CN103833962A - Selenophen-silole di (benzo thiadiazole) copolymer and its preparation and application - Google Patents

Abstract

The invention provides a selenophen-silole di (benzo thiadiazole) copolymer and its preparation and application, the selenophen-silole di (benzo thiadiazole) copolymer is a compound P with the following general formula, wherein R1, R2 and R3 are C1-C20 alkyls, and n is an integer between 1-100. The selenophen-silole di (benzo thiadiazole) copolymer contains a novel silole di (benzo thiadiazole) conjugated unit, is high in solar spectrum matching degree, and is a plane conjugate structure, the carrier mobility rate is high, the energy conversion efficiency is improved, the preparation method is simple and controllable, and the selenophen-silole di (benzo thiadiazole) copolymer has good application prospects in the fields of polymer solar cells, organic electroluminescent luminous devices and other photoelectric materials.

Description

Cough up and two (diazosulfide) multipolymers and preparation and application containing selenophen-thiophene

Technical field

The present invention relates to photoelectric material technical field, particularly relate to a kind of selenophen-thiophene that contains and cough up also two (diazosulfide) multipolymer and preparation method thereof and application.

Background technology

The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell is because complex manufacturing, cost are high at present, and application is restricted.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C ₆₀between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.

At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.And the absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, it is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor, improve absorbing sun power.

The multipolymer that contains selenophen unit and diazosulfide unit for photoelectric material appears in the newspapers, but the effciency of energy transfer obtaining is in actual applications still lower.Therefore, develop new polymer materials, improve the effciency of energy transfer of photoelectric material for the great significance of organic solar batteries.

Summary of the invention

For addressing the above problem, the present invention aims to provide a kind of selenophen-thiophene that contains and coughs up also two (diazosulfide) multipolymer.

The present invention also aims to provide containing selenophen-thiophene and cough up also preparation method and the application of two (diazosulfide) multipolymer.

First aspect, the invention provides a kind of selenophen-thiophene that contains and coughs up also two (diazosulfide) multipolymer, for thering is the copolymer p of following general formula:

In formula, R ₁, R ₂, R ₃for C ₁~ C ₂₀alkyl, n is the integer between 1 ~ 100.Of the present invention containing selenophen-thiophene cough up and two (diazosulfide) copolymer structure in, above substituting group is used for modifying agent structure, for example conventionally can on selenophen unit, introduce heterocycle, many aromatic rings or fragrant heterocycle molecule, can increase the cloud density on polymer backbone, improve carrier transmission performance, stability or film-forming properties, or regulate containing selenophen-thiophene and cough up the also processing characteristics such as dissolving and film forming of two (diazosulfide) multipolymer by alkyl substituent carbonatoms.

Provided by the invention containing selenophen-thiophene cough up and the structure of two (diazosulfide) multipolymer in contain that new thiophene is coughed up and two (diazosulfide) unit, diazosulfide unit is common functional unit, there is excellent reduction reversibility, approach with the work content value of the metallic cathode such as magnesium, aluminium, belong to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, it is the good body unit that is subject to, there is good electronic transport property, can also regulate the energy gap of material, and thiophene is coughed up and in structural unit, is had σ simultaneously ^*-π ^*conjugation, makes thiophene cough up the minimum occupied orbital energy level (LUMO) of unit lower, makes it have good electron affinity and electronic mobility simultaneously.Of the present invention containing selenophen-thiophene cough up and two (diazosulfide) multipolymer in the new thiophene that contains cough up and two (diazosulfide) copolymer unit combines the constitutional features of above two kinds of unit, there is narrower band gap and stronger conjugated nature, make multipolymer there is excellent electronic transmission performance, can be applicable to the fields such as organic solar batteries.

Meanwhile, thiophene is five-membered ring structure, has moderate band gap, wider spectral response, preferably thermostability and film forming properties, and the radius ratio sulphur atom of selenium atom is large, can strengthen molecule between copolymer chain overlapping, promote the conduction of electric charge, make selenophen there are low band gap and 2,3,4,5 easily modify and replace, and have caused in recent years the very big concern of researcher.

