CN103833978B - Contain also [3,4-b] two thiophene-thiophene to cough up and two (diazosulfide) multipolymer and Synthesis and applications thereof - Google Patents

Contain also [3,4-b] two thiophene-thiophene to cough up and two (diazosulfide) multipolymer and Synthesis and applications thereof Download PDF

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CN103833978B
CN103833978B CN201210490400.6A CN201210490400A CN103833978B CN 103833978 B CN103833978 B CN 103833978B CN 201210490400 A CN201210490400 A CN 201210490400A CN 103833978 B CN103833978 B CN 103833978B
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thiophene
diazosulfide
reaction
multipolymer
diazosulfides
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CN103833978A (en
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周明杰
管榕
黎乃元
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/549—Organic PV cells

Abstract

The invention provides containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer and Synthesis and applications thereof, describedly to cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer is the copolymer p with following general formula, in formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for the integer that H or F, n are between 1 ~ 100.Of the present invention containing also [3,4-b] two thiophene-thiophene is coughed up and two (diazosulfide) multipolymer contains new thiophene coughs up and two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, effciency of energy transfer is improved, and preparation method is simply controlled, has good application prospect in the field of photovoltaic materials such as polymer solar battery, organic electroluminescence device.

Description

Contain also [3,4-b] two thiophene-thiophene to cough up and two (diazosulfide) multipolymer and Synthesis and applications thereof
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of also [3,4-b] two thiophene-thiophene that contains and cough up and 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 of photovoltaic art always.At present business-like silicon solar cell due to complex manufacturing, cost high, application is restricted.In order to reduce costs, expansive approach scope, 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 low in raw material price, quality are light, flexibility, simple, the available coating of production technique, printing such as to prepare at the advantage.Above conjugated polymers and C is reported at SCIENCE (N.SSariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) from N.S.Sariciftci in 1992 etc. 60between Photo-induced electron transfer phenomenon after, people have dropped into large quantity research in polymer solar battery, and achieve development at full speed.
The effciency of energy transfer of current polymer solar battery is still low than silicon solar cell, and one of reason is due to the carrier mobility of polymkeric substance several orders of magnitude lower than the mobility of inorganic monocrystalline material.And the absorption spectrum of the conjugated polymers photocell material used at present can not mate well with solar spectrum, it is another major reason causing energy transfer efficiency low.For improving the performance of polymer solar battery further, the pole narrow band gap polymkeric substance had compared with wide absorption spectrum can be adopted to do to body and acceptor, improve absorbing sun power.
The conjugated polymers containing 1,4-Dithiapentalene unit and diazosulfide unit for photoelectric material appears in the newspapers, but the effciency of energy transfer obtained in actual applications is still lower.Therefore, develop new polymer materials, improve the great significance of effciency of energy transfer for organic solar batteries of photoelectric material.
Summary of the invention
For solving the problem, the present invention aims to provide a kind of also [3,4-b] two thiophene-thiophene that contains and coughs up and two (diazosulfide) multipolymer.
The present invention also aims to provide and contain preparation method and the application that also [3,4-b] two thiophene-thiophene coughs up also two (diazosulfide) multipolymer.
First aspect, the invention provides a kind of also [3,4-b] two thiophene-thiophene that contains and coughs up and two (diazosulfide) multipolymer, for having the copolymer p of following general formula:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for the integer that H or F, n are between 1 ~ 100.
Provided by the invention containing also [3,4-b] two thiophene-thiophene coughs up and to cough up and two (diazosulfide) unit containing new thiophene in the structure of two (diazosulfide) multipolymer, diazosulfide unit is common functional unit, there is excellent reduction reversibility, close 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, excellent in body unit, there is good electronic transport property, can also regulate the energy gap of material, and thiophene is coughed up in structural unit and be there is 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 also [3,4-b] two thiophene-thiophene is coughed up and in two (diazosulfide) multipolymer, the new thiophene that contains is coughed 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 have excellent electronic transmission performance, can be applicable to the fields such as organic solar batteries.
Simultaneously, and [3,4-b] two thiophene have good electronics bulk property, polymkeric substance can be made to have higher carrier mobility as polymkeric substance component units, and also [3,4-b] two thiophene unit can form quinonoid structure, functional group can be introduced at main chain to modify, thus change also [3,4-b] two band gap of thiophene unit and polymkeric substance, in the photoelectric materials such as this unit widespread use at present and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
The present invention obtain having on the basis of above two kinds of unit novel planar conjugated structure containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, there is excellent carrier mobility ability and configuration flexibility, have a extensive future.
