CN104004164A - Alkylene fluorene and thieno[3, 4-b]pyrazine containing polymer, preparation method thereof and organic solar cell - Google Patents

Alkylene fluorene and thieno[3, 4-b]pyrazine containing polymer, preparation method thereof and organic solar cell Download PDF

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CN104004164A
CN104004164A CN201310060330.5A CN201310060330A CN104004164A CN 104004164 A CN104004164 A CN 104004164A CN 201310060330 A CN201310060330 A CN 201310060330A CN 104004164 A CN104004164 A CN 104004164A
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thieno
pyrazine
polymkeric substance
reaction
alkyl
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CN104004164B (en
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周明杰
管榕
黄佳乐
黎乃元
李满园
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
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Abstract

The invention provides an alkylene fluorene and thieno[3, 4-b]pyrazine containing polymer, a preparation method thereof and an organic solar cell. The alkylene fluorene and thieno[3, 4-b]pyrazine containing polymer is a polymer P with a general formula as the following, wherein R1 is straight chain or branched chain alkyl of C4-C40; R2 is H atom, F atom or straight chain or branched chain alkyl of C4-C40; and n is an integer of 10-100. The polymer can increase the transmission performance of a charge carrier, is conducive to effective transfer of the charge carrier, and increases the spectral absorption range. Also, the preparation method is simple and mature, and can effectively improve the light conversion efficiency of a solar cell when used for preparation of the organic solar cells. (formula of polymer P).

Description

Containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance and preparation method thereof and organic solar batteries
Technical field
The present invention relates to photoelectron material field, particularly relate to containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance and preparation method thereof and organic solar batteries.
Background technology
High efficiency solar cell is normally taking inorganic semiconductor as raw material, but main silicon wafer solar cell is due to production process technology complexity in the market, and seriously polluted, power consumption is large, and cost is high, has suppressed the development of its commercial applications.Therefore utilize cheap material to prepare low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Organic semiconductor material is all better because the environmental stability of organic materials is good, synthetic cost is low, function is easy to modulation, snappiness and film-forming properties on the one hand; On the other hand because the organic solar batteries course of processing is relatively simple, can cold operation, element manufacturing cost also receives much concern compared with the advantage such as low, becomes the most cheap and attractive solar cell material.In addition, the potential advantages of organic solar batteries also comprise: can realize big area manufacture, can use flexible substrate, environmental friendliness, light portable etc.
At present, the research of organic polymer solar cell mainly concentrates on to body, acceptor co-mixing system, adopts polyphenyl 1,4-Dithiapentalene (PTB7) and fullerene derivate PC 71the energy conversion efficiency of BM co-mixing system has reached 9.2%, but still much lower than the efficiency of conversion of inorganic solar cell.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance.The present invention also aims to provide preparation method and the organic solar batteries containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance.
First aspect, the invention provides a kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, for having the polymer P of following general formula:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
R 1and R 2group contributes to realize the resolvability of this polymkeric substance in specific organic solvent.
Preferably, be 5000 ~ 300000 containing the weight-average molecular weight of alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, molecular weight distribution (PDI) is 1.2 ~ 5.0.
Above-mentioned containing in alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be sp on 9 in alkylidene group fluorenes 2the carbon atom of hydridization it and common sp 3the alkyl fluorenes of hydridization compare, have better conjugate planes.With it be used as the backbone structure of organic photovoltaic material, π-the π that can strengthen polymer solids material is stacking, being conducive to increase the transmission performance of current carrier, thereby improving photoelectric transformation efficiency, is therefore a kind of the novel to body unit of organic photovoltaic devices donor material that can be used for.
Thieno-[3,4-b] pyrazine a kind of good two dimensional structure that has, the body unit that is subject to that contains a five-ring and six-ring skeleton, and there is intramolecular charge transfer character, excellent electrochemical reduction character.So it has a wide range of applications aspect organic solar batteries.The LUMO value of thieno-[3,4-b] pyrazine is-1.41eV to compare the unit such as conventional quinoxaline and have stronger electron-withdrawing power.Therefore, it is often as be incorporated in photoelectric material to regulate bandwidth and reduction potential by body unit.Thieno-[3,4-b] pyrazine unit also has stronger modifiability, can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance.Therefore it also has a wide range of applications in the photoelectric materials such as organic photovoltaic battery.
By alkylidene group fluorenes and derivative and thieno-[3,4-b] pyrazine class monomer carries out after copolymerization, the polymkeric substance obtaining can increase the transmission performance of current carrier, is conducive to current carrier and more effectively transmits in active layer material inside, and increase the absorption region of spectrum.Above-mentioned polymer semiconducting material is a kind of donor-receiver (D-A) type electron donor material, it and electron acceptor material make photovoltaic device annealed after, can effectively increase order and the regularity between the interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, and then improve photoelectric transformation efficiency.
Second aspect, the invention provides a kind of preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, comprises the following steps:
The compd A and the compd B that provide respectively following structural formula to represent:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100;
Under anaerobic state, according to mol ratio 1:1:0.005 ~ 0.05, compd A, compd B and catalyzer are dissolved in the first organic solvent, add alkaline solution, back flow reaction 24 ~ 72 hours under 60 ° of C ~ 100 ° C, after separation and purification, obtain containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, described is the polymer P with following general formula containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
Preferably, catalyzer is three (dibenzalacetone) two palladium (Pd 2(dba) 3), two (triphenyl phosphorus) palladium chloride (Pd (PPh 3) 2cl 2) and tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) in one.