The present invention obtains having coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene of novel planar conjugated structure on the basis of above two kinds of unit, has excellent carrier mobility ability and configuration flexibility, has a extensive future.

Second aspect, the invention provides containing selenophen-thiophene and coughs up the also preparation method of two (diazosulfide) multipolymer, comprises following operation steps:

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

In formula, R ₁, R ₂, R ₃for C ₁~ C ₂₀alkyl;

In atmosphere of inert gases, 1:1.5 ~ 1.5:1 is dissolved in described compd A and compd B in organic solvent in molar ratio, add catalyzer, at 50 DEG C ~ 120 DEG C, carry out Stille coupling reaction 6 ~ 100 hours, after separation and purification, obtain coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene, describedly cough up and two (diazosulfide) multipolymer is the compound P with following general formula containing selenophen-thiophene:

In formula, n is the integer between 1 ~ 100.

The reaction formula of Stille coupling reaction is:

Preferably, described catalyzer is organic palladium catalyzer, is three (dibenzalacetone) two palladium (Pd ₂(dba) ₃), tetrakis triphenylphosphine palladium (Pd (PPh ₃) ₄) and two (triphenylphosphine) palladium chloride (Pd (PPh ₃) ₂cl ₂) in one.

Preferably, 0.5% ~ 20% of the amount of substance that the mole dosage of described catalyzer is compd A.

Preferably, described rare gas element is the one in nitrogen and argon gas.

Preferably, described organic solvent is the one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene.Described solvent is enough.

Preferably, described preparation method's operating process is: compd A is mixed with compd B and organic solvent, vacuumize deoxygenation and be filled with rare gas element, add catalyzer, be heated to 50 ~ 120 DEG C, reaction times is 6 ~ 100 hours, and reaction finishes, and obtains coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene after separation and purification.

Preferably, being operating as of described separation and purification: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, taking toluene as elutriant, separate with neutral alumina chromatography column, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene.

The preparation method of described compd A comprises following operation steps:

(1), 4-oil of mirbane-1,2-diamines reacts with thionyl chloride and pyridine, separate obtain 5-nitro-2,1,3 diazosulfide, reaction formula is:

Preferably, described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/L, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 DEG C, and the time is 24h.

(2), 5-nitro-2,1,3 diazosulfide and Hydrogen bromide and bromine generation bromination reaction, obtain the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide, reaction formula is:

Preferably, described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides are 4:1mol/L with hydrobromic molecular volume ratio, described 5-nitro-2,1,3 diazosulfides: the molecular volume of bromine is than being 5.3:1mol/L, and described temperature of reaction is 127 DEG C, and the reaction times is 4h.

(3), 4, the bromo-5-of 7-bis-nitro-2, under copper powder catalysis, there is linked reaction in 1,3 diazosulfide, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:

Preferably, described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 DEG C, the reaction times is 3 hours.

(4), 4,4 '-bis-bromo-6, the nitro in 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides is through tindichloride (SnCl ₂) be reduced to after amino, under the condition existing at hydrochloric acid, carry out diazotization reaction with Sodium Nitrite, then react with potassiumiodide, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:

Preferably, described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1: 10, the temperature of described reduction reaction is 100 DEG C, the time is 10h; Described 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: the mol ratio of the hydrogenchloride (HCl) in hydrochloric acid is 0.92:1,4,4 '-bis-is bromo-6,6 '-dinitrobenzene- Lian 2,1,3 diazosulfides: the mol ratio of Sodium Nitrite is 0.53:1, the temperature of described diazotization reaction is below 5 DEG C, the time is 30min; Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of potassiumiodide is 0.054:1, the described time of reacting with potassiumiodide is 12h.

