CN103833988A - Anthracene-silolo-di(benzothiadiazole)-containing copolymer as well as preparation method and application thereof - Google Patents

Abstract

The invention relates to an anthracene-silolo-di(benzothiadiazole)-containing copolymer as well as a preparation method and application thereof. The copolymer has a following structural formula (described in the description), wherein n represents an integer of 1-100, and R1 and R2 represent C1-C20 alkyl, R3 and R4 represent H, C1-C20 alkyl or C1-C20 alkoxy. The copolymer has a very strong donor- receptor structure which is helpful to improve the stability of the anthracene-silolo-di(benzothiadiazole)-containing copolymer on the other hand and reduce the energy band gap of the anthracene-silolo-di(benzothiadiazole)-containing copolymer, so that the absorption range of the sunlight is extended, and the photoelectric converting efficiency is increased.

Description

Cough up also two (diazosulfide) multipolymer and its preparation method and application containing anthracene-thiophene

Technical field

The present invention relates to photoelectron material field, particularly relate to a kind of anthracene-thiophene that contains and cough up also two (diazosulfide) multipolymer 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.

Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.But, the band gap (energy level difference between HOMO energy level and lumo energy) of the existing polymkeric substance that contains diazosulfide unit is wider, reduce the specific absorption to photon in solar spectral, thereby made to use the effciency of energy transfer of the organic solar batteries that contains the polymkeric substance that joins thiazole unit lower.

Summary of the invention

Based on this, be necessary to provide a kind of anthracene-thiophene that contains of the effciency of energy transfer that can improve solar cell device to cough up also two (diazosulfide) multipolymer and its preparation method and application.

A kind of anthracene-thiophene that contains is coughed up also two (diazosulfide) multipolymer, has following structural formula:

Wherein, the integer that n is 1 ~ 100; R ₁, R ₂for C ₁~ C ₂₀alkyl; R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

A kind of anthracene-thiophene that contains is coughed up the also preparation method of two (diazosulfide) multipolymer, comprises the steps:

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

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl;

The structural formula of compd B is:

Wherein, R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under anaerobic state, be that 1:1.5 ~ 1.5:1 compd A and compd B carry out Suzuki coupling reaction in the organic solvent of the aqueous solution that contains organic palladium catalyzer and alkali by mol ratio, wherein, the mol ratio of described catalyzer and described compd A is 1:2000 ~ 1:5, in the aqueous solution of described alkali, the molar weight of alkali is compd B 2 ~ 20 times, after separation and purification, obtain coughing up and two (diazosulfide) multipolymer containing anthracene-thiophene, describedly cough up and the general molecular formula of two (diazosulfide) multipolymer is containing anthracene-thiophene:

Wherein, the integer that n is 1 ~ 100.

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

In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column with silica gel, remove chloroform, again use methyl alcohol precipitating, the solid obtaining after filtration is with again using methyl alcohol precipitating after acetone extracting, and the anthracene-thiophene that contains after filtering after dry purification being coughed up also two (diazosulfide) multipolymer.

In a preferred embodiment, the temperature of reaction of described Suzuki coupling reaction is 50 ℃ ~ 120 ℃, and the reaction times is 6 hours ~ 100 hours.

In a preferred embodiment, described organic solvent is selected from least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene, and described alkali is selected from least one in salt of wormwood, cesium carbonate, potassium tert.-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and saleratus.

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

The Compound C and the Compound D that provide following structural formula to represent,

C is:

d is: wherein R ₁, R ₂for C ₁~ C ₂₀alkyl;

Under anaerobic reaction conditions, in Compound C, inject DMF, under-90 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of n-Butyl Lithium and Compound C is x, and then 2≤x ﹤ 4 adds Compound D, after being warmed up to room temperature, react 10 hours, separation and purification obtains described compd A, and wherein, the mol ratio of Compound D and Compound C is 2:1.

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

After reaction finishes, water wash, with anhydrous diethyl ether extraction, by organic layer anhydrous sodium sulfate drying, after filtering, underpressure distillation is except desolventizing, and recycle silicon glue chromatography column separates the compd A after being purified.

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

The compd E and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent,

E is:

f is:

wherein R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under anhydrous and oxygen-free reaction conditions, in compd E, inject tetrahydrofuran solvent, under-78 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of compd E and n-Butyl Lithium is 1:2, then at-78 ℃, slowly injects compound F 17-hydroxy-corticosterone, react after being warmed up to room temperature after 1 hour and react 6 hours, separation and purification obtains described compd B, and wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 2:1.