Preferably, the first organic solvent is the one in toluene and DMF.
Preferably, alkaline solution is aqueous sodium carbonate.
Preferably, 5 ~ 20 times of the amount of substance that in alkaline solution, the amount of substance of alkali is compd A.
Preferably, separation and purification comprises the following steps: after reaction, in reaction system, add toluene and deionized water to extract, get organic phase, underpressure distillation is to 5 milliliters to 15 milliliters of organic phase residues, add in anhydrous methanol, stir, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, described pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, collect chromatographic solution concentrated by rotary evaporation, splash into again in methanol solvate and stirred for several hour, dry, obtain crude product, finally with apparatus,Soxhlet's by crude product extracting, obtain described containing alkylidene group fluorenes and thieno-[3, 4-b] pyrazine polymkeric substance.
Compd B can directly be buied by market.
Compd A can directly be buied or be prepared by market.
Preferably, compd A makes by the following method:
The Compound C that provides following structural formula to represent:
In formula, R 1for C 4~ C 40the alkyl of straight or branched;
In anhydrous response device, under the protection of nitrogen, Compound C is added in reactor, then add the second organic solvent, under ° C condition of-70 ° of C ~-85, slowly add n-Butyl Lithium (n-BuLi), stirring reaction 0.5 ~ 4 hour; After reaction, under ° C condition of-70 ° of C ~-85, in reaction system, slowly add 2-isopropoxy-4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-, reacts 10 ~ 48 hours after being warmed up to room temperature, and separation and purification obtains described compd A, and reaction formula is:
In formula, R 1for C 4~ C 40the alkyl of straight or branched.
More preferably, the second organic solvent is tetrahydrofuran (THF).
Obtain by the following method refining tetrahydrofuran (THF): put up water distilling apparatus, the tetrahydrofuran solvent being dried with potassium hydroxide is added in single port bottle, then add thin sodium piece and benzophenone, constantly stir, the system of being back to is intense violet color, steam tetrahydrofuran (THF), stand-by.
More preferably, the mol ratio of Compound C and n-Butyl Lithium (n-BuLi) is 1:2 ~ 4.
More preferably, n-Butyl Lithium and 2-isopropoxy-4,4,5,5-tetramethyl--1, the mol ratio of 3,2-, bis-assorted oxygen pentaboranes is 1:1 ~ 2.
More preferably, carry out following separation and purification operation and obtain described compd A: add saturated common salt solution washing, with chloroform extraction, anhydrous sodium sulphate (Na 2sO 4) dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product, then taking methylene dichloride as leacheate, crude product is carried out to silica gel column chromatography separation, obtain the described compd A after purifying.
Compound C can directly be buied or be prepared by market.
Preferably, Compound C makes by the following method:
The Compound D that provides following structural formula to represent:
Under-10 ° of C ~-5 ° C and nitrogen protection condition, Compound D is dissolved in to the 3rd organic solvent and constantly stirs, then add alkyl magnesium bromide (R 1mgBr) diethyl ether solution, remains under-20 ° of C ~ 0 ° C conditions and reacts 35 ~ 40 minutes, wherein R 1for C 4~ C 40the alkyl of straight or branched; Then add tetrachloro to close the tetrahydrofuran solution stirring reaction 4 ~ 8 hours of copper acid two lithiums, then carry out neutralization reaction 10 ~ 20 minutes with sodium hydroxide solution, separation and purification obtains described Compound C, and reaction formula is:
Wherein, R 1for C 4~ C 40the alkyl of straight or branched.
More preferably, the 3rd organic solvent is tetrahydrofuran (THF).
More preferably, alkyl magnesium bromide (R 1the concentration of diethyl ether solution MgBr) is 1mol/L.
More preferably, the bromo-9-of 2,7-bis-(two thiomethyls) methylene radical fluorenes and R 1the mol ratio of MgBr is 1:2.0 ~ 2.4.
More preferably, to close the mol ratio of copper acid two lithiums be 25 ~ 50:1 for the bromo-9-of 2,7-bis-(two thiomethyls) methylene radical fluorenes and tetrachloro.
More preferably, carry out following separation and purification operation and obtain described Compound C: after reaction, by reaction product diatomite filtration, collect filtrate, then by ethyl acetate, filtrate is extracted, then the aqueous sodium hydroxide solution that is 10% by organic phase with massfraction, saturated sodium metabisulfite solution and salt solution wash successively, with dried over sodium sulfate underpressure distillation, finally taking sherwood oil as leacheate, product silica gel column chromatography is separated, collect chromatographic solution, after underpressure distillation, carry out recrystallization at-35 ° of C ~-40 ° C with 2-methylpentane, obtain described Compound C.
Compound D can directly be buied or be prepared by market.