(5) provide suc as formula the Compound C shown in C, wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl;

In dimethyl formamide (DMF) solvent and under oxygen free condition, at-90 DEG C, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides react with n-Butyl Lithium, then at room temperature react with Compound C, obtain compd A, and reaction formula is:

Preferably, described n-Butyl Lithium and 4, the mol ratio of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is x, 2≤x ﹤ 4, described Compound C and 4, the mol ratio of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is 2:1.Preferably, the described time of reacting with n-Butyl Lithium is 2h, and the described time of reacting with Compound C is 10h.

In an embodiment, for convenience of statement, compd A is used respectively compd A 1, A2, and the expressions such as A3, Compound C is used respectively Compound C 1, C2, the expressions such as C3, name is all as the criterion with the title in each embodiment.

The preparation method of described compd B comprises following operation steps:

Compound D is provided, wherein, R ₃for C ₁~ C ₂₀alkyl:

Under protection of inert gas, Compound D is added in tetrahydrofuran (THF) (THF), be cooled to-78 DEG C; under-78 DEG C of conditions, add n-Butyl Lithium; Compound D: the mol ratio of n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2h adds tributyltin chloride (SnBu under-78 DEG C of conditions ₃cl), Compound D: the mol ratio of tributyltin chloride is 1:2 is reacted 1 hour at-78 DEG C, is then warming up to room temperature, reacts 6 hours, obtains compd B after separating-purifying, and reaction formula is:

Preferably, described rare gas element is nitrogen or argon gas.

In an embodiment, for convenience of statement, compd B is used respectively the expressions such as compound B-11, B2, B3, B4, and Compound D is used respectively Compound D 1, D2, and D3, the expressions such as D4, name is all as the criterion with the title in each embodiment.

The third aspect, the invention provides containing selenophen-thiophene and coughs up and the application of two (diazosulfide) multipolymer, containing selenophen-thiophene cough up and two (diazosulfide) multipolymer for the preparation of polymer solar cell device.Described containing selenophen-thiophene cough up and two (diazosulfide) multipolymer as described in first aspect.

One provided by the invention is coughed up also two (diazosulfide) multipolymer and preparation method thereof and application containing selenophen-thiophene, has following beneficial effect:

1, of the present invention containing selenophen-thiophene cough up and two (diazosulfide) multipolymer in, thiophene is coughed up and two (diazosulfide) unit has the advantages such as simple in structure, symmetrical, electron delocalization performance is good, and be two dimensional structure, it is a kind of very excellent donor material, the formation of being combined with selenophen thiophthene unit has the copolymer material of donor-receiver structure, can improve on the one hand the stability of material, can reduce on the other hand the band gap of material, thereby expand sunlight absorption region, improve electricity conversion;

2, provided by the inventionly cough up and two (diazosulfide) multipolymer contains new thiophene and coughs up and two (diazosulfide) conjugate unit containing selenophen-thiophene, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and can improve by introducing alkyl solvability and the molecular weight of multipolymer, be conducive to film forming processing, and preparation method is simply ripe;

3, reaction conditions mild condition, be easy to control, and productive rate is high.

Brief description of the drawings

Fig. 1 is the structural representation of the polymer solar cell device in 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 coughs up and two (diazosulfide) multipolymer containing selenophen-thiophene, for thering is the copolymer p of following general formula:

In formula: R ₁, R ₂, R ₃for C ₁~ C ₂₀alkyl, n is the integer between 1 ~ 100.

Embodiment 1

A kind of selenophen-thiophene that contains is coughed up also two (diazosulfide) multipolymer, and poly-{ 3-octyl group selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (n=45), are designated as copolymer p 1, and structural formula is as follows:

Preparation method comprises the following steps:

(1), 4,9-bis-is bromo-6,7-dioctyl-benzo [2,1-e:3,4-e] two (diazosulfide) preparation method (A1) comprises following operation steps:

(1) prepare compound 5-nitro-2,1,3 diazosulfide, reaction formula is:

In there-necked flask, add 4-oil of mirbane-1,2-diamines (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, after heating in 80 ~ 90 DEG C of back flow reaction 24h, stopped reaction, being heated to 80 DEG C revolves and steams after excessive thionyl chloride, reaction product is cooled to room temperature, in the large water gaging of impouring, stirs, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.