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

After reaction finishes, add saturated NaCl solution termination reaction, use anhydrous diethyl ether extraction, re-use anhydrous Na ₂sO ₄dry organic phase, collects filtrate after suction filtration, obtain crude product except after desolventizing, described crude product is carried out to silica gel column chromatography separation, the compd B after being purified.

Above-mentioned anthracene-the thiophene that contains is coughed up the also application of two (diazosulfide) multipolymer in solar cell device and organic electroluminescence device.

Above-mentioned anthracene-the thiophene that contains is coughed up also two (diazosulfide) multipolymer and preparation method thereof, compound anthracene and thiophene are coughed up and two (diazosulfides) carry out copolymerization, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, obtain containing anthracene-thiophene cough up and two (diazosulfide) multipolymer there is very strong donor-receiver structure, be conducive to improve on the one hand containing anthracene-thiophene and coughed up the also stability of two (diazosulfide) multipolymer, be conducive on the other hand reduce containing anthracene-thiophene and cough up the also band gap of two (diazosulfide) multipolymer, thereby expand sunlight absorption region, improve electricity conversion.

Accompanying drawing explanation

Fig. 1 is coughing up and two (diazosulfide) multipolymer preparation method schema containing anthracene-thiophene of an embodiment;

Fig. 2 for cough up containing anthracene-thiophene and two (diazosulfide) multipolymer as the structural representation of the organic solar batteries device of active layer material;

Fig. 3 for cough up containing anthracene-thiophene and two (diazosulfide) multipolymer as the structural representation of the organic electroluminescence device of luminescent layer material.

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.

Coughing up and two (diazosulfide) multipolymer containing anthracene-thiophene of one embodiment, has following structural formula:

Wherein, the integer that n is 1 ~ 100; R ₁, R ₂for C ₁~ C ₂₀alkyl; R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

Above-mentioned anthracene-the thiophene that contains is coughed up also two (diazosulfide) multipolymer, compound anthracene and thiophene are coughed up and two (diazosulfides) carry out copolymerization, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, obtain containing anthracene-thiophene cough up and two (diazosulfide) multipolymer there is very strong donor-receiver structure, be conducive to improve on the one hand containing anthracene-thiophene and coughed up the also stability of two (diazosulfide) multipolymer, be conducive on the other hand reduce containing anthracene-thiophene and cough up the also band gap of two (diazosulfide) multipolymer, thereby expand sunlight absorption region, improve electricity conversion.

Refer to Fig. 1, the anthracene-thiophene that contains of an embodiment is coughed up the also preparation method of two (diazosulfide) multipolymer, comprises the steps:

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

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl;

The structural formula of compd B is:

Wherein, R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Step S120, under anaerobic state, be that 1:1.5 ~ 1.5:1 compd A and compd B carry out Suzuki coupling reaction in the organic solvent of the aqueous solution that contains organic palladium catalyzer and alkali by mol ratio, wherein, the mol ratio of catalyzer and compd A is 1:2000 ~ 1:5, in the aqueous solution of alkali, the molar weight of alkali is compd B 2 ~ 20 times, after separation and purification, obtain coughing up and two (diazosulfide) multipolymer containing anthracene-thiophene, cough up and the general molecular formula of two (diazosulfide) multipolymer is containing anthracene-thiophene:

Wherein, the integer that n is 1 ~ 100;

The reaction formula of this step is:

Preferably, Na ₂cO ₃the concentration of the aqueous solution is 2mol/L.

Preferably, organic solvent is selected from least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene.

Preferably, organic palladium catalyzer is selected from 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) at least one.It should be noted that, catalyzer is not limited to above-mentioned several catalyzer, other organic palladium catalyzer also can, if can catalytic cpd A and compd B react.

Preferably, the temperature of reaction of Suzuki coupling reaction is 50 ℃ ~ 120 ℃, and the reaction times is 6 hours ~ 100 hours.

Preferably, alkali is selected from least one in salt of wormwood, cesium carbonate, potassium tert.-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and saleratus.

Preferably, the purification procedures in step S120 is:

In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column with silica gel, remove chloroform, again use methyl alcohol precipitating, the solid obtaining after filtration is with again using methyl alcohol precipitating after acetone extracting, and the anthracene-thiophene that contains after filtering after dry purification being coughed up also two (diazosulfide) multipolymer.