Preferably, Compound D makes by the following method:
Under nitrogen protection and room temperature condition; by 2; 7-dibromo fluorenes is dissolved in anhydrous dimethyl sulphoxide; under uniform stirring, add potassium tert.-butoxide again; add afterwards dithiocarbonic anhydride, stirring reaction 10 ~ 20 minutes, then drips and continues stirring reaction 4 ~ 6 hours after methyl iodide again; after separation and purification, obtain described Compound D, reaction formula is:
More preferably, the mol ratio of 2,7-dibromo fluorenes and potassium tert.-butoxide is 1:2.0 ~ 2.4.
More preferably, the mol ratio of 2,7-dibromo fluorenes and dithiocarbonic anhydride is 1:1.0 ~ 1.2.
More preferably, carry out following separation and purification operation and obtain described Compound D: after reaction, reaction product is poured in mixture of ice and water, add again strong aqua to remove unreacted methyl iodide, then filter, collect colature, washing, after oven dry, the ethyl acetate that is 2:1 by volume ratio and the mixed solvent of tetrahydrofuran (THF) carry out recrystallization, obtain described Compound D.
The third aspect, the invention provides a kind of organic solar batteries, comprise negative electrode, active coating, anode, the material of described active coating be described in first aspect present invention containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, for thering is the polymer P of following general formula:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
One provided by the invention, containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance and preparation method thereof and organic solar batteries, has following beneficial effect:
The present invention is by alkylidene group fluorenes and derivative and thieno-[3,4-b] pyrazine class monomer carries out after copolymerization, the transmission performance that obtains increasing containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance current carrier, is conducive to current carrier and more effectively transmits in active layer material inside, and increase the absorption region of spectrum, and preparation method is simple and ripe, and productive rate is high, mild condition, product is easy to control
While containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance for the preparation of organic solar batteries, can effectively improve transmission speed and the efficiency of carrier mobility, and then improve the efficiency of conversion of solar cell to light.
Brief description of the drawings
Fig. 1 is the structural representation of the organic solar batteries device of embodiment 6.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Involved in the present invention containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be the polymer P shown in structural formula as follows:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
Embodiment 1
A kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be designated as polymer P 1(n=10), structural formula is as follows:
The preparation process of P1 is as follows:
The preparation of (1) the bromo-9-bis-of 2,7-bis-(thiomethyl) methylene radical fluorenes (Compound D 1):
Under the room temperature condition of logical nitrogen protection; dissolve 2 toward adding in reaction flask; 7-dibromo fluorenes (48.6g; 1L anhydrous dimethyl sulphoxide (DMSO) 0.15mol) adds (33.6g, 0.30mol) potassium tert.-butoxide under the condition of uniform stirring; then inject (9mL with syringe; 0.15mol) dithiocarbonic anhydride stirring reaction 10 minutes, then continues within 5 minutes, slowly to drip 0.15mol with dropping funnel, continues stirring reaction 4 hours after 9.3mL methyl iodide again.After reaction, resultant is poured in mixture of ice and water, then added 2mL strong aqua to remove unreacted methyl iodide.Then filter, by throw out washing, after oven dry, carry out recrystallization with the mixed solvent that ethyl acetate and tetrahydrofuran (THF) volume ratio are 2:1, finally obtain yellow spicule crystal 2, the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes, productive rate 71%.GC-MS(EI-m/z):428(M+)。
The preparation of (2) the bromo-9-bis-of 2,7-bis-(dodecyl) methylene radical fluorenes (Compound C 1):
Under-5 ° of C and nitrogen protection condition, get step 1 and react the 0.025mol making, 64.2g 2, the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes is dissolved in the anhydrous tetrahydrofuran solvent of 150mL and constantly stirs, then slowly adding 50mL concentration is the diethyl ether solution of the dodecyl bromination magnesium of 1mol/L, this process remains on 0 ° of C reaction 40 minutes, then adding 10mL concentration is the tetrahydrofuran solution stirring reaction 4 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 10 minutes with 10% sodium hydroxide solution of 100mL, finally product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then 10% aqueous sodium hydroxide solution with 200mL by extract, saturated sodium metabisulfite solution and salt solution wash successively, finally with dried over sodium sulfate underpressure distillation.Product is crossed to silica gel column chromatography with sherwood oil, and the product after underpressure distillation is that solvent carries out recrystallization at-35 ° of C with 2-methylpentane, finally obtains yellow spicule crystal 2, the bromo-9-bis-of 7-bis-(dodecyl) methylene radical fluorenes, productive rate 59%.GC-MS(EI-m/z):673(M+)。
The preparation of (3) 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(dodecyl) methylene radical fluorenes (compd A 1):
Put up tetrahydrofuran (THF) (THF) water distilling apparatus, will be join in single port bottle with the KOH tetrahydrofuran solvent of dry 2 days, then add thin sodium piece and the 5g benzophenone of 10g, constantly stir, the system of being back to is intense violet color, steams THF stand-by.Under strict anhydrous and oxygen-free reaction conditions; by nitrogen protection; in reaction flask, add 0.01mol; 6.73g 2; the bromo-9-bis-of 7-bis-(dodecyl) methylene radical fluorenes; inject the tetrahydrofuran solvent of the refining and distilling of 300mL with syringe, under-70 ° of C conditions, slowly inject the n-Butyl Lithium hexane solution of the 1.6mol/L of 0.02mol with syringe, stirring reaction 2 hours.Then under-70 ° of C conditions, inject 4mL with syringe, 2-isopropoxy-4 of 0.02mol, 4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, is warmed up to room temperature reaction 10 hours, obtains final product 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(dodecyl) methylene radical fluorenes.After reaction finishes, add saturated brine (NaCl) solution washing, chloroform extraction, anhydrous Na 2sO 4dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product.It is that leacheate carries out silica gel column chromatography separation that crude product is selected to dichloromethane solvent, obtains 2 after purifying, 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(dodecyl) methylene radical fluorenes, productive rate 54%.GC-MS(EI-m/z):767(M+)。
(4) preparation of P1:
In reactor, add 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(dodecyl) methylene radical fluorenes (1mmol, 0.767g), 5, the bromo-thieno-[3 of 7-bis-, 4-b] Na of pyrazine (1mmol, 0.294g), tetrakis triphenylphosphine palladium (0.005mmol, 0.006g), 2mol/L 2cO 3aqueous solution 2.5mL and toluene solvant 30mL, by repeatedly leading to N 2make reaction system in anaerobic state with vacuumizing, under 60 ° of C conditions, react 24h.