(2) prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide, reaction formula is:

In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and the massfraction Hydrogen bromide 15ml that is 40%, be warming up to 127 DEG C of backflows, in 30min, slowly drip bromine 11.3ml the 4h that refluxes, heat filtering, refilters after filtrate is cooling, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide 10.2g, productive rate 50%.

(3) prepare 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:

In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF (DMF) of 90ml, was heated to 120 DEG C of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate is used saturated sodium-chloride water solution and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, use dehydrated alcohol recrystallization, obtain product 4,4 '-bis-bromo-6,6 '-dinitrobenzene- Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.

(4) prepare 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:

In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran THF that 300ml is dry, add 40g tindichloride (SnCl ₂) (200mmol), be warming up to 100 DEG C, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtain solid crude product, be put in there-necked flask, add the hydrochloric acid (amount of substance of HCl is 21.7mmol) of 58ml, in 30 minutes, the amount of substance of agitation and dropping sodium nitrite solution 20ml(Sodium Nitrite is 37.7mmol), temperature is controlled at below 5 DEG C, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g is that 0.373mol potassiumiodide adds 100ml water dissolution to obtain liquor kalii iodide) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, carry out silica gel column chromatography separation taking sherwood oil as elutriant, then carry out recrystallization with methyl alcohol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.

(5) provide structural formula suc as formula the Compound C 1 shown in C1, i.e. dioctyl dichlorosilane;

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50ml DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.015mol) of 6.0mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, and stirring reaction 2 hours at-90 DEG C, adds 4.73ml Compound C 1(10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, carry out silica gel column chromatography separation taking sherwood oil as elutriant to distilling rear surplus materials, obtain 4.43g product 4,8-bis-is bromo-6, and 6-dioctyl thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A1), productive rate 65%, reaction formula is:

The structured testing data of compd A 1 are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.08（d，2H），1.30-1.42（m，28H）,0.93（d，6H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：160.3,155.8,140.0,136.3,134.2,114.5,33.0,31.8,29.5,24.0,22.6,14.2,13.6。

(2), 3-octyl group-2, the preparation method of 5-bis-(tributyl tin) selenophen (B1) comprises the following steps:

Provide Compound D 1, i.e. 3-octyl group-2,5-dibromo selenophen;

Under the protection of nitrogen, in there-necked flask, add Compound D 1 (6.02g, 0.015mol) with 60ml tetrahydrofuran (THF), under-78 DEG C of conditions, slowly inject the hexane solution (12.0mL of n-Butyl Lithium with syringe, 2.5M, 0.03mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (8.4mL with syringe, 0.03mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours, in there-necked flask, add saturated sodium-chloride water solution 30ml termination reaction, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate to be dried, after suction filtration by filtrate collection and revolve and evaporate ether, obtain crude product, normal hexane/methylene dichloride the mixed solvent that is 9:1 by volume ratio is elutriant, crude product is carried out to separating-purifying with neutral alumina chromatography column, obtain product 3-octyl group-2, 5-bis-(tributyl tin) selenophen (B1), productive rate 72%, reaction formula is:

(3), (P1), reaction formula is in preparation poly-{ 3-octyl group selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection; compound B-11 (the 164.2mg that adds step (two) to prepare in round-bottomed flask; compd A 1 (the 136.2mg that 0.2mmol), step () prepares; 0.2mmol) with tetrahydrofuran (THF) 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₂cl ₂(7.13 × 10 ^-3mmol), be heated to 90 DEG C of reaction 72h.

After reaction finishes, add deionized water and toluene to extract to round-bottomed flask, take out organic phase, underpressure distillation is to about 5ml, splash in 400ml dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, carry out silica gel column chromatography separation taking toluene as elutriant, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3-octyl group selenophen-6, 6 dioctyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P1).