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, the Compound C and the Compound D that provide following structural formula to represent,

C is:

d is:

wherein R ₁, R ₂for C ₁~ C ₂₀alkyl.

Step S112, under anaerobic reaction conditions, in Compound C, inject DMF, under-90 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of n-Butyl Lithium and Compound C is x, and then 2≤x ﹤ 4 adds Compound D, after being warmed up to room temperature, react 10 hours, separation and purification obtains described compd A, and wherein, the mol ratio of Compound D and Compound C is 2:1.

The reaction formula of this step is as follows:

Preferably, in reaction process, in reaction system, pass into nitrogen or argon gas.

Preferably, reaction is carried out under the condition of anhydrous and oxygen-free.

Preferably, the purification procedures in step S112 is:

After reaction finishes, water wash, with anhydrous diethyl ether extraction, by organic layer anhydrous sodium sulfate drying, after filtering, underpressure distillation is except desolventizing, and recycle silicon glue chromatography column separates the compd A after being purified.

Wherein the preparation of Compound C comprises the following steps:

Step 1,2-amino-5-N-methyl-p-nitroaniline is added to thionyl chloride (SOCl ₂) in, drip while stirring pyridine, wherein 2-amino-5-N-methyl-p-nitroaniline is the ratio of 6:1(amount of substance with the solid-to-liquid ratio of pyridine), be heated to afterwards 80 ℃ ~ 90 ℃ back flow reaction 24 hours, remove afterwards excessive thionyl chloride, add deionized water precipitating after cooling, collect dry 5-nitro-2 that obtain of solids wash final vacuum, 1,3 diazosulfide.

The reaction formula of this step is:

Step 2, by 5-nitro-2, 1, after mixing, 3 diazosulfides and hydrobromic acid solution reflux at 127 ℃, to 5-nitro-2, 1, in the mixed solution forming after 3 diazosulfides and hydrobromic acid solution mix, drip bromine, back flow reaction 4 hours, heat filtering afterwards, after filtrate is cooling, refilter, the solid obtaining washes with water rear dry, obtain 4 with Glacial acetic acid and Gossypol recrystallized from chloroform successively again, the bromo-5-of 7-bis-nitro-2, 1, 3 diazosulfides, wherein, hydrobromic mass concentration is 40%, 5-nitro-2, 1, 3 diazosulfides and mass concentration are that 40% hydrobromic ratio is 4mol:1L, 5-nitro-2, 1, the ratio of 3 diazosulfides and bromine is 60mol:11.3L.

The reaction formula of this step is:

Step 3, be 102:95 by mass ratio 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfides and copper powder add DMF (DMF), react 3 hours at 120 ℃, after reaction solution is cooling, add toluene agitation and filtration, the aqueous solution and water washing by filtrate with saturated sodium-chlor, merge organic phase, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide.

The reaction formula of this step is:

Preferably, the bromo-5-of 4,7-bis-nitro-2, the solid-to-liquid ratio of 1,3 diazosulfide and DMF is 1mol:3L, the volume ratio of DMF and toluene is 1:1.

Step 4, to be 1:10 by mol ratio 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfide and SnCl ₂add tetrahydrofuran (THF) (THF), be warming up to 100 ℃, back flow reaction 10 hours, cooling rear use sodium hydroxide solution is adjusted to 8 by the pH value of reaction solution, use afterwards anhydrous diethyl ether extraction, the organic solvent of collecting organic phase and remove wherein obtains solid crude product, after solid crude product and mixed in hydrochloric acid, drip sodium nitrite solution, carry out below diazotization reaction 30 minutes at 5 ℃, reaction solution is added dropwise in liquor kalii iodide, vigorous stirring reaction 12 hours, then with sodium hydroxide solution, the pH value of reaction solution is adjusted to 7, extract with anhydrous diethyl ether, collect organic phase after washing, filter, remove afterwards the organic solvent in filtrate, separate with silica gel column chromatography, obtain Compound C (4 by recrystallizing methanol again, 4 '-bis-bromo-6, 6 '-bis-iodo-2, 1, 3 diazosulfides):

Preferably, 4,4 '-bis-bromo-6, the mol ratio of 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides and hydrochloric acid is 20:21.7,4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2, the mol ratio of 1,3 diazosulfide and Sodium Nitrite is 20:37.7,4,4 '-bis-bromo-6, the mass ratio of 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides and potassiumiodide is 10.3:62.