After reaction 24h, in product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to 5mL, splashed in 350mL anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtained pressed powder.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer tetra-triphenylphosphine palladium, finally polymkeric substance/chloroformic solution is revolved and steam to surplus 5mL, splashed in methanol solvate and stir 3 hours, finally polymer P 1 is collected to oven dry.With Soxhlet extractor by polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 1 after purifying is carried out to gel permeation chromatography (Gel Permeation Chromatography, GPC) test, and recording number-average molecular weight is 6470, and polymkeric substance monodispersity is 1.71.
Embodiment 2
A kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be designated as polymer P 2(n=100), structural formula is as follows:
The preparation process of P2 is as follows:
The preparation of (1) the bromo-9-bis-of 2,7-bis-(thiomethyl) methylene radical fluorenes:
Concrete operations are with basic identical in embodiment 1, and difference is: the molar weight of 2,7-dibromo fluorenes is 0.3mol, 97.2g, and the molar weight of potassium tert.-butoxide is 0.72mol, 80.6g; The molar weight of dithiocarbonic anhydride is 0.36mol, 21.7mL, and stirring reaction 20 minutes; And with dropping funnel continue 10 minutes drip molar weight be 0.36mol, after the methyl iodide of 22.4mL, stirring reaction 6 hours.
The preparation of the bromo-9-bis-of (2) 2,7-bis-(2-ethylhexyl) methylene radical fluorenes (Compound C 2):
Under-5 ° of C and nitrogen protection condition; get step 1 and react the 0.02mol making; 8.56g2; the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes is dissolved in the anhydrous tetrahydrofuran (THF) of 160mL and constantly and stirs; then slowly adding 48mL concentration is the diethyl ether solution of the 2-ethylhexyl magnesium bromide of 1mol/L; this process remains on 0 ° of C reaction 35 minutes, and then adding 4mL concentration is that the tetrachloro of 0.1mol/L closes copper acid two lithium (Li 2cuCl 4) tetrahydrofuran solution stirring reaction 8 hours, carry out neutralization reaction 20 minutes with 10% sodium hydroxide solution of 100mL, finally product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then 10% aqueous sodium hydroxide solution of 200mL, saturated sodium metabisulfite solution and salt solution for extract are washed successively, finally with dried over sodium sulfate underpressure distillation.Product is crossed to silica gel column chromatography with sherwood oil, and the product after underpressure distillation is that solvent carries out recrystallization at-40 ° of C with 2-methylpentane, finally obtains yellow spicule crystal 2, the bromo-9-bis-of 7-bis-(2-ethylhexyl) methylene radical fluorenes, productive rate 62%.GC-MS(EI-m/z):560(M+)。
The preparation of (3) 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(2-ethylhexyl) methylene radical fluorenes (compd A 2):
Put up tetrahydrofuran (THF) water distilling apparatus, will be join in single port bottle with the KOH tetrahydrofuran solvent of dry 1 day, then add the thin sodium piece of 10g and 5g benzophenone, constantly stir, the system of being back to is intense violet color, steams THF stand-by.Under strict anhydrous and oxygen-free reaction conditions; by nitrogen protection; in reaction flask, add 0.01mol; 5.56g2; the bromo-9-bis-of 7-bis-(2-ethylhexyl) methylene radical fluorenes; inject the refining tetrahydrofuran solvent of appropriate 250mL with syringe, under-85 ° of C conditions, slowly inject the n-Butyl Lithium hexane solution of the 1.6mol/L of 0.04mol with syringe, stirring reaction 4 hours.Then under-85 ° of C conditions, inject 0.08mol with syringe, 2-isopropoxy-4 of 16mL, 4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, is warmed up to room temperature reaction 48 hours, obtains final product 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(2-ethylhexyl) methylene radical fluorenes.After reaction finishes, add saturated brine (NaCl) solution washing, chloroform extraction, anhydrous Na 2sO 4dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product.It is that leacheate carries out silica gel column chromatography separation that crude product is selected to methylene dichloride, obtains 2 after purifying, 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(2-ethylhexyl) methylene radical fluorenes, productive rate 67%.GC-MS(EI-m/z):655(M+)。
(4) preparation of P2:
In reactor, add 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(2-ethylhexyl) methylene radical fluorenes (1mmol, 0.654g), 5,7-bis-is bromo-2,3-bis-(1-methyl-propyl)-thieno-[3,4-b] pyrazine (1mmol, 0.406g), the Na of three (dibenzalacetone) two palladiums (0.05mmol, 0.046g), 2mol/L 2cO 3aqueous solution 5mL and DMF solvent 40mL, by repeatedly leading to N 2make reaction system in anaerobic state with vacuumizing, under 100 ° of C conditions, react 72h.