Gained poly-{ 3-octyl group selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P1) is carried out to gel chromatography (GPC) test, record number-average molecular weight=35640, n=45, polymkeric substance monodispersity coefficient is 2.2.

Embodiment 2

A kind of selenophen-thiophene that contains is coughed up also two (diazosulfide) multipolymer, and poly-{ 3-methyl selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (n=28), are designated as copolymer p 2, and structural formula is as follows:

Preparation method comprises the following steps:

(1), 6,6-dioctyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) preparation (A1):

Concrete operations are with embodiment 1 step ().

(2), 3-methyl-2, the preparation method of 5-bis-(tributyl tin) selenophen (B2) comprises the following steps:

Provide structural formula suc as formula the Compound D 2 shown in D2, i.e. 3-methyl-2,5-dibromo selenophen;

Under the protection of nitrogen, in there-necked flask, add Compound D 2 (3.03g, 0.01mol), add the tetrahydrofuran (THF) of 30ml, under-78 DEG C of conditions, slowly inject the hexane solution (8.0mL of n-Butyl Lithium with syringe, 2.5M, 0.02mol), continue stirring reaction 1.5h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours, reacted reaction solution adds termination reaction in 30ml saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulphate layer is dry, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, normal hexane/methylene dichloride the mixed solvent that is 9:1 by volume ratio is elutriant, crude product is carried out to neutral alumina column chromatography for separation, obtain 3-methyl-2, 5-bis-(tributyl tin) selenophen (B2), productive rate 70%, reaction formula is:

(3), poly-{ 3-methyl selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P2) comprises the following steps:

Under argon shield; to the compd B 2 (144.6mg that add step (two) to prepare in round-bottomed flask; compd A 1 (the 136.2mg that 0.2mmol), prepared by step (); 0.2mmol) with glycol dimethyl ether 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh ₃) ₄(4.33 × 10 ^-3mmol), be heated to 90 DEG C of reaction 72h.

After reaction, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 6ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out the separation of neutral alumina chromatography column with toluene, chromatographic solution underpressure distillation is removed to organic solvent, with suction filtration after methyl alcohol sedimentation, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3-methyl selenophen-6, 6 dioctyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P2), reaction formula is as follows:

Poly-{ 3-methyl selenophen-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P2) are carried out to gel chromatography (GPC) test, record number-average molecular weight Mn=19432, n=28, monodispersity coefficient is 2.3.

Embodiment 3

A kind of selenophen-thiophene that contains is coughed up also two (diazosulfide) multipolymer, and poly-{ 3-NSC 62789 base selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (n=32), are designated as copolymer p 3, and structural formula is as follows:

Preparation method comprises the following steps:

(1), 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) preparation method (A2) and is comprised following operation steps:

Prepare 4 according to (1) of embodiment 1 step ()-(4) step, 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

Provide structural formula suc as formula the Compound C 2 shown in C2, i.e. dimethyldichlorosilane(DMCS).

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50ml DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.01mol) of 4.0mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, and at-90 DEG C, stirring reaction 2 hours, adds 10mmol Compound C 2, rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, carry out silica gel column chromatography separation taking sherwood oil as elutriant to distilling rear surplus materials, obtain 3.38g product 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A2), productive rate 70%, reaction formula is:

The structured testing data of compd A 2 are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.08（d，2H），0.68（d，6H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：160.3,155.8,140.0,136.3,134.2,114.5,-1.8。

(2), 3-NSC 62789 base-2, the preparation method of 5-bis-(tributyl tin) selenophen (B3) comprises the following steps:

Provide structural formula suc as formula the compound d3 shown in D3, i.e. 3-NSC 62789 base-2,5-dibromo selenophen;