In step S111, compd B can be by being purchased or preparing.Preferably, described compd B is adopted preparation with the following method:

Step S121, the compd E and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent,

E is:

f is:

wherein R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

Step S122, under anhydrous and oxygen-free reaction conditions, in compd E, inject tetrahydrofuran solvent, under-78 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of compd E and n-Butyl Lithium is 1:2, then at-78 ℃, slowly injects compound F 17-hydroxy-corticosterone, react after being warmed up to room temperature after 1 hour and react 6 hours, separation and purification obtains described compd B, and wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 2:1.

The reaction formula of this step is:

In step S122, the step that separation and purification obtains compd B is:

After reaction finishes, add saturated NaCl solution termination reaction, use anhydrous diethyl ether extraction, re-use anhydrous Na ₂sO ₄dry organic phase, collects filtrate after suction filtration, obtain crude product except after desolventizing, described crude product is carried out to silica gel column chromatography separation, the compd B after being purified.

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 1,4, the preparation 1 of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, 5-nitro-2, the preparation of 1,3 diazosulfide:

In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, after heating, in 80 ~ 90 ℃ of back flow reaction 24h, stopped reaction, is heated to 80 ℃ and revolves and steam excessive SOCl ₂after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.

2,4, the bromo-5-of 7-bis-nitro-2, the preparation of 1,3 diazosulfide:

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

3,4,4 '-bis-is bromo-6, the preparation of 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides:

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 ℃ of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.

4,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides:

In there-necked flask, add 4, 4 '-bis-bromo-6, 6 '-dinitrobenzene-Lian 2, 1, 3 diazosulfide (10.3g, 20mmol), add the tetrahydrofuran (THF) that 300ml is dry (THF), add 40g SnCl2 (200mmol), be warming up to 100 ℃, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolve and steam gained organic layer, obtain solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20ml(37.7mmol in 30 minutes), temperature is controlled at below 5 ℃, it is yellow that solution is, after dropwising, react 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide+100ml water) 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, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.

Step 2,4,8-bis-is bromo-6, and 6-dioctyl-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides):

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), 50ml DMF, passes into nitrogen gas stirring 20min, slowly drips n-Butyl Lithium (6mL, 2.5M, 0.015mol), half hour, drips off, controlling temperature is-90 ℃, remains at-90 ℃ and stirs 2 hours, adds 4.73ml dioctyl dichlorosilane (10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 4.43g product 4,8-bis-bromo-6,6-dioctyl-thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), productive rate 65%.

Step 3,2,6-dioctyl-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-dioctyl-9; 10-dibromoanthracene (5.60g, 0.01mol), adds the tetrahydrofuran solvent of 60ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL with syringe again; 2.5M, 0.02mol), continue stirring reaction 2h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 92%.

Step 4, poly-the preparation of { 2,6-dioctyl anthracene-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 2,6-dioctyl-9; 10-bis-(4,4,5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (131mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and toluene 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (5mg, 0.0043mmol) Pd (PPh ₃) ₄, 1ml Na ₂cO ₃(2M, 2mmol), is heated to 90 ℃ of reaction 90h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P1) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 52360, n=55, polymkeric substance monodispersity is 2.6.

Embodiment 2

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

The preparation process of P2 is as follows:

Step 1,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With the step 1 of embodiment 1.

Step 2,4,8-bis-is bromo-6, and 6-dioctyl-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides)

With the step 2 of embodiment 1.

Step 3,2,6-bis-octyloxy-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-bis-octyloxy-9; 10-dibromoanthracene (5.92g, 0.01mol), adds the tetrahydrofuran solvent of 60ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL with syringe again; 2.5M, 0.02mol), continue stirring reaction 2h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 93%.

The preparation of step 4, poly-{ 2,6-, bis-octyloxy anthracene-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 2,6-, bis-octyloxy-9; 10-bis-(4,4,5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (137.4mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and tetrahydrofuran (THF) 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (5mg, 0.0043mmol) Pd (PPh ₃) ₄, 1ml K ₂cO ₃(2M, 2mmol), is heated to 100 ℃ of reaction 24h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P2) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 48216, n=49, polymkeric substance monodispersity is 2.5.

Embodiment 3

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

Step 1,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With the step 1 of embodiment 1.