After reaction 72h, in product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to 5mL, splashed in 400mL anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtained pressed powder.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer three (dibenzalacetone) two palladiums, finally polymkeric substance/chloroformic solution is revolved and steam to surplus 11mL, splashed in methanol solvate and stirred for several hour, finally polymer P 2 is collected to oven dry.With Soxhlet extractor by polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 2 after purifying is carried out to GPC test, and recording number-average molecular weight is 67700, and polymkeric substance monodispersity is 2.63.
Embodiment 3
A kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be designated as polymer P 3(n=71), structural formula is as follows:
The preparation of (1) the bromo-9-bis-of 2,7-bis-(thiomethyl) methylene radical fluorenes:
Concrete operations are with basic identical in embodiment 1, and difference is: the molar weight of 2,7-dibromo fluorenes is 0.02mol(6.48g), the molar weight of potassium tert.-butoxide is 0.044mol(4.928g); The molar weight of dithiocarbonic anhydride is 0.022mol(1.3mL), and stirring reaction 15 minutes; And with dropping funnel continue 8 minutes drip molar weight be 0.022mol(1.4mL) methyl iodide after, stirring reaction 5 hours.
The preparation (Compound C 3) of the bromo-9-dibutyl of (2) 2,7-bis-methylene radical fluorenes:
Under-8 ° of C and nitrogen protection condition; get step 1 react make 2; the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (0.02mol; 8.56g) be dissolved in the anhydrous tetrahydrofuran solvent of 150mL and constantly stir, then slowly adding 44mL concentration is the normal-butyl bromination magnesium (C of 1mol/L 4h 9mgBr) diethyl ether solution, this process remains on-10 ° of C reactions 38 minutes, then adding 5mL concentration is the tetrahydrofuran solution stirring reaction 6 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 15 minutes with 10% sodium hydroxide solution of 100mL, finally product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then 10% aqueous sodium hydroxide solution of 250mL, saturated sodium metabisulfite solution and salt solution for extract are washed successively, finally with dried over sodium sulfate underpressure distillation.Product is crossed to silica gel column chromatography with sherwood oil, and the product after underpressure distillation is that solvent carries out recrystallization at-38 ° of C with 2-methylpentane, finally obtains yellow spicule crystal 2, the bromo-9-dibutyl of 7-bis-methylene radical fluorenes, productive rate 68%.GC-MS(EI-m/z):448(M +)。
The preparation of (3) 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes (compound A-13):
Put up tetrahydrofuran (THF) water distilling apparatus, will be join in single port bottle with the KOH tetrahydrofuran solvent of dry 1 day, then add the thin sodium piece of 12g and 4g benzophenone, constantly stir, the system of being back to is intense violet color, steams THF stand-by.Under strict anhydrous and oxygen-free reaction conditions; by nitrogen protection; in reaction flask, add 0.01mol; 4.48g2; the bromo-9-dibutyl of 7-bis-methylene radical fluorenes; with the refining tetrahydrofuran solvent of syringe injection 300mL, under-80 ° of C conditions, slowly inject the n-Butyl Lithium hexane solution of the 1.6mol/L of 0.03mol with syringe, stirring reaction 2 hours.Then under-80 ° of C conditions, inject 0.045mol with syringe, 2-isopropoxy-4 of 9mL, 4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, is warmed up to room temperature reaction 24 hours, obtains final product 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes.After reaction finishes, add saturated brine (NaCl) solution washing, chloroform extraction, anhydrous Na 2sO 4dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product.Select eluent methylene chloride liquid to carry out silica gel column chromatography separation crude product, obtain 2 after purifying, 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes, productive rate 71%.GC-MS(EI-m/z):543(M +)。
(4) preparation of P3:
In reactor, add 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes (1mmol, 0.542g), 5,7-bis-is bromo-2,3-bis-(tetracontyl)-thieno-[3,4-b] pyrazine (lmmol, 1.416g), the Na of two (triphenyl phosphorus) palladium chlorides (0.02mmol, 0.0142g), 2mol/L 2cO 3aqueous solution 4mL and DMF solvent 40mL, by repeatedly leading to N 2make reaction system in anaerobic state with vacuumizing, under 80 ° of C conditions, react 48h.
After reaction 48h, in product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to 5mL, splashed in 400mL anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtained pressed powder.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove two (triphenyl phosphorus) palladium chlorides of catalyzer, finally polymkeric substance/chloroformic solution is revolved and steam to surplus 15mL, splashed in methanol solvate and stirred 3 hours, finally polymer P 3 being collected to oven dry.With Soxhlet extractor by polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 3 after purifying is carried out to GPC test, and recording number-average molecular weight is 110800, and polymkeric substance monodispersity is 1.97.
