CN103833959A - Alkylidene fluorene and fluorene containing organic polymer semi conducting material and its preparation method and application - Google Patents

Abstract

The invention relates to an alkylidene fluorene and fluorene containing organic polymer semi conducting material and its preparation method and application. The alkylidene fluorene and fluorene containing organic polymer semi conducting material has the following structural formula (shown in the specification), n is an integer of 10-100; R1 is a C4-C40 straight chain or branched chain alkyl; and R2 is a C4-C40 straight chain or branched chain alkyl. After annealing of a solar energy battery component prepared from the alkylidene fluorene and fluorene containing organic polymer semi conducting material and an electron acceptor material, orderliness and regularity of arrangement in and among chain segments of material molecular can be improved, the current carrier mobility of the solar energy battery component can be improved, and the photoelectric conversion efficiency is improved.

Description

Contain organic polymer semiconductor material of alkylidene group fluorenes and fluorenes and its preparation method and application

Technical field

The present invention relates to photoelectron material field, particularly relate to a kind of organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes and its preparation method and application.

Background technology

High efficiency solar cell is normally take 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 polymer solar battery 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 7.4%, but still much lower than the efficiency of conversion of inorganic solar cell.

Summary of the invention

Based on this, be necessary organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes providing a kind of effciency of energy transfer that can improve solar cell device and its preparation method and application.

Containing an organic polymer semiconductor material for alkylidene group fluorenes and fluorenes, there is following structural formula:

Wherein, n is the integer between 10 ~ 100; R ₁for C ₄~ C ₄₀the alkyl of straight or branched; R ₂for C ₄~ C ₄₀the alkyl of straight or branched.

A preparation method who contains the organic polymer semiconductor material of alkylidene group fluorenes and fluorenes, comprises the steps:

Compd A and compd B are provided, and the structural formula of compd A is:

Wherein, R ₁for H or C ₄~ C ₄₀alkyl;

The structural formula of compd B is:

Wherein, R ₂for H or C ₄~ C ₄₀alkyl, R ₁and R ₂when different, be H; And

Under anaerobic state, compd A, compd B and catalyzer are dissolved in to Na according to the mol ratio of 1:1:0.005 ~ 0.05 ₂cO ₃the aqueous solution, wherein said Na ₂cO ₃na in the aqueous solution ₂cO ₃the molar weight that adds be 5 ~ 10 times of compd A, add toluene as solvent, back flow reaction 24 ~ 72 hours under 60 ° of C ~ 100 ° C, after separation and purification, obtain the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes, the general molecular formula of the described organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes is:

Wherein, n is the integer between 10 ~ 100.

In a preferred embodiment, the step of described separation and purification is:

In reaction system, add toluene, and deionized water extracts, get organic phase, described organic phase is evaporated to 5 milliliters to 15 milliliters by the method for underpressure distillation, again described organic phase is splashed in anhydrous methanol and constantly stir, there is gradually solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column to remove catalyzer with neutral alumina, finally by being spin-dried for, the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes after being purified.

In a preferred embodiment, described compd A is adopted preparation with the following method:

Compound C is provided, and the structural formula of Compound C is:

Under anhydrous and oxygen-free reaction conditions, in Compound C, inject tetrahydrofuran solvent, under-70 ° of C ~-85 ° C, slowly inject n-Butyl Lithium, stirring reaction 0.5 ~ 4 hour, wherein the mol ratio of Compound C and n-Butyl Lithium is 1:2 ~ 4, then under-70 ° of C ~-85 ° C with slowly injecting 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, separation and purification obtains described compd A, wherein, 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.

In a preferred embodiment, the step of described separation and purification is:

After reaction finishes, add saturated NaCl solution washing, use chloroform extraction, re-use anhydrous Na ₂sO ₄or anhydrous MgSO ₄dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product, use methylene dichloride to carry out silica gel column chromatography separation, the compd A after being purified for leacheate described crude product.