Step 2,4,8-bis-is bromo-6, and 6-dimethyl-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides):

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), 50ml DMF, passes into nitrogen gas stirring 20min, slowly drips n-Butyl Lithium (4mL, 2.5M, 0.01mol), half hour, drips off, controlling temperature is-90 ℃, remains at-90 ℃ and stirs 2 hours, adds 4.73ml dimethyldichlorosilane(DMCS) (10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 3.38g product 4,8-bis-bromo-6,6-dimethyl-thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), productive rate 70%.

Step 3,2,6-bis-(NSC 62789 oxygen base)-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-bis-(NSC 62789 oxygen base)-9; 10-dibromoanthracene (9.29g, 0.01mol), adds the tetrahydrofuran solvent of 100ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (15.2mL with syringe again; 2.5M, 0.38mol), continue stirring reaction 1.5h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 94%.

The preparation of step 4, poly-{ 2,6-bis-(NSC 62789 oxygen base) anthracene-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 2,6-bis-(NSC 62789 oxygen base)-9; 10-bis-(4,4,5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (204.6mg; 0.2mmol), 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (96.8mg, 0.2mmol) and glycol dinitrate ether solvents 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (5mg, 0.0055mmol) Pd ₂(dba) ₃, 1ml Cs ₂cO ₃(2M, 2mmol), is heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance (P3) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 28100, n=25, polymkeric substance monodispersity is 2.7.

Embodiment 4

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

Step 1,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With the step 1 of embodiment 1.

Step 2,4,8-bis-is bromo-6, and 6-dioctyl-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides)

With the step 2 of embodiment 1.

Step 3,2,6-dimethoxy-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-dimethoxy-9; 10-dibromoanthracene (3.96g, 0.01mol), adds the tetrahydrofuran solvent of 40ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL with syringe again; 2.5M, 0.02mol), continue stirring reaction 1.5h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 80%.

The preparation of step 4, poly-{ 2,6-dimethoxy anthracene-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 2,6-dimethoxy-9; 10-bis-(4,4,5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (98mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and benzene solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (5mg, 0.0071mmol) Pd (PPh ₃) ₂cl ₂, 1ml potassium tert.-butoxide (2M, 2mmol), is heated to 80 ℃ of reaction 48h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 22036, n=28, polymkeric substance monodispersity is 3.2.

Embodiment 5

The open following polymer P 5 of structure of the present embodiment:

Step 1,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is with the step 1 of embodiment 1.

Step 2 ,-4,8-bis-is bromo-6, and 6-bis-(NSC 62789 base) thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides):

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide 5mmol, 50mlDMF, pass into nitrogen gas stirring 20min, slowly drip n-Butyl Lithium (10.9mL, 2.5M, 0.0195mol), half hour, drips off, and controlling temperature is-90 ℃, remain at-90 ℃ and stir 2 hours, add 9.86ml bis-(NSC 62789 base) dichlorosilane (20mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 2.79g product 4,8-bis-bromo-6,6-bis-(NSC 62789 base)-thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), productive rate 55%.

Step 3,9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 9; 10-dibromoanthracene (3.36g; 0.01mol); add the tetrahydrofuran solvent of 40ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (12mL, 2.5M with syringe again; 0.03mol); continue stirring reaction 1.5h, under-78 ℃ of conditions, inject 2-isopropoxy-4,4 with syringe; 5; 5-tetramethyl--1, the assorted oxygen pentaborane (4.3mL of 3,2-bis-; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 80%.

The preparation of step 4, poly-{ anthracene-6,6-bis-(NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 9,10-bis-((4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) anthracene (86mg, 0.2mmol), 6; 6-dioctyl-4,8-dibromo thiophene is coughed up also [3,2-e:4; 5-e] two (diazosulfide) (136.2mg, 0.2mmol) and toluene solvant 40ml, vacuumize deoxygenation and be filled with nitrogen; then add (5mg, 0.0043mmol) Pd (PPh ₃) ₄, 1ml sodium tert-butoxide (2M, 2mmol), is heated to 70 ℃ of reaction 56h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 23408, n=22, polymkeric substance monodispersity is 3.0.

Embodiment 6

The open following polymer P 6 of structure of the present embodiment:

Step 1,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With the step 1 of embodiment 1.

Step 2,4,8-bis-is bromo-6, and 6-bis-(NSC 62789 base)-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides)

With the step 2 of embodiment 5.