Embodiment 4
A kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be designated as polymer P 4(n=35), structural formula is as follows:
The preparation of (1) the bromo-9-bis-of 2,7-bis-(thiomethyl) methylene radical fluorenes:
Concrete operations are with basic identical in embodiment 1, and difference is: the molar weight of 2,7-dibromo fluorenes is 0.02mol(6.48g), the molar weight of potassium tert.-butoxide is 0.048mol(5.376g); The molar weight of dithiocarbonic anhydride is 0.024mol(1.45mL), and stirring reaction 12 minutes; And with dropping funnel continue 6 minutes drip molar weight be 0.022mol(1.37mL) methyl iodide after, stirring reaction 6 hours.
The preparation of (2) the bromo-9-bis-of 2,7-bis-(tetracontyl) methylene radical fluorenes (Compound C 4):
Under-10 ° of C and nitrogen protection condition; get that above-mentioned reaction makes 2; the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (0.02mol; 8.56g) be dissolved in the anhydrous tetrahydrofuran solvent of 150mL and constantly stir, then slowly adding 45mL concentration is the tetracontyl magnesium bromide (C of 1mol/L 40h 81mgBr) diethyl ether solution, this process remains on-20 ° of C reactions 36 minutes, then adding 5mL concentration is the tetrahydrofuran solution stirring reaction 5 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 15 minutes with 10% sodium hydroxide solution of 100mL, finally product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then 10% aqueous sodium hydroxide solution of 300mL, saturated sodium metabisulfite solution and salt solution for extract are washed successively, finally with dried over sodium sulfate underpressure distillation.Product is crossed to silica gel column chromatography with sherwood oil, and the product after underpressure distillation is that solvent carries out recrystallization at-38 ° of C with 2-methylpentane, finally obtains yellow spicule crystal 2, the bromo-9-bis-of 7-bis-(tetracontyl) methylene radical fluorenes, productive rate 78%.GC-MS(EI-m/z):1458(M +)。
The preparation of (3) 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(tetracontyl) methylene radical fluorenes (compd A 4):
Put up tetrahydrofuran (THF) water distilling apparatus, will be join in single port bottle with the KOH tetrahydrofuran solvent of dry 2 days, then add the thin sodium piece of 10g and 3g benzophenone, constantly stir, the system of being back to is intense violet color, steams THF, obtains refining tetrahydrofuran (THF).Under strict anhydrous and oxygen-free reaction conditions; by nitrogen protection; in reaction flask, add 2; the bromo-9-bis-of 7-bis-(tetracontyl) methylene radical fluorenes (0.01mol; 14.58g); with the refining tetrahydrofuran solvent of syringe injection 350mL, under-80 ° of C conditions, slowly inject the n-Butyl Lithium hexane solution of the 1.6mol/L of 0.021mol with syringe, stirring reaction 3 hours.Then under-80 ° of C conditions, inject 0.025mol with syringe, 2-isopropoxy-4 of 5mL, 4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, is warmed up to room temperature reaction 48 hours, obtains final product 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes.After reaction finishes, add saturated brine (NaCl) solution washing, toluene solvant extraction, anhydrous Na 2sO 4dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product.It is that leacheate carries out silica gel column chromatography separation that crude product is selected to dichloromethane solvent, obtains 2 after purifying, 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(tetracontyl) methylene radical fluorenes, productive rate 73%.GC-MS(EI-m/z):1552(M +)。
(4) preparation of P4:
In reactor, add 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(tetracontyl) methylene radical fluorenes (1mmol, 1.552g), 5,7-bis-is bromo-2, the fluoro-thieno-of 3-bis-[3,4-b] pyrazine (1mmol, 0.330g), the Na of tetrakis triphenylphosphine palladium (0.02mmol, 0.023g), 2mol/L 2cO 3aqueous solution 10mL and toluene solvant 40mL, by repeatedly leading to N 2make reaction system in anaerobic state with vacuumizing, under 80 ° of C conditions, carry out Suzuki coupling reaction 72h.
After reaction 72h, in product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to 5mL, splashed in 400mL anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtained pressed powder.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer tetrakis triphenylphosphine palladium, finally polymkeric substance/chloroformic solution is revolved and steam to surplus 8mL, splashed in methanol solvate and stir 3 hours, finally polymer P 4 is collected to oven dry.With Soxhlet extractor by polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 4 after purifying is carried out to GPC test, and recording number-average molecular weight is 52500, and polymkeric substance monodispersity is 1.84.
Embodiment 5
A kind of containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, be designated as polymer P 5(n=61), structural formula is as follows:
The preparation of (1) the bromo-9-bis-of 2,7-bis-(thiomethyl) methylene radical fluorenes:
Concrete operations are with basic identical in embodiment 1, and difference is: the molar weight of 2,7-dibromo fluorenes is 0.02mol(6.48g), the molar weight of potassium tert.-butoxide is 0.044mol(4.928g); The molar weight of dithiocarbonic anhydride is 0.022mol(1.3mL), and stirring reaction 15 minutes; And with dropping funnel continue 8 minutes drip molar weight be 0.022mol(1.4mL) methyl iodide after, stirring reaction 5 hours.