Second aspect, the invention provides and cough up and the preparation method of two (diazosulfide) multipolymer containing also [3,4-b] two thiophene-thiophene, comprise following operation steps:
There is provided compd A and compd B, the structural formula of compd A and B is respectively:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for H or F;
In atmosphere of inert gases, described compd A and compd B are dissolved in organic solvent by 1:1.5 ~ 1.5:1 in molar ratio, add catalyzer, Stille coupling reaction is carried out 6 ~ 100 hours at 50 DEG C ~ 120 DEG C, obtain containing also [3 after separation and purification, 4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, describedly to cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer is the copolymer p with following general formula:
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) or two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2).More preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2).
Preferably, the mole dosage of described catalyzer is 0.5% ~ 20% of the amount of substance of compd A.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described organic solvent is the one in tetrahydrofuran (THF), glycol dimethyl ether, Benzene and Toluene.Described solvent is enough.
Preferably, the operating process of described preparation method is: mixed with compd B and organic solvent by compd A, vacuumize deoxygenation and be filled with rare gas element, add catalyzer, be heated to 50 ~ 120 DEG C, the reaction times is 6 ~ 100 hours, and reaction terminates, obtain containing also [3,4-b] two thiophene-thiophene after separation and purification to cough up and two (diazosulfide) multipolymer.
Preferably, being operating as of described separation and purification: after reaction, deionized water is added and toluene extracts in reaction solution, get organic phase, add after underpressure distillation in dehydrated alcohol, separate out precipitation, suction filtration, pressed powder is obtained after oven dry, after pressed powder being dissolved with chloroform, take toluene as elutriant, be separated with silica gel column chromatography, methyl alcohol sedimentation is used after chromatographic solution underpressure distillation, suction filtration, gained solid acetone extracts three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum filtration spends the night, obtain containing also [3, 4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer.
The preparation method of described compd A comprises following operation steps:
(1), 4-oil of mirbane-1,2-diamines and thionyl chloride and pyridine react, and be separated and 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 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide, reaction formula is:
Preferably, described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides and hydrobromic molecular volume are than being 4:1mol/L, 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), there is linked reaction in 4,7-bis-bromo-5-nitro-2,1,3 diazosulfides under copper powder catalysis, and obtain 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides, reaction formula is:
Preferably, described 4,7-bis-bromo-5-nitro-2,1,3 diazosulfides: the mol ratio of copper powder is 0.2:1, and described temperature of reaction is 120 DEG C, and the reaction times is 3 hours.
(4), 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, the nitro in 3 diazosulfides is through tindichloride (SnCl 2) be reduced to amino after, under hydrochloric acid existent condition, carry out diazotization reaction with Sodium Nitrite, then react with potassiumiodide, obtain 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction formula is:
Preferably, described 4,4 '-two 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, and the time is 10h; Described 4,4 '-two 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 '-two 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 less than 5 DEG C, and the time is 30min; Described 4,4 '-two 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 such 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 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides and n-Butyl Lithium react, and then at room temperature react with Compound C, obtain compd A, reaction formula is:
Preferably, described n-Butyl Lithium and 4,4 '-two bromo-6,6 '-two iodo-2, the mol ratio of 1,3 diazosulfides is x, 2≤x < 4, described Compound C and 4,4 '-two bromo-6,6 '-two iodo-2, the mol ratio of 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 uses the expressions such as compd A 1, A2, A3 respectively, the expressions such as Compound C uses Compound C 1 respectively, C2, C3, and 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 H or C 1~ C 20alkyl, R 4for H or F:
Under protection of inert gas, Compound D is added in tetrahydrofuran (THF) (THF), be cooled to-78 DEG C; n-Butyl Lithium is added under-78 DEG C of conditions; Compound D: the mol ratio of n-Butyl Lithium is 1:2, and 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, react 1 hour at-78 DEG C, be then warming up to room temperature, react 6 hours, obtain compd B after separation, reaction formula is:
Preferably, described rare gas element is nitrogen or argon gas.
In an embodiment, for convenience of statement, compd B uses compound B-11 respectively, the expressions such as B2, B3, B4, and Compound D uses the expressions such as Compound D 1, D2, D3, D4 respectively, and name is all as the criterion with the title in each embodiment.