Step 3,2,6-bis-(NSC 62789 base)-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-bis-(NSC 62789 base)-9; 10-dibromoanthracene (8.97g, 0.01mol), adds the tetrahydrofuran solvent of 90ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL with syringe again; 2.5M, 0.02mol), continue stirring reaction 1.5h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 90%.

The preparation of step 4, poly-{ 2,6-bis-(NSC 62789 base) anthracene-6,6-bis-(NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection; add 2; 6-bis-(NSC 62789 base)-9; 10-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) anthracene (297.3mg, 0.3mmol), 6; 6-bis-(NSC 62789 base)-4; 8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) (203.4mg; 0.2mmol) with toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (46.16mg, 0.0399mmol) Pd (PPh ₃) ₄, 3ml sodium bicarbonate (2M, 6mmol), is heated to 120 ℃ of reaction 100h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 162500, n=100, polymkeric substance monodispersity is 4.8.

Embodiment 7

The open following polymer P 7 of structure of the present embodiment:

Step 1,, the preparation of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With the step 1 of embodiment 1.

Step 2,4,8-bis-is bromo-6, and 6-dimethyl-thiophene is coughed up also the preparation of [3,2-e:4,5-e] two (diazosulfides)

With the step 2 of embodiment 3.

Step 3,2,6-dimethyl-9, the preparation of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene:

Under the protection of nitrogen; in there-necked flask, add 2; 6-dimethyl-9; 10-dibromoanthracene (3.64g, 0.01mol), adds the tetrahydrofuran solvent of 40ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (16mL with syringe again; 2.5M, 0.04mol), continue stirring reaction 1.5h; under-78 ℃ of conditions, inject 2-isopropoxy-4 with syringe; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane (4.3mL, 0.02mol) of 2-bis-, reacts and after 1 hour, is warming up under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 87%.

The preparation of step 4, poly-{ 2,6-dimethylanthracene-6,6-dimethyl thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) }:

Under nitrogen protection, add 2,6-dimethyl-9; 10-bis-(4,4,5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (91.6mg; 0.2mmol), 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (145.2mg, 0.3mmol) and toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add (0.17mg, 0.000147mmol) Pd (PPh ₃) ₄, 0.2ml saleratus (2M, 0.4mmol), is heated to 50 ℃ of reaction 6h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 559, n=1.

Embodiment 8

Prepare organic solar cell device to cough up also two (diazosulfide) copolymer p containing anthracene-thiophene as active coating 14 electron donor materials, its structure is as Fig. 2.Organic solar batteries device comprises the substrate of glass 11 stacking gradually, anode 12, middle supplementary layer 13, active coating 14 and negative electrode 15.Anode 12 is ITO, is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and middle supplementary layer 13 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, be called for short PEDOT:PSS(CLEVIOS P VP A1 4083); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material is polymkeric substance prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); Negative electrode 15 is aluminium, and this device architecture can briefly be described as its structure and is: glass/ITO/PEDOT:PSS/P:PCBM/Al.

Wherein, substrate of glass 11, as bottom, is chosen ito glass (with anode 12ITO layer, can buy) when making, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then supplementary layer 13 in the middle of applying on ito glass, material is PEDOT:PSS, thickness is 120nm; The multipolymer of again being prepared by the 10mg embodiment of the present invention is dissolved in 0.4ml dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4ml chlorobenzene obtains, and is spun on PEDOT:PSS rete, and thickness is about 100nm, obtains active coating 14; At vacuum condition (2 × 10 ^-3pa) lower evaporation negative electrode 15, material is aluminium, thickness is 120nm, obtains organic solar batteries device.Preparation method and the structure of the organic solar batteries device that contains multipolymer of the present invention are not limited to the present embodiment, can device suitably be improved or be modified.

Adopt aforesaid method to prepare organic solar cell device the multipolymer of embodiment 1 ~ 3 preparation (adopting respectively P1 ~ P3 to replace) respectively.The electrical property of organic solar batteries device, i.e. I-E characteristic, is obtained by Keithley236 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 0.91 ~ 1.31, these show of the present inventionly to cough up and two (diazosulfides) containing anthracene-thiophene } multipolymer coughs up and two (diazosulfide) conjugate unit owing to containing new 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.