In a preferred embodiment, described Compound C is adopted preparation with the following method:

Compound D is provided, and the structural formula of Compound D is:

Under-5 ° of C and nitrogen protection condition, by Compound D, 2, the bromo-9-of 7-bis-(two thiomethyls) methylene radical fluorenes is dissolved in tetrahydrofuran solvent and constantly stirs, then to add concentration be the alkyl magnesium bromide (R of 1mol/L ₁mgBr) diethyl ether solution, remains on the following reaction of 0 ° of C 35 ~ 40 minutes, wherein R ₁for H or C ₄~ C ₄₀alkyl, the bromo-9-of 2,7-bis-(two thiomethyls) methylene radical fluorenes and alkyl magnesium bromide (R ₁mgBr) mol ratio is 1:2.0 ~ 2.4, then adding concentration is the tetrahydrofuran solution stirring reaction 4 ~ 8 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 10 ~ 20 minutes with 10% sodium hydroxide solution again, separation and purification obtains described Compound C, wherein 2, the mol ratio that the bromo-9-of 7-bis-(two thiomethyls) methylene radical fluorenes and tetrachloro close copper acid two lithiums is 25 ~ 50:1.

In a preferred embodiment, the step of described separation and purification is:

Reaction product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then the aqueous sodium hydroxide solution of mass concentration 10%, saturated sodium metabisulfite solution and salt solution for described extract are washed successively, again with dried over sodium sulfate underpressure distillation, and cross silica gel column chromatography with sherwood oil, product after underpressure distillation is that solvent carries out recrystallization at-35 ° of C ~-40 ° C with 2-methylpentane, finally obtains the Compound C after purifying.

In a preferred embodiment, described Compound D is adopted preparation with the following method:

Under the room temperature condition of logical nitrogen protection; under uniform stirring toward having dissolved 2; in the anhydrous dimethyl sulphoxide of 7-dibromo fluorenes, add potassium tert.-butoxide; wherein 2, the mol ratio of 7-dibromo fluorenes and potassium tert.-butoxide is 1:2.0 ~ 2.4, then injects dithiocarbonic anhydride stirring reaction 10 ~ 20 minutes; wherein 2; the mol ratio of 7-dibromo fluorenes and dithiocarbonic anhydride is 1:1.0 ~ 1.2, then drips after methyl iodide and continues stirring reaction 4 ~ 6 hours again, obtains Compound D after separation and purification.

In a preferred embodiment, the step of described separation and purification is:

Reacted resultant is poured in mixture of ice and water, then added strong aqua to remove unreacted methyl iodide, then filter, washing, after oven dry, carry out recrystallization with the mixed solvent of ethyl acetate and tetrahydrofuran (THF) 2:1, finally obtain the Compound D after purifying.

The application of the above-mentioned organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes in polymer solar cell device.

Alkylidene group fluorenes and derivative thereof and fluorenes class monomer are carried out after copolymerization, and the polymer semiconducting material 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.The device of preparing according to above-mentioned polymer semiconducting material, after high temperature annealing, can effectively increase order and the regularity between the interior each group of molecule and molecule segment, arranged, improves transmission speed and the efficiency of carrier mobility, and then improves photoelectric transformation efficiency.

Accompanying drawing explanation

Fig. 1 is the organic polymer method for preparing semi-conducting material schema containing alkylidene group fluorenes and fluorenes of an embodiment;

Fig. 2 is that the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes of embodiment 1 is as the structural representation of the organic solar batteries device of active coating.

Embodiment

For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.

The organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes of one embodiment, has following structural formula:

Wherein, n is the integer between 10 ~ 100; R ₁for C ₄~ C ₄₀the alkyl of straight or branched; R ₂for C ₄~ C ₄₀the alkyl of straight or branched.R ₁and R ₂group contributes to realize the resolvability of this polymkeric substance in specific organic solvent.

Preferably, the weight-average molecular weight Mw of this polymer semiconducting material is 5000 ~ 300000, and molecular weight distribution (PDI) is 1.2 ~ 5.0.

In above-mentioned polymer semiconducting material, 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 novel Donor unit that can be used for organic photovoltaic devices donor material.

The structural formula of fluorenes is as follows:

Fluorenes is also a kind of important organic photoelectrical material intermediate, and structural formula is as above schemed.Fluorenes and derivative thereof be owing to having the structure of easy modification, wide energy gap, and the conjugation performance that can effectively extend polymkeric substance reduces the bandwidth of polymkeric substance.Thereby caused materials chemistry man and physicist's attention, research has linear structure fluorenes class conjugation material and has very important effect in organic photoelectric field.