Under the protection of nitrogen, in there-necked flask, add Compound D 2 (5.75g, 0.01mol), add the tetrahydrofuran (THF) of 60ml, under-78 DEG C of conditions, slowly inject the hexane solution (8.0mL of n-Butyl Lithium with syringe, 2.5M, 0.02mol), continue stirring reaction 1h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours, reacted reaction solution adds termination reaction in 30ml saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulphate layer is dry, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, normal hexane/methylene dichloride the mixed solvent that is 9:1 by volume ratio is elutriant, crude product is carried out to neutral alumina column chromatography for separation, obtain 3-NSC 62789 base-2, 5-bis-(tributyl tin) selenophen (B3), productive rate 55%, reaction formula is:

(3) poly-{ 3-NSC 62789 base selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P3) comprises the following steps:

Under nitrogen protection; to the compd B 3 (198mg, 0.2mmol) that adds in round-bottomed flask step (two) to prepare, compd A 2 (96.8mg, 0.2mmol) and toluene 40ml prepared by step (); vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd ₂(dba) ₃(5.46 × 10 ^-3mmol), be heated to 90 DEG C of reaction 72h.

After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out the separation of neutral alumina chromatography column with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3-NSC 62789 base selenophen-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P3), reaction formula is as follows:

Poly-{ 3-NSC 62789 base selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P3) are carried out to gel chromatography (GPC) test, record number-average molecular weight Mn=24488, n=32, monodispersity coefficient is 2.3.

Embodiment 4

A kind of cough up and two (diazosulfide) multipolymer containing selenophen-thiophene, poly-3-NSC 62789 base selenophen-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) } (n=100), be designated as copolymer p 4, structural formula is as follows:

(1), 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) preparation method (A3) and is comprised following operation steps:

Prepare 4 according to (1) of embodiment 1 step ()-(4) step, 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

Provide structural formula suc as formula the Compound C 3 shown in C3, i.e. two (NSC 62789 base) dichlorosilane.

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50ml DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.0195mol) of 7.8mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, stirring reaction 2 hours at-90 DEG C, add Compound C 3(6.62g, 10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, normal hexane/methylene dichloride mixed solvent taking volume ratio as 10:1 carries out silica gel column chromatography separation to distilling rear surplus materials as elutriant, obtain 2.79g product 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A3), productive rate 55%, reaction formula is:

The structured testing data of compound A-13 are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.08（d，2H），1.47（d，4H），1.27-1.35（m，72H?）0.95（d，6H?）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：160.3,155.8,140.0,136.3,134.2,114.5,33.0，31.8，29.6，29.3，24.0，22.9，14.0，13.7。

(2), 3-NSC 62789 base-2, the preparation method of 5-bis-(tributyl tin) selenophen (B3):

Concrete steps are with embodiment 3 steps (two).

(3), poly-{ 3-NSC 62789 base selenophen-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P4) comprises following operation steps:

Under nitrogen protection; compd B 3 (the 297mg that add step (two) to prepare in round-bottomed flask; compound A-13 (the 203.4mg that 0.3mmol), prepared by step (); 0.2mmol) with benzene 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 28.04mg Pd (PPh ₃) ₂cl ₂(0.04mmol), be heated to 120 DEG C of reaction 100h.After reaction finishes, add deionized water and toluene to extract to round-bottomed flask, take out organic phase, underpressure distillation is to about 5ml, splash in 400ml dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, dissolve with chloroform, be that elutriant carries out the separation of neutral alumina chromatography column with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain poly-{ 3-NSC 62789 base selenophen-6 of product, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P4), reaction formula is:

Gained is gathered 3-NSC 62789 base selenophen-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfides) } (P4) carry out gel chromatography (GPC) test, number-average molecular weight=129700, n=100, monodispersity coefficient is 4.2.

Embodiment 5

A kind of selenophen-thiophene that contains is coughed up also two (diazosulfide) multipolymer, and poly-{ 3-methyl selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (n=1), are designated as copolymer p 5, and structural formula is as follows:

Preparation method comprises the following steps:

(1), preparation 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) (A2):

Concrete operation step is with the step in embodiment 3 (one).

(2), prepare 3-methyl-2,5-bis-(tributyl tin) selenophen (B2):

Concrete operation step is with the step in embodiment 2 (two).