The third aspect, the invention provides containing also [3,4-b] two thiophene-thiophene coughs up and the application of two (diazosulfide) multipolymer, cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer for the preparation of polymer solar cell device and organic electroluminescence device.Described cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer as described in relation to the first aspect.
One provided by the invention contains also [3,4-b] two thiophene-thiophene and coughs up and two (diazosulfide) multipolymer and preparation method thereof and application, has following beneficial effect:
1, of the present invention containing also [3,4-b] two thiophene-thiophene cough up and two (diazosulfide) multipolymer in, thiophene is coughed up and two (diazosulfide) unit has the advantages such as structure is simple, symmetrical, electron delocalization performance is good, and be two dimensional structure, it is a kind of very excellent donor material, with also [3,4-b] two thiophene units combine to be formed has the copolymer material of donor-receiver structure, the stability of material can be improved on the one hand, the band gap of material can be reduced on the other hand, thus expand sunlight absorption region, improve electricity conversion;
2, provided by the invention containing also [3,4-b] two thiophene-thiophene is coughed up and two (diazosulfide) multipolymer contains new thiophene coughs up and two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, ratio and charge collection efficiency that current carrier arrives electrode can be improved, thus raising effciency of energy transfer, and solvability and the molecular weight of multipolymer is improved by introducing alkyl, be conducive to film forming processing, and preparation method is simply ripe;
3, reaction conditions is gentle, is easy to control, and productive rate is high.
Accompanying drawing explanation
Fig. 1 is the structural representation of polymer solar cell device in embodiment 7.
Fig. 2 is the structural representation of organic electroluminescence device in embodiment 8.
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 also [3, the 4-b] two thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, for having the copolymer p of following general formula:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for the integer that H or F, n are between 1 ~ 100.
Embodiment 1
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, i.e. poly-{ 4-octyl group also [3,4-b] two thiophene-6,6 dioctyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (n=52), be designated as copolymer p 1, structural formula is as follows:
Preparation method comprises the following steps:
(1), the preparation method of 4,9-bis-bromo-6,7-dioctyls-benzo [2,1-e:3,4-e] two (diazosulfide) (A1) comprises following operation steps:
(1) prepare compound 5-nitro-2,1,3 diazosulfide, reaction formula is:
4-oil of mirbane-1,2-diamines (22.95g, 0.15mol) and 100mL thionyl chloride is added in there-necked flask, stir and slowly drip 2mL pyridine, in 80 ~ 90 DEG C of back flow reaction 24h after heating, stopped reaction, be heated to 80 DEG C revolve and steam excessive thionyl chloride after, reaction product is cooled to room temperature, in the large water gaging of impouring, stirs, filter, wash final vacuum drying, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
(2) prepare compound 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide, reaction formula is:
5-nitro-2,1,3 diazosulfide (10.35g is added in there-necked flask, 60mmol) and massfraction be 40% Hydrogen bromide 15mL, be warming up to 127 DEG C of backflows, slowly drip bromine 11.3mL in 30min and the 4h that refluxes, heat filtering, refilters after filtrate cooling, and solid is also dry with a large amount of water washings, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 4, the bromo-5-nitro-2 of 7-bis-, 1,3 diazosulfide 10.2g, productive rate 50%.
(3) prepare 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides, reaction formula is:
The bromo-5-nitro-2,1 of 4,7-bis-is added in there-necked flask, 3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g and 90mLN, dinethylformamide (DMF), is heated to 120 DEG C of reactions after 3 hours, stopped reaction, be cooled to room temperature, add 90mL toluene, stir 30 minutes, filter, filtrate saturated sodium-chloride water solution and water washing, merge organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, use dehydrated alcohol recrystallization, obtain product 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.
(4) prepare 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction formula is:
In there-necked flask, add 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide (10.3g, 20mmol), adds the tetrahydrofuran THF of 300mL drying, adds 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 extracts, and 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, agitation and dropping sodium nitrite solution 20mL (amount of substance of Sodium Nitrite is 37.7mmol) in 30 minutes, temperature controls below 5 DEG C, solution, in yellow, after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide adds 100mL water and obtains liquor kalii iodide), vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer is washed, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, be that elutriant carries out silica gel column chromatography separation with sherwood oil, then carry out recrystallization with methyl alcohol, obtain 4.1g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, productive rate is 30%.