Alkylidene group fluorenes and derivative thereof and fluorenes class monomer are carried out after copolymerization, and the polymer semiconducting material 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 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.

The present invention also provides a convenient-to-running synthetic route containing alkylidene group fluorenes and derivative and fluorenes class monomer copolymer.

Refer to Fig. 1, the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes of an embodiment, comprises the steps:

Step S110, provide compd A and compd B.The structural formula of compd A is:

Wherein, R ₁for C ₄~ C ₄₀the alkyl of straight or branched.

The structural formula of compd B is:

Wherein, R ₂for C ₄~ C ₄₀the alkyl of straight or branched.

Step S120, under anaerobic state, compd A, compd B and catalyzer are dissolved in to Na according to the mol ratio of 1:1:0.005 ~ 0.05 ₂cO ₃the aqueous solution, wherein said Na ₂cO ₃na in the aqueous solution ₂cO ₃the molar weight that adds be 5 ~ 10 times of compd A, add toluene as solvent, back flow reaction 24 ~ 72 hours under 60 ° of C ~ 100 ° C, after separation and purification, obtain the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes, the general molecular formula of the described organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes is:

Wherein, n is the integer between 10 ~ 100.

Preferably, the purification procedures in step S120 is:

In reaction system, add toluene, and deionized water extracts, get organic phase, described organic phase is evaporated to 5 milliliters to 15 milliliters by the method for underpressure distillation, again described organic phase is splashed in anhydrous methanol and constantly stir, there is gradually solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column to remove catalyzer with neutral alumina, finally by being spin-dried for, the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes after being purified.

In step S110, compd A can be by being purchased or preparing.Preferably, compd A can be adopted preparation with the following method:

Step S111, provide Compound C, the structural formula of Compound C is:

Step S112, under anhydrous and oxygen-free reaction conditions, in Compound C, inject tetrahydrofuran (THF) (THF) solvent, under-70 ° of C ~-85 ° C, slowly inject n-Butyl Lithium (n-BuLi), stirring reaction 0.5 ~ 4 hour, wherein the mol ratio of Compound C and n-BuLi is 1:2 ~ 4, then under-70 ° of C ~-85 ° C with slowly injecting 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-, after being warmed up to room temperature, react 10 ~ 48 hours, separation and purification obtains described compd A, wherein, n-BuLi and 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the mol ratio of 2-bis-assorted oxygen pentaboranes is 1:1 ~ 2.

Preferably, the purification procedures in step S112 is:

After reaction finishes, add saturated NaCl solution washing, use chloroform extraction, use anhydrous Na ₂sO ₄or anhydrous MgSO ₄dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product, use methylene dichloride to carry out silica gel column chromatography separation, the compd A after being purified for leacheate described crude product.

In step S111, Compound C can be by being purchased or preparing.Preferably, Compound C can be adopted preparation with the following method:

Step S121, provide Compound D, the structural formula of Compound D is:

Step S122, under-5 ° of C and nitrogen protection condition, bromo-2,7-bis-9-(two thiomethyls) methylene radical fluorenes be dissolved in to tetrahydrofuran solvent and constantly stir, then to add concentration be the R of 1mol/L ₁the diethyl ether solution of MgBr, remains on the following reaction of 0 ° of C 35 ~ 40 minutes, wherein R ₁for H or C ₄~ C ₄₀alkyl, 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, then adding concentration is the tetrahydrofuran solution stirring reaction 4 ~ 8 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 10 ~ 20 minutes with 10% sodium hydroxide solution again, separation and purification obtains described Compound C, wherein 2, the mol ratio that the bromo-9-of 7-bis-(two thiomethyls) methylene radical fluorenes and tetrachloro close copper acid two lithiums is 25 ~ 50:1.

Preferably, the purification procedures in step S122 is:

Reaction product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then the aqueous sodium hydroxide solution of mass concentration 10%, saturated sodium metabisulfite solution and salt solution for described extract are washed successively, again with dried over sodium sulfate underpressure distillation, and cross silica gel column chromatography with sherwood oil, product after underpressure distillation is that solvent carries out recrystallization at-35 ° of C ~-40 ° C with 2-methylpentane, finally obtains the Compound C after purifying.