The preparation (Compound C 5) of the bromo-9-dihexyl of (2) 2,7-bis-methylene radical fluorenes:
Under-8 ° of C and nitrogen protection condition; get step 1 react make 2; the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (0.02mol; 8.56g) be dissolved in the anhydrous tetrahydrofuran solvent of 150mL and constantly stir, then slowly adding 44mL concentration is the n-hexyl magnesium bromide (C of 1mol/L 6h 13mgBr) diethyl ether solution, this process remains on-10 ° of C reactions 38 minutes, then adding 5mL concentration is the tetrahydrofuran solution stirring reaction 6 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 15 minutes with 10% sodium hydroxide solution of 100mL, finally product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then 10% aqueous sodium hydroxide solution of 250mL, saturated sodium metabisulfite solution and salt solution for extract are washed successively, finally with dried over sodium sulfate underpressure distillation.Product is crossed to silica gel column chromatography with sherwood oil, and the product after underpressure distillation is that solvent carries out recrystallization at-38 ° of C with 2-methylpentane, finally obtains yellow spicule crystal 2, the bromo-9-dihexyl of 7-bis-methylene radical fluorenes, productive rate 64%.GC-MS(EI-m/z):504(M +)。
The preparation of (3) 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dihexyl methylene radical fluorenes (compound A-45):
Put up tetrahydrofuran (THF) water distilling apparatus, will be join in single port bottle with the KOH tetrahydrofuran solvent of dry 1 day, then add the thin sodium piece of 12g and 4g benzophenone, constantly stir, the system of being back to is intense violet color, steams THF stand-by.Under strict anhydrous and oxygen-free reaction conditions; by nitrogen protection; in reaction flask, add 0.01mol; 5.04g2; the bromo-9-dihexyl of 7-bis-methylene radical fluorenes; with the refining tetrahydrofuran solvent of syringe injection 300mL, under-80 ° of C conditions, slowly inject the n-Butyl Lithium hexane solution of the 1.6mol/L of 0.03mol with syringe, stirring reaction 2 hours.Then under-80 ° of C conditions, inject 0.045mol with syringe, 2-isopropoxy-4 of 9mL, 4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, is warmed up to room temperature reaction 24 hours, obtains final product 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dihexyl methylene radical fluorenes.After reaction finishes, add saturated brine (NaCl) solution washing, chloroform extraction, anhydrous Na 2sO 4dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product.Select eluent methylene chloride liquid to carry out silica gel column chromatography separation crude product, obtain 2 after purifying, 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dihexyl methylene radical fluorenes, productive rate 72%.GC-MS(EI-m/z):598(M +)。
(4) preparation of P5:
In reactor, add 2,7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dihexyl methylene radical fluorenes (1mmol, 0.542g), 5,7-bis-is bromo-2,3-dihexyl-thieno-[3,4-b] pyrazine (lmmol, 0.462g), the Na of two (triphenyl phosphorus) palladium chlorides (0.02mmol, 0.0142g), 2mol/L 2cO 3aqueous solution 4mL and DMF solvent 40mL, by repeatedly leading to N 2make reaction system in anaerobic state with vacuumizing, under 80 ° of C conditions, react 48h.
After reaction 48h, in product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to 5mL, splashed in 400mL anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtained pressed powder.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove two (triphenyl phosphorus) palladium chlorides of catalyzer, finally polymkeric substance/chloroformic solution is revolved and steam to surplus 15mL, splashed in methanol solvate and stirred 3 hours, finally polymer P 5 being collected to oven dry.With Soxhlet extractor by polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 5 after purifying is carried out to GPC test, and recording number-average molecular weight is 41300, and polymkeric substance monodispersity is 1.87.
Embodiment 6
Prepare polymer solar cell device using P1 as active coating electron donor material, its structure, as Fig. 1, comprises the glass 101 stacking gradually, anode 102, buffer layer 103, active coating 104, negative electrode 105.Prepare by the following method:
The method that adopts spin coating is 4:1 by P1 and PCBM(mass ratio) after the ultrasonic blend of chlorobenzene solution, be spin-coated to the speed of 3000 revs/min on the electrode surface of ito glass/PEDOT:PSS.Wherein, PCBM is (6,6)-phenyl-C61-methyl-butyrate, and molecular formula is C 72h 14o 2; Ito glass is indium tin oxide conductive glass; PEDOT:PSS is poly-(3, the 4-ethylene two oxy thiophene) of polystyrolsulfon acid doping.
And then adopt the method for hot evaporation, and plating the translucent aluminium lamination of one deck and make negative potential, thickness is 20nm.
Finally by device with after epoxy encapsulation, be placed under 120 ° of C air tight conditions and anneal 4 hours, then drop to room temperature.Obtain a kind of solar cell device, representation is: glass/ITO/PEDOT:PSS/P1:PCBM/Al, the active area of device is 36mm 2, use 78.2mW/cm 2white light irradiate on one side from ITO electrode.Photovoltaic parameter with Keithley mensuration device under room temperature normal pressure.