(3) poly-{ 3-methyl selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P5) comprises the following steps:

Under nitrogen protection; to the compd B 2 (144.6mg that add step (two) to prepare in round-bottomed flask; compd A 2 (the 145.2mg that 0.2mmol), prepared by step (); 0.3mmol) with tetrahydrofuran (THF) 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 1.05mg Pd (PPh ₃) ₂cl ₂(1.5 × 10 ^-3mmol), be heated to 50 DEG C of reaction 6h.

After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out the separation of neutral alumina chromatography column with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3-methyl selenophen-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P5), reaction formula is as follows:

Poly-{ 3-methyl selenophen-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P5) are carried out to gel chromatography (GPC) test, record number-average molecular weight Mn=498, n=1.

Embodiment 6

Prepare taking the embodiment of the present invention containing selenophen-thiophene cough up and two (diazosulfide) multipolymer be active coating, prepare polymer solar cell device, comprise the substrate of glass 1 stacking gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, see Fig. 1.Wherein, anode 2 for square resistance be the tin indium oxide ITO of 10 Ω/mouths, the material of middle supplementary layer 3 is for gathering (3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) matrix material (PEDOT:PSS, trade name is CLEVIOS P VPAl 4083); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor material is that the selenophen-thiophene that contains prepared by the embodiment of the present invention is coughed up also two (diazosulfide) multipolymer, electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (PCBM); The material of negative electrode 5 is aluminium.

Wherein, substrate of glass 1, as bottom, can be chosen ito glass,, can buy as anode 2 with ITO layer, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen plasma (oxygen-Plasma) processing; Then on ito glass, apply PEDOT:PSS, supplementary layer 3 in the middle of obtaining, thickness is 120nm; Prepared by the 10mg embodiment of the present invention coughs up and two (diazosulfide) multipolymer is dissolved in 0.4ml dimethylbenzene and obtains solution 1 containing selenophen-thiophene, 8mg PCBM is dissolved in 0.4ml chlorobenzene and obtains solution 2, in the middle of being spun on after solution 1 and solution 2 are mixed on supplementary layer, obtain active coating 4, thickness is 150nm; At vacuum condition (2 × 10 ^-3pa) lower AM aluminum metallization obtains negative electrode 5, and thickness is 120nm, obtains polymer solar cell device.Contain that the present invention coughs up containing selenophen-thiophene and preparation method and the structure of the polymer solar cell device of two (diazosulfide) multipolymer are not limited to the present embodiment, can device suitably be improved or be modified.

Taking embodiment 1,2 and 3 preparation containing selenophen-thiophene cough up and two (diazosulfide) copolymer p 1, P2, P3 as example, it is prepared to polymer solar cell device as stated above as the material of active coating respectively, obtain device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.

By the I-E characteristic of Keithley236 current/voltage source-measuring system and test polymer solar cell device, obtain performance data in table 1.

Table 1 is coughed up and the performance data of the polymer solar cell device that two (diazosulfide) multipolymer is prepared as active coating containing selenophen-thiophene taking of the present invention

As seen from the data in Table 1, taking the energy conversion efficiency of coughing up the polymer solar cell device that also two (diazosulfide) multipolymer is prepared as active coating containing selenophen-thiophene of the present invention as 0.91 ~ 1.31.Show of the present inventionly to cough up and two (diazosulfide) multipolymer contains new thiophene and coughs up and two (diazosulfide) unit containing selenophen-thiophene, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, 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.

The above 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.

Claims (9)

1. cough up and two (diazosulfide) multipolymer containing selenophen-thiophene, it is characterized in that, for thering is the compound P of following general formula:

In formula, R ₁, R ₂, R ₃for C ₁~ C ₂₀alkyl, n is the integer between 1 ~ 100.