In step S121, Compound D can be by being purchased or preparing.Preferably, Compound D can be adopted preparation with the following method:

Step S131, under the room temperature condition of logical nitrogen protection; under uniform stirring toward having dissolved 2; in the anhydrous dimethyl sulphoxide (DMSO) of 7-dibromo fluorenes, add potassium tert.-butoxide; wherein 2, the mol ratio of 7-dibromo fluorenes and potassium tert.-butoxide is 1:2.0 ~ 2.4, then injects dithiocarbonic anhydride stirring reaction 10 ~ 20 minutes; wherein 2; the mol ratio of 7-dibromo fluorenes and dithiocarbonic anhydride is 1: 1.0 ~ 1.2, then drips after methyl iodide and continues stirring reaction 4 ~ 6 hours again, obtains Compound D after separation and purification.

Preferably, the purification procedures in step S131 is:

Reacted resultant is poured in mixture of ice and water, then added strong aqua to remove unreacted methyl iodide, then filter, washing, after oven dry, carry out recrystallization with the mixed solvent of ethyl acetate and tetrahydrofuran (THF) 2:1, finally obtain the Compound D after purifying.

Further illustrate by specific embodiment below.

Embodiment 1

The open following polymer P 1 of structure of the present embodiment:

The preparation process of P1 is as follows:

Step 1,2, the preparation of the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (Compound D):

Under the room temperature condition of logical nitrogen protection; dissolve 2 toward adding in reaction flask; 7-dibromo fluorenes (48.6g; the anhydrous DMSO of 1L 0.15mol); under the condition of uniform stirring, add 33.6g(0.30mol) potassium tert.-butoxide; then inject 9mL dithiocarbonic anhydride (0.15mol) stirring reaction 10 minutes with syringe, continue again stirring reaction 4 hours after then continuing slowly to drip for 5 minutes 9.3mL methyl iodide (0.15mol) with dropping funnel.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, the ethyl acetate that is 2:1 by volume ratio and the mixed solvent of tetrahydrofuran (THF) carry out recrystallization, 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+)。

Step 2,2, the preparation of the bromo-9-bis-of 7-bis-(dodecyl) methylene radical fluorenes (Compound C):

Under-5 ° of C and nitrogen protection condition; get step 1 react make 2; the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (0.025mol; 64.2g) be dissolved in the anhydrous tetrahydrofuran solvent of 150mL and constantly stir, then slowly adding 50mL concentration is the dodecyl bromination magnesium (C of 1mol/L ₁₂h ₂₅mgBr) diethyl ether solution, this process remains on the following reaction of 0 ° of C 35 minutes, and then adding 10mL concentration is that the tetrachloro of 0.1mol/L closes copper acid two lithium (Li ₂cuCl ₄) tetrahydrofuran solution stirring reaction 4 hours, 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 of 100mL, 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-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+)。

Step 3,2, the preparation of 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(dodecyl) methylene radical fluorenes (compd A):

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 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; pass into nitrogen protection; in reaction flask, add 2; the bromo-9-bis-of 7-bis-(dodecyl) methylene radical fluorenes (0.01mol; 6.73g); with the refining tetrahydrofuran solvent of syringe injection 250mL, under-75 ° 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-75 ° of C conditions, inject 4mL2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1, the assorted oxygen pentaborane (0.02mol) of 3,2-bis-, be warmed up to room temperature reaction 10 hours, obtain 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 methylene dichloride, 2 after being purified, 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+)。

The preparation of step 4, 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), 2,7-bis-bromo-9, the Na of 9-dibutyl fluorenes (1mmol, 0.436g), 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 about 5ml left and right, splashed in 350ml anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtain 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 left and right, 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 GPC test, number-average molecular weight Mn ≈ 7910, polymkeric substance monodispersity is 1.97.In the present embodiment, record n=10.

Embodiment 2

The open following polymer P 2 of structure of the present embodiment:

The preparation process of P2 is as follows:

Step 1,2, the preparation of the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (Compound D):

Step 1 in this step 1 and embodiment 1 is roughly the same, and difference is: the molar weight of 2,7-dibromo fluorenes is 0.3mol(97.2g), 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(22.4mL) methyl iodide after, stirring reaction 6 hours.