Embodiment 9

The copolymer p 1 of preparing take embodiment 1, as luminescent layer material, is prepared with organic electroluminescence devices, and its structure as shown in Figure 3, comprises the glass substrate 21 stacking gradually, transparent anode 22, luminescent layer 23, buffer layer 24 and negative electrode 25.Wherein, transparent anode 22 for square resistance be 10-20 Ω/mouth tin indium oxide (ITO) (150nm), the copolymer p 1(100nm that luminescent layer 23 is prepared for the embodiment of the present invention 1), buffer layer 24 is LiF (1.5nm), negative electrode 25 is metal A l (150nm), the structure of device is: glass/ITO/ copolymer 1/LiF/Al, but the structure of practical devices is not limited to this.

Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 15.6cd/A, and high-high brightness is 1170cd/m ².

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. cough up and two (diazosulfide) multipolymer containing anthracene-thiophene, it is characterized in that thering is following structural formula:

Wherein, the integer that n is 1 ~ 100; R ₁, R ₂for C ₁~ C ₂₀alkyl; R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

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

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

Wherein, R ₁, R ₂for C ₁~ C ₂₀alkyl;

The structural formula of compd B is:

Wherein, R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under anaerobic state, be that 1:1.5 ~ 1.5:1 compd A and compd B carry out Suzuki coupling reaction in the organic solvent of the aqueous solution that contains organic palladium catalyzer and alkali by mol ratio, wherein, the mol ratio of described catalyzer and described compd A is 1:2000 ~ 1:5, in the aqueous solution of described alkali, the molar weight of alkali is compd B 2 ~ 20 times, after separation and purification, obtain coughing up and two (diazosulfide) multipolymer containing anthracene-thiophene, describedly cough up and the general molecular formula of two (diazosulfide) multipolymer is containing anthracene-thiophene:

Wherein, the integer that n is 1 ~ 100.

3. anthracene-the thiophene that contains according to claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the step of described separation and purification is:

In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, after suction filtration, oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column with silica gel, remove chloroform, again use methyl alcohol precipitating, the solid obtaining after filtration is with again using methyl alcohol precipitating after acetone extracting, and the anthracene-thiophene that contains after filtering after dry purification being coughed up also two (diazosulfide) multipolymer.

4. anthracene-the thiophene that contains according to claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the temperature of reaction of described Suzuki coupling reaction is 50 ℃ ~ 120 ℃, and the reaction times is 6 hours ~ 100 hours.

5. anthracene-the thiophene that contains according to claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described organic solvent is selected from least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene, and described alkali is selected from least one in salt of wormwood, cesium carbonate, potassium tert.-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and saleratus.

6. anthracene-the thiophene that contains according to claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described compd A is adopted preparation with the following method:

The Compound C and the Compound D that provide following structural formula to represent, C is:

d is: wherein R ₁, R ₂for C ₁~ C ₂₀alkyl; Under anaerobic reaction conditions, in Compound C, inject DMF, under-90 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of n-Butyl Lithium and Compound C is x, and then 2≤x ﹤ 4 adds Compound D, after being warmed up to room temperature, react 10 hours, separation and purification obtains described compd A, and wherein, the mol ratio of Compound D and Compound C is 2:1.

7. anthracene-the thiophene that contains according to claim 6 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the step that described separation and purification obtains described compd A is:

After reaction finishes, water wash, with anhydrous diethyl ether extraction, by organic layer anhydrous sodium sulfate drying, after filtering, underpressure distillation is except desolventizing, and recycle silicon glue chromatography column separates the compd A after being purified.

8. anthracene-the thiophene that contains according to claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described compd B is adopted preparation with the following method:

The compd E and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent,

E is:

f is:

wherein R ₃, R ₄for H, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under anhydrous and oxygen-free reaction conditions, in compd E, inject tetrahydrofuran solvent, under-78 ° of C, slowly add n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of compd E and n-Butyl Lithium is 1:2, then at-78 ℃, slowly injects compound F 17-hydroxy-corticosterone, react after being warmed up to room temperature after 1 hour and react 6 hours, separation and purification obtains described compd B, and wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 2:1.

9. anthracene-the thiophene that contains according to claim 8 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the step that described separation and purification obtains described compd B is:

After reaction finishes, add saturated NaCl solution termination reaction, use anhydrous diethyl ether extraction, re-use anhydrous Na ₂sO ₄dry organic phase, collects filtrate after suction filtration, obtain crude product except after desolventizing, described crude product is carried out to silica gel column chromatography separation, the compd B after being purified.

10. anthracene-the thiophene that contains as claimed in claim 1 is coughed up the also application of two (diazosulfide) multipolymer in solar cell device and organic electroluminescence device.

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