2. cough up the also preparation method of two (diazosulfide) multipolymer containing selenophen-thiophene, it is characterized in that, comprise following operation steps:

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

In formula, R ₁, R ₂, R ₃for C ₁~ C ₂₀alkyl;

In atmosphere of inert gases, 1:1.5 ~ 1.5:1 is dissolved in described compd A and compd B in organic solvent in molar ratio, add catalyzer, at 50 DEG C ~ 120 DEG C, carry out Stille coupling reaction 6 ~ 100 hours, after separation and purification, obtain coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene, describedly cough up and two (diazosulfide) multipolymer is the compound P with following general formula containing selenophen-thiophene:

In formula, n is the integer between 1 ~ 100.

3. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the preparation method of described compd A comprises following operation steps:

(1) 4-oil of mirbane-1,2-diamines reacts with thionyl chloride and pyridine, and separate and obtain 5-nitro-2,1,3 diazosulfide, reaction formula is:

Described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/L, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 DEG C, and the time is 24h;

(2) 5-nitro-2,1,3 diazosulfide and Hydrogen bromide and bromine generation bromination reaction, obtain the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide, reaction formula is:

Described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides are 4:1mol/L with hydrobromic molecular volume ratio, described 5-nitro-2,1,3 diazosulfides: the molecular volume of bromine is than being 5.3:1mol/L, and described temperature of reaction is 127 DEG C, and the reaction times is 4h;

(3) by bromo-4,7-bis-5-nitro-2, there is linked reaction in 1,3 diazosulfide under copper powder catalysis, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:

Described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 DEG C, the reaction times is 3 hours;

(4) 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides, after tindichloride is reduced to amino, carries out diazotization reaction with Sodium Nitrite under the condition existing, then react with potassiumiodide at hydrochloric acid, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:

Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1:10, the temperature of described reduction reaction is 100 DEG C, the time is 10h; Described 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: in hydrochloric acid, the mol ratio of hydrogenchloride is 0.92:1,4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: the mol ratio of Sodium Nitrite is 0.53:1, the temperature of described diazotization reaction is below 5 DEG C, the time is 30min; Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of potassiumiodide is 0.054:1, the described time of reacting with potassiumiodide is 12h;

(5) provide suc as formula the Compound C shown in C, wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl;

In solvent dimethylformamide and under oxygen free condition, at-90 DEG C, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides react with n-Butyl Lithium, then at room temperature react with Compound C, obtain compd A, and reaction formula is:

Described n-Butyl Lithium and 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1, the mol ratio of 3 diazosulfides is x, 2≤x ﹤ 4, described Compound C and 4,4 '-bis-bromo-6, the mol ratio of 6 '-bis-iodo-2,1,3 diazosulfides is 2:1, the described time of reacting with n-Butyl Lithium is 2h, and the described time of reacting with Compound C is 10h.

4. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the preparation method of compd B comprises following operation steps:

Compound D is provided, wherein, R ₃for C ₁~ C ₂₀alkyl:

Under protection of inert gas, Compound D is added in tetrahydrofuran (THF), be cooled to-78 DEG C; under-78 DEG C of conditions, add n-Butyl Lithium; Compound D: the mol ratio of n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2h adds tributyltin chloride under-78 DEG C of conditions; Compound D: the mol ratio of tributyltin chloride is 1:2; at-78 DEG C, react 1 hour, be then warming up to room temperature, react 6 hours; after separating-purifying, obtain compd B, reaction formula is:

5. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described catalyzer is the one in three (dibenzalacetone) two palladiums, two (triphenylphosphine) palladium chlorides and tetrakis triphenylphosphine palladium.

6. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the mole dosage of described catalyzer is 0.5% ~ 20% of compd A mole dosage.

7. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described organic solvent is the one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene.

8. selenophen-the thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, being operating as of described separation and purification: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, taking toluene as elutriant, separate with neutral alumina chromatography column, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain coughing up and two (diazosulfide) multipolymer containing selenophen-thiophene.

9. as claimed in claim 1ly cough up and the application of two (diazosulfide) multipolymer containing selenophen-thiophene, it is characterized in that, described containing selenophen-thiophene cough up and two (diazosulfide) multipolymer for the preparation of polymer solar battery.

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