Step 2,2, the preparation of 7-bis-bromo-9-bis-(2-ethylhexyl) methylene radical fluorenes (Compound C):

Under-5 ° 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 160mL and constantly stir, then slowly adding 48mL concentration is the diethyl ether solution of the 2-ethylhexyl magnesium bromide of 1mol/L, this process remains on the following reaction of 0 ° of C 40 minutes, then adding 4mL concentration is the tetrahydrofuran solution stirring reaction 8 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, 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 by 200mL 10% aqueous sodium hydroxide solution for 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-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+)。

Step 3,2, the preparation of 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):

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 2; the bromo-9-bis-of 7-bis-(2-ethylhexyl) methylene radical fluorenes (0.01mol; 5.56g); inject the refining tetrahydrofuran solvent of 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 2-isopropoxy-4 of 16mL with syringe, 4,5,5-tetramethyl--1, the assorted oxygen pentaborane (0.08mol) of 3,2-bis-, be warmed up to room temperature reaction 48 hours, obtain 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 solvent extraction, anhydrous MgSO 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, 2 after being purified, 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+)。

The preparation of step 4, 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), 2,7-bis-bromo-9, the Na of 9-bis-(2-ethylhexyl) fluorenes (1mmol, 0.548g), tetrakis triphenylphosphine palladium (0.05mmol, 0.058g), 2mol/L ₂cO ₃aqueous solution 5ml and toluene solvant 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 about 15ml left and right, splashed in 400ml anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtain 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 15ml left and right, 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, number-average molecular weight Mn ≈ 79100, polymkeric substance monodispersity is 1.72.In the present embodiment, n=100.

Embodiment 3

The open following polymer P 3 of structure of the present embodiment:

Step 1,2, the preparation of the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (Compound D):

Step 1 in this step 1 and embodiment 1 is roughly the same, 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.

Step 2,2, the preparation of the bromo-9-dibutyl of 7-bis-methylene radical fluorenes (Compound C):

Under-5 ° 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 diethyl ether solution of the normal-butyl bromination magnesium of 1mol/L, this process remains on the following reaction of 0 ° of C 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 with 250mL 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-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 ⁺)。

Step 3,2, the preparation of 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-dibutyl methylene radical fluorenes (compd A):

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; pass into nitrogen protection; in reaction flask, add 2; the bromo-9-dibutyl of 7-bis-methylene radical fluorenes (0.01mol; 4.48g); with the refining tetrahydrofuran solvent of syringe note 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 2-isopropoxy-4 of 9mL with syringe, 4,5,5-tetramethyl--1, the assorted oxygen pentaborane (0.045mol) of 3,2-bis-, be warmed up to room temperature reaction 24 hours, obtain 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.It is that leacheate carries out silica gel column chromatography separation that crude product is selected to methylene dichloride, 2 after being purified, 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 ⁺)。

The preparation of step 4, 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), 2,7-bis-bromo-9, the Na of 9-bis-(tetracontyl) fluorenes (lmmol, 1.446g), tetrakis triphenylphosphine palladium (0.02mmol, 0.0231g), 2mol/L ₂cO ₃aqueous solution 4ml and toluene solvant 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 about 11ml left and right, splashed in 400ml anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtain 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 11ml left and right, splashed in methanol solvate and stirred for several hour, finally polymer P 3 is 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, number-average molecular weight Mn ≈ 105600, polymkeric substance monodispersity is 1.42.In the present embodiment, n=67.

Embodiment 4

The open following polymer P 4 of structure of the present embodiment:

Step 1,2, the preparation of the bromo-9-bis-of 7-bis-(thiomethyl) methylene radical fluorenes (Compound D):

Step 1 in this step 1 and embodiment 1 is roughly the same, 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.