(5) provide structural formula such as formula the Compound C 1 shown in C1, i.e. dioctyl dichlorosilane;
4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 diazosulfide (3.4g, 5mmol) and 50mLDMF, 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, control 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 after washing, obtains organic layer to reaction solution, add anhydrous sodium sulfate drying, filter, underpressure distillation, be that elutriant carries out silica gel column chromatography separation to surplus materials after distillation with sherwood oil, obtain bromo-6, the 6-dioctyl thiophenes of 4.43g product 4,8-bis-and cough up also [3,2-e:4,5-e] two (diazosulfide) (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), 4-octyl group-2,6-bis-(tributyl tin) and [3,4-b] two the preparation method of thiophene (B1) comprise the following steps:
There is provided Compound D 1, i.e. 4-octyl group-2,6-dibromo also [3,4-b] two thiophene;
Under the protection of nitrogen, Compound D 1 (4.1g is added in there-necked flask, 0.01mol) with 50mL tetrahydrofuran (THF), slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe under-78 DEG C of conditions, 0.02mol), continue stirring reaction 2h, tributyltin chloride (5.6mL is injected with syringe under-78 DEG C of conditions, 0.02mol), react and rise to stirring at room temperature after 1 hour and react 6 hours, saturated sodium-chloride water solution 30mL termination reaction is added in there-necked flask, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate and carry out drying, after suction filtration, filtrate collection is revolved and evaporates ether, obtain crude product, be elutriant with sherwood oil, with neutral alumina chromatography column, crude product is carried out separating-purifying, obtain product 4-octyl group-2, 6-bis-(tributyl tin) [3, 4-b] two thiophene (B1), productive rate 68%, reaction formula is:
(3), preparation poly-4-octyl group also [3,4-b] two thiophene-6,6 dioctyl thiophene cough up also [3,2-e:4,5-e] two (diazosulfide) (P1), reaction formula is:
Under nitrogen protection; compound B-11 (the 166.2mg that step (two) prepares is added in round-bottomed flask; 0.2mmol), the compd A 1 (136.2mg for preparing of step (); 0.2mmol) with tetrahydrofuran (THF) 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh 3) 2cl 2(5mg, 7.12 × 10 -3mmol), 90 DEG C of reaction 72h are heated to.
After reaction terminates, deionized water is added and toluene extracts to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, be added dropwise in 400mL dehydrated alcohol and constantly stir, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, pressed powder chloroform is dissolved, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation removing organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, gathered { 4-octyl group also [3, 4-b] two thiophene-6, 6 dioctyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P1).
By poly-for gained { 4-octyl group also [3,4-b] two thiophene-6,6 dioctyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfides) (P1) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=41652, n=52, polymkeric substance monodispersity coefficient is 2.3.
Embodiment 2
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, i.e. poly-{ 4-NSC 62789 base also [3,4-b] two thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (n=28), be designated as copolymer p 2, structural formula is as follows:
Preparation method comprises the following steps:
(1) preparation method that, 6,6-dimethyl-4,8-dibromo thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) (A2) comprises following operation steps:
4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides according to (1)-(4) step of embodiment 1 step ().
There is provided structural formula such as formula the Compound C 2 shown in C2, i.e. dimethyldichlorosilane(DMCS).
4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 diazosulfide (3.4g, 5mmol) and 50mLDMF, 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, control 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 after washing, obtains organic layer to reaction solution, add anhydrous sodium sulfate drying, filter, underpressure distillation, be that elutriant carries out silica gel column chromatography separation to surplus materials after distillation with sherwood oil, obtain 3.38g product 6,6-dimethyl-4,8-dibromo thiophene and cough up also [3,2-e:4,5-e] two (diazosulfide) (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), 4-NSC 62789 base-2,6-bis-(tributyl tin) and [3,4-b] two the preparation method of thiophene (B2) comprise the following steps:
There is provided structural formula such as formula the Compound D 2 shown in D2, i.e. 4-NSC 62789 base-2,6-dibromo also [3,4-b] two thiophene;
Under the protection of nitrogen, Compound D 2 (5.79g is added in there-necked flask, 0.01mol), add the tetrahydrofuran (THF) of 90mL, slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe under-78 DEG C of conditions, 0.02mol), continue stirring reaction 1h, tributyltin chloride (5.6mL is injected with syringe under-78 DEG C of conditions, 0.02mol), react and be warming up to stirred at ambient temperature after 1 hour and react 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, filtrate collection is revolved and evaporates anhydrous diethyl ether, obtain crude product, be elutriant with sherwood oil, crude product is carried out neutral alumina column chromatography for separation, obtain 4-NSC 62789 base-2, 6-bis-(tributyl tin) [3, 4-b] two thiophene (B2), productive rate 70%, reaction formula is:
(3), poly-4-NSC 62789 base also [3,4-b] two thiophene-6,6 dimethyl thiophene cough up also [3,2-e:4,5-e] two (diazosulfide) preparation method of (P2) comprises the following steps:
Under argon shield; compd B 2 (199.8mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compd A 2 (136.2mg for preparing of step (); 0.2mmol) with glycol dimethyl ether 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh 3) 4(5mg, 4.33 × 10 -3mmol), 70 DEG C of reaction 36h are heated to.