The active coating area of organic solar batteries is 36mm 2, the material of its active coating adopts respectively the polymkeric substance (adopting respectively P1 ~ P5 to replace) of embodiment 1 ~ 5 preparation.The electrical property of organic solar batteries, i.e. I-E characteristic, is obtained by Keithley current/voltage source-measuring system and test component test, in table 1.
The I-E characteristic of table 1 organic solar batteries
From the data of table 1, the energy conversion efficiency of the organic solar batteries that the polymkeric substance making with the present invention is prepared as active coating is 1.12 ~ 1.25, these show of the present invention containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, can mate preferably with solar spectrum, and utilize alkylidene group fluorenes and thieno-[3,4-b] carrier mobility of pyrazine is higher, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.
Because the chemical structure of the annealed rear material of device is more regular orderly, improve transmission speed and the efficiency of current carrier, thereby improved photoelectric transformation efficiency, the photoelectric transformation efficiency of P1 ~ P5 is followed successively by 1.62%, 1.69%, and 1.73%, 1.86% and 1.84%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. one kind contains alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, it is characterized in that, for thering is the polymer P of following general formula:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
2. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, is characterized in that, comprises the following steps:
The compd A and the compd B that provide respectively following structural formula to represent:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100;
Under anaerobic state, according to mol ratio 1:1:0.005 ~ 0.05, compd A, compd B and catalyzer are dissolved in the first organic solvent, add alkaline solution, back flow reaction 24 ~ 72 hours under 60 ° of C ~ 100 ° C, after separation and purification, obtain containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, described is the polymer P with following general formula containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
3. as claimed in claim 2 containing alkylidene group fluorenes and thieno-[3,4-b] preparation method of pyrazine polymkeric substance, it is characterized in that, described catalyzer is the one in three (dibenzalacetone) two palladiums, two (triphenyl phosphorus) palladium chloride and tetrakis triphenylphosphine palladium.
4. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 2, is characterized in that, described the first organic solvent is the one in toluene and DMF.
5. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 2, is characterized in that, 5 ~ 20 times of the amount of substance that in described alkaline solution, the amount of substance of alkali is compd A, and described alkaline solution is aqueous sodium carbonate.
6. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 2, is characterized in that, described separation and purification comprises the following steps:
After reaction, in reaction system, add toluene and deionized water to extract, get organic phase, underpressure distillation is to 5 milliliters to 15 milliliters of organic phase residues, add in anhydrous methanol, stir, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, described pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, collect chromatographic solution concentrated by rotary evaporation, splash into again in methanol solvate and stirred for several hour, dry, obtain crude product, finally with apparatus,Soxhlet's by crude product extracting, obtain described containing alkylidene group fluorenes and thieno-[3, 4-b] pyrazine polymkeric substance.
7. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 2, is characterized in that, described compd A makes by the following method:
The Compound C that provides following structural formula to represent:
In formula, R 1for C 4~ C 40the alkyl of straight or branched;
In anhydrous response device, under the protection of nitrogen, Compound C is added in reactor, then add the second organic solvent, under ° C condition of-70 ° of C ~-85, slowly add n-Butyl Lithium, stirring reaction; After reaction, under ° C condition of-70 ° of C ~-85, in reaction system, slowly add 2-isopropoxy-4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-, reacts 10 ~ 48 hours after being warmed up to room temperature, and separation and purification obtains described compd A, and reaction formula is:
In formula, R 1for C 4~ C 40the alkyl of straight or branched.
8. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 7, is characterized in that, described Compound C makes by the following method:
The Compound D that provides following structural formula to represent:
Under-5 ° of C～-10 ° C and nitrogen protection condition, Compound D is dissolved in to the 3rd organic solvent and constantly stirs, then add alkyl magnesium bromide (R 1mgBr) diethyl ether solution, remains under the condition of-20 ° of C ~ 0 ° C and reacts 35 ~ 40 minutes, wherein R 1for C 4~ C 40the alkyl of straight or branched; Then add tetrachloro to close the tetrahydrofuran solution stirring reaction 4 ~ 8 hours of copper acid two lithiums, then carry out neutralization reaction 10 ~ 20 minutes with sodium hydroxide solution, separation and purification obtains described Compound C, and reaction formula is:
In formula, R 1for C 4~ C 40the alkyl of straight or branched.
9. the preparation method containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance as claimed in claim 8, is characterized in that, described Compound D makes by the following method:
Under nitrogen protection and room temperature condition; by 2; 7-dibromo fluorenes is dissolved in anhydrous dimethyl sulphoxide; under uniform stirring, add potassium tert.-butoxide again; add afterwards dithiocarbonic anhydride, stirring reaction 10 ~ 20 minutes, then drips and continues stirring reaction 4 ~ 6 hours after methyl iodide again; after separation and purification, obtain described Compound D, reaction formula is:
10. an organic solar batteries, comprises negative electrode, active coating, anode, it is characterized in that, the material of described active coating is claimed in claim 1 containing alkylidene group fluorenes and thieno-[3,4-b] pyrazine polymkeric substance, for having the polymer P of following general formula:
In formula, R 1for C 4~ C 40the alkyl of straight or branched; R 2for H atom, F atom or C 4~ C 40the alkyl of straight or branched; N is the integer between 10 ~ 100.
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