characterized in that, its useIn preparing photovoltaic device.
36. purposes as claimed in claim 35, is characterized in that, described photovoltaic device is organic solarBattery.
37. purposes as claimed in claim 35, is characterized in that, it is for the preparation of organic solar batteriesDonor material.
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