After reaction, deionized water is added and toluene extracts in round-bottomed flask, get organic phase, underpressure distillation is to about about 6mL, instilled in 500mL dehydrated alcohol and constantly stirred, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, pressed powder chloroform is dissolved, be that elutriant carries out silica gel column chromatography separation with toluene, by chromatographic solution underpressure distillation removing organic solvent, with suction filtration after methyl alcohol sedimentation, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, gathered { 4-NSC 62789 base also [3, 4-b] two thiophene-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P2), reaction formula is as follows:
To poly-{ 4-NSC 62789 base also [3,4-b] two thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfides) (P2) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=23190, n=28, monodispersity coefficient is 2.7.
Embodiment 3
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, i.e. poly-{ the positive decyl of 4--5-fluorine also [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (n=72), be designated as copolymer p 3, structural formula is as follows:
Preparation method comprises the following steps:
(1), 6,6-bis-(NSC 62789 base)-4,8-the dibromo thiophene preparation method that coughs up also [3,2-e:4,5-e] two (diazosulfide) (A3) comprise following operation steps:
4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides according to (1)-(4) step of embodiment 1 step ().
There is provided structural formula such as formula the Compound C 3 shown in C3, i.e. two (NSC 62789 base) dichlorosilane.
4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 diazosulfide (3.4g, 5mmol) and 50mLDMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.02) of 8.0mL n-Butyl Lithium, within 0.5 hour, drip off, control temperature is-90 DEG C, and stirring reaction 2 hours at-90 DEG C, adds 4.93mL Compound C 3 (10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction after washing, obtains organic layer to reaction solution, add anhydrous sodium sulfate drying, filter, underpressure distillation, with volume ratio be 10:1 normal hexane/methylene dichloride mixed solvent for elutriant to distillation after surplus materials carry out silica gel column chromatography separation, obtain 2.79g product 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene and cough up also [3,2-e:4,5-e] two (diazosulfide) (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), fluoro-2,6-bis-(tributyl tins) of the positive decyl of 4--5-and [3,4-b] two the preparation method of thiophene (B3) comprise the following steps:
There is provided structural formula such as formula the compound d3 shown in D3, i.e. fluoro-2, the 6-dibromos of the positive decyl of 4--5-also [3,4-b] two thiophene;
Under the protection of nitrogen, compound d3 (4.56g is added in there-necked flask, 0.01mol) with 50mL tetrahydrofuran (THF), slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe under-78 DEG C of conditions, 0.02mol), continue stirring reaction 1h, tributyltin chloride (5.6mL is injected with syringe under-78 DEG C of conditions, 0.02mol), react and rise to stirring at room temperature after 1 hour and react 6 hours, saturated sodium-chloride water solution 30mL termination reaction is added in there-necked flask, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate and carry out drying, after suction filtration, filtrate collection is revolved and evaporates ether, obtain crude product, be elutriant with sherwood oil, with neutral alumina chromatography column, crude product is carried out separating-purifying, obtain the positive decyl of product 4--5-fluoro-2, 6-bis-(tributyl tin) [3, 4-b] two thiophene (B3), productive rate 68%, reaction formula is as follows:
(3) preparation method of poly-{ the positive decyl of 4--5-fluorine is [3,4-b] two thiophene-6 also, and 6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (P3) comprises the following steps:
Under nitrogen protection; compd B 3 (175.4mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compound A-13 (203.4mg for preparing of step (); 0.2mmol) with toluene 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd 2(dba) 3(1.16mg, 0.001mmol), is heated to 80 DEG C of reaction 48h.