Step 2,2, the preparation of the bromo-9-bis-of 7-bis-(tetracontyl) methylene radical fluorenes (Compound C):

Under-5 ° 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 the following reaction of 0 ° of C 37 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 ⁺)。

Step 3,2, the preparation of 7-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-9-bis-(tetracontyl) methylene radical fluorenes (compd A):

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 stand-by.Under strict anhydrous and oxygen-free reaction conditions; pass into nitrogen protection; in reaction flask, add 2 of 14.58g; the bromo-9-bis-of 7-bis-(tetracontyl) methylene radical fluorenes (0.01mol); inject the refining tetrahydrofuran solvent of 350mL with syringe; 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 2-isopropoxy-4 of 5mL with syringe, 4,5,5-tetramethyl--1, the assorted oxygen pentaborane (0.025mol) of 3,2-bis-, be warmed up to room temperature reaction 48 hours, obtain 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.It is that leacheate carries out silica gel column chromatography separation that crude product is selected to methylene dichloride, 2 after being purified, 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 ⁺)。

The preparation of step 4, 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), 2,7-bis-bromo-9, the Na of 9-dioctyl fluorene (1mmol, 0.548g), tetra-triphenylphosphine palladium (0.02mmol, 0.023g), 2mol/L ₂cO ₃aqueous solution 3.5ml 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 about 10ml left and right, splashed in 400ml anhydrous methanol and constantly stirred, and have solid precipitation to separate out, after suction filtration, oven dry, obtain 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 10ml left and right, splashed in methanol solvate and stirred for several hour, 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, number-average molecular weight Mn ≈ 52400, polymkeric substance monodispersity is 1.74.In the present embodiment, n=31.

Embodiment 5

Prepare polymer solar cell device using P1 as active coating electron donor material, its structure is: Glass/ITO/PEDOT:PSS/P1:PCBM/Al, its structure is as Fig. 2.

Adopt the method for spin coating, P1 and PCBM are pressed to (w/w=4:1) after the ultrasonic blend of chlorobenzene solution, the speed turning with per minute 3000 is evenly spin-coated on the electrode surface of ito glass/PEDOT:PSS.Wherein ito glass is indium tin oxide conductive glass, and PEDOT:PSS is poly-(3, the 4-ethylene two oxy thiophene) of polystyrolsulfon acid doping, and is formed on ito glass by spin-coating method.And then adopt the method for hot evaporation, plate the translucent aluminium lamination of one deck and make negative potential, the about 20nm of thickness.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.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 multipolymer (adopting respectively P1 ~ P4 to replace) of embodiment 1 ~ 4 preparation.The electrical property of its organic solar batteries, i.e. I-E characteristic, is obtained by Keithley current/voltage source-measuring system and test component test, in table 1.

Table 1

As seen from the data in Table 1, the energy conversion efficiency of the organic solar batteries that the multipolymer making with the present invention is prepared as active coating is 1.03 ~ 1.11, these show the multipolymer containing alkylidene group fluorenes and Thienopyrroles diketone of the present invention, can mate preferably with solar spectrum, and utilize the carrier mobility of alkylidene group fluorenes and Thienopyrroles diketone 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, be 1.74%.

The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. containing an organic polymer semiconductor material for alkylidene group fluorenes and fluorenes, it is characterized in that thering is following structural formula:

Wherein, n is the integer between 10 ~ 100; R ₁for C ₄~ C ₄₀the alkyl of straight or branched; R ₂for C ₄~ C ₄₀the alkyl of straight or branched.

2. a preparation method who contains the organic polymer semiconductor material of alkylidene group fluorenes and fluorenes, is characterized in that, comprises the steps:

Compd A and compd B are provided, and the structural formula of compd A is:

Wherein, R ₁for C ₄~ C ₄₀the alkyl of straight or branched;

The structural formula of compd B is:

Wherein, R ₂for C ₄~ C ₄₀the alkyl of straight or branched;

Under anaerobic state, compd A, compd B and catalyzer are dissolved in to Na according to the mol ratio of 1:1:0.005 ~ 0.05 ₂cO ₃the aqueous solution, wherein said Na ₂cO ₃na in the aqueous solution ₂cO ₃the molar weight that adds be 5 ~ 10 times of compd A, add toluene as solvent, back flow reaction 24 ~ 72 hours under 60 ° of C ~ 100 ° C, after separation and purification, obtain the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes, the general molecular formula of the described organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes is:

Wherein, n is the integer between 10 ~ 100.

3. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 2, is characterized in that, the step of described separation and purification is:

In reaction system, add toluene, and deionized water extracts, get organic phase, described organic phase is evaporated to 5 milliliters to 15 milliliters by the method for underpressure distillation, again described organic phase is splashed in anhydrous methanol and constantly stir, there is gradually solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column to remove catalyzer with neutral alumina, finally by being spin-dried for, the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes after being purified.

4. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 2, is characterized in that, described compd A is adopted preparation with the following method:

Compound C is provided, and the structural formula of Compound C is:

Under anhydrous and oxygen-free reaction conditions, in Compound C, inject tetrahydrofuran solvent, under-70 ° of C ~-85 ° C, slowly inject n-Butyl Lithium, stirring reaction 0.5 ~ 4 hour, wherein the mol ratio of Compound C and n-Butyl Lithium is 1:2 ~ 4, then under-70 ° of C ~-85 ° C with slowly injecting 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, separation and purification obtains described compd A, wherein, 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.

5. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 4, is characterized in that, the step of described separation and purification is:

After reaction finishes, add saturated NaCl solution washing, use chloroform extraction, re-use anhydrous Na ₂sO ₄or anhydrous MgSO ₄dry, after suction filtration, collect filtrate, revolve after evaporating solvent and obtain crude product, use methylene dichloride to carry out silica gel column chromatography separation, the compd A after being purified for leacheate described crude product.

6. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 4, is characterized in that, described Compound C is adopted preparation with the following method: Compound D is provided, and the structural formula of Compound D is:

Under-5 ° of C and nitrogen protection condition, Compound D is dissolved in to tetrahydrofuran solvent and constantly stirs, then to add concentration be the diethyl ether solution of the alkyl magnesium bromide of 1mol/L, remain on the following reaction of 0 ° of C 35 ~ 40 minutes, wherein R ₁for H or C ₄~ C ₄₀alkyl, the mol ratio of Compound D and alkyl magnesium bromide is 1:2.0 ~ 2.4, then adding concentration is the tetrahydrofuran solution stirring reaction 4 ~ 8 hours that the tetrachloro of 0.1mol/L closes copper acid two lithiums, carry out neutralization reaction 10 ~ 20 minutes with 10% sodium hydroxide solution again, separation and purification obtains described Compound C, and wherein to close the mol ratio of copper acid two lithiums be 25 ~ 50:1 for Compound D and tetrachloro.

7. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 6, is characterized in that, the step of described separation and purification is:

Reaction product is collected with diatomite filtration, then by ethyl acetate, the liquid phase filtrate layers after diatomite filtration is extracted, then the aqueous sodium hydroxide solution of mass concentration 10%, saturated sodium metabisulfite solution and salt solution for described extract are washed successively, again with dried over sodium sulfate underpressure distillation, and cross silica gel column chromatography with sherwood oil, product after underpressure distillation is that solvent carries out recrystallization at-35 ° of C ~-40 ° C with 2-methylpentane, finally obtains the Compound C after purifying.

8. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 6, is characterized in that, described Compound D is adopted preparation with the following method:

Under the room temperature condition of logical nitrogen protection; under uniform stirring toward having dissolved 2; in the anhydrous dimethyl sulphoxide of 7-dibromo fluorenes, add potassium tert.-butoxide; wherein 2, the mol ratio of 7-dibromo fluorenes and potassium tert.-butoxide is 1:2.0 ~ 2.4, then injects dithiocarbonic anhydride stirring reaction 10 ~ 20 minutes; wherein 2; the mol ratio of 7-dibromo fluorenes and dithiocarbonic anhydride is 1:1.0 ~ 1.2, then drips after methyl iodide and continues stirring reaction 4 ~ 6 hours again, obtains Compound D after separation and purification.

9. the preparation method of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes according to claim 8, is characterized in that, the step of described separation and purification is:

Reacted resultant is poured in mixture of ice and water, then added strong aqua to remove unreacted methyl iodide, then filter, washing, after oven dry, carry out recrystallization with the mixed solvent of ethyl acetate and tetrahydrofuran (THF) 2:1, finally obtain the Compound D after purifying.

10. the application of the organic polymer semiconductor material containing alkylidene group fluorenes and fluorenes as claimed in claim 1 in polymer solar cell device.

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