After reaction terminates, deionized water is added and toluene extracts in round-bottomed flask, get organic phase, underpressure distillation is to about about 5mL, be added dropwise in 400mL dehydrated alcohol and constantly stirred, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, pressed powder chloroform is dissolved, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation removing organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, gathered { the positive decyl of 4--5-fluorine also [3, 4-b] two thiophene-6, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P3), reaction formula is as follows:
To poly-{ the positive decyl of 4--5-fluorine also [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (P3) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=85248, n=72, monodispersity coefficient is 3.8.
Embodiment 4
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, namely gather and [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (n=20), be designated as copolymer p 4, structural formula is as follows:
(1), prepare 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene to cough up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step () in embodiment 3.
(2), 2,6-bis-(tributyl tins) and [3,4-b] two the preparation method of thiophene (B4) comprise the following steps:
There is provided structural formula such as formula the Compound D 4 shown in D4, i.e. 2,6-dibromos also [3,4-b] two thiophene;
Under the protection of nitrogen, Compound D 4 (2.98g is added in there-necked flask, 0.01mol) with 30mL tetrahydrofuran (THF), slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe under-78 DEG C of conditions, 0.02mol), continue stirring reaction 2h, tributyltin chloride (5.6mL is injected with syringe under-78 DEG C of conditions, 0.02mol), react and rise to stirring at room temperature after 1 hour and react 6 hours, saturated sodium-chloride water solution 30mL termination reaction is added in there-necked flask, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate and carry out drying, after suction filtration, filtrate collection is revolved and evaporates ether, obtain crude product, be elutriant with sherwood oil, with neutral alumina chromatography column, crude product is carried out separating-purifying, obtain product 2, 6-bis-(tributyl tin) [3, 4-b] two thiophene (B4), productive rate 50%, reaction formula is as follows:
(3), the preparation method of poly-{ and [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (P4) comprises following operation steps:
Under nitrogen protection; compd B 4 (143.6mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compound A-13 (203.4mg for preparing of step (); 0.2mmol) with benzene 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh 3) 2cl 2(5mg, 7.12 × 10 -3mmol), 90 DEG C of reaction 72h are heated to.
After reaction terminates, deionized water is added and toluene extracts to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, be added dropwise in 400mL dehydrated alcohol and constantly stir, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, dissolve with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation removing organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain product poly-{ and [3, 4-b] two thiophene-6, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P4), reaction formula is:
Gained is gathered and [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (P4) carry out gel chromatography (GPC) test, number-average molecular weight=20520, n=20, monodispersity coefficient is 2.8.
Embodiment 5
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, i.e. poly-{ 4-NSC 62789 base also [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (n=100), be designated as copolymer p 5, structural formula is as follows:
(1), prepare 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene to cough up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step () in embodiment 3.
(2), 4-NSC 62789 base-2,6-bis-(tributyl tin) is prepared and [3,4-b] two thiophene (B2):
Concrete operations are with the step (two) in embodiment 2.
(3), poly-{ 4-NSC 62789 base also [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } preparation method of (P5) comprises following operation steps:
Under nitrogen protection; compd B 2 (299.7mg prepared by step (two) is added in round-bottomed flask; 0.3mmol), the compound A-13 (203.4mg for preparing of step (); 0.2mmol) with tetrahydrofuran (THF) 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh 3) 2cl 2(28.04mg, 3.99 × 10 -2mmol), 120 DEG C of reaction 100h are heated to.
After reaction terminates, deionized water is added and toluene extracts to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, be added dropwise in 400mL dehydrated alcohol and constantly stir, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, dissolve with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation removing organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain poly-{ the 4-NSC 62789 base also [3 of product, 4-b] two thiophene-6, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P5), reaction formula is:
By poly-for gained { 4-NSC 62789 base also [3,4-b] two thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (P5) carry out gel chromatography (GPC) test, number-average molecular weight=130600, n=100, monodispersity coefficient is 5.2.
Embodiment 6
A kind of containing also [3,4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, i.e. poly-{ 4-methyl also [3,4-b] two thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (n=1), be designated as copolymer p 6, structural formula is as follows:
Preparation method comprises the following steps:
(1), prepare 6,6-dimethyl-4,8-dibromo thiophene to cough up also [3,2-e:4,5-e] two (diazosulfide) (A2)
Concrete operations are with the step () in embodiment 2.
(2), 4-methyl-2,6-bis-(tributyl tin) and [3,4-b] two the preparation method of thiophene (B5) comprise the following steps:
There is provided structural formula such as formula the Compound D 5 shown in D5, namely 4,4 '-dimethyl-5,5 '-two bromo-2,2 '-and [3,4-b] two thiophene;
Under the protection of nitrogen, Compound D 5 (3.12g is added in there-necked flask, 0.01mol) with 40mL tetrahydrofuran (THF), slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe under-78 DEG C of conditions, 0.02mol), continue stirring reaction 2h, tributyltin chloride (5.6mL is injected with syringe under-78 DEG C of conditions, 0.02mol), react and rise to stirring at room temperature after 1 hour and react 6 hours, saturated sodium-chloride water solution 30mL termination reaction is added in there-necked flask, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate and carry out drying, after suction filtration, filtrate collection is revolved and evaporates ether, obtain crude product, be elutriant with sherwood oil, with neutral alumina chromatography column, crude product is carried out separating-purifying, obtain product 4-methyl-2, 6-bis-(tributyl tin) [3, 4-b] two thiophene (B5), productive rate 60%, reaction formula is as follows:
(3) poly-4-methyl also [3,4-b] two thiophene-6,6 dimethyl thiophene cough up also [3,2-e:4,5-e] two (diazosulfide) preparation method of (P6) comprises the following steps:
Under nitrogen protection; compd B 5 (146.4mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compd A 2 (145.2mg for preparing of step (); 0.3mmol) with tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh 3) 2cl 2(28.08mg, 0.04mmol), is heated to 50 DEG C of reaction 6h.
After reaction terminates, deionized water is added and toluene extracts in round-bottomed flask, get organic phase, underpressure distillation is to about about 5mL, be added dropwise in 400mL dehydrated alcohol and constantly stirred, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, pressed powder chloroform is dissolved, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation removing organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, gathered { 4-methyl also [3, 4-b] two thiophene-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P6), reaction formula is as follows:
To poly-4-methyl also [3,4-b] two thiophene-6,6 dimethyl thiophene cough up also [3,2-e:4,5-e] two (diazosulfide) (P6) carry out gel chromatography (GPC) test, records number-average molecular weight Mn=507, n=1.
Embodiment 7
With the embodiment of the present invention prepare containing also [3,4-b] two thiophene-thiophene is coughed up and two (diazosulfide) multipolymer is active coating, prepare polymer solar cell device, comprise the substrate of glass 1 stacked 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, sees Fig. 1.Wherein, anode 2 for square resistance be the tin indium oxide (ITO) of 10 Ω/mouth, the material of middle supplementary layer 3 is poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) matrix material, be expressed as PEDOT:PSS (trade name is CLEVIOSPVPAl4083); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor material be the embodiment of the present invention prepare containing also [3,4-b] two thiophene-thiophene coughs up and 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 choose ito glass, and with ITO layer as anode 2, can buy, thickness is 1.1mm, after ultrasonic cleaning, processes with oxygen plasma (oxygen-Plasma); Then on ito glass, apply PEDOT:PSS, obtain middle supplementary layer 3, thickness is 110nm; Prepared by the 10mg embodiment of the present invention containing also [3,4-b] two thiophene-thiophene is coughed up and two (diazosulfide) multipolymer is dissolved in 0.4mL dimethylbenzene, obtain solution 1,8mgPCBM is dissolved in 0.4mL chlorobenzene and obtains solution 2, be spun on middle supplementary layer after solution 1 and solution 2 are mixed, obtain active coating 4, thickness is 150nm; At vacuum condition (2 × 10 -3pa) under, AM aluminum metallization prepares negative electrode 5, and thickness is 120nm, obtains polymer solar cell device.To cough up containing also [3,4-b] two thiophene-thiophene containing the present invention and the preparation method of the polymer solar cell device of two (diazosulfide) multipolymer and structure are not limited to the present embodiment, can suitably improve device or modify.
Respectively with embodiment 1,2 and 3 prepare containing also [3,4-b] two thiophene-thiophene is coughed up and two (diazosulfide) copolymer p 1, P2, P3 prepare polymer solar cell device as stated above as the material of active coating, obtain device 1,2 and 3, all preparation process are all carried out in the glove box providing nitrogen inert atmosphere.
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 to be coughed up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer is the performance data of polymer solar cell device prepared by active coating with of the present invention
As seen from the data in Table 1, the energy conversion efficiency of the polymer solar cell device that also two (diazosulfide) multipolymer is prepared as active coating is coughed up for 0.98 ~ 1.42 with also [3, the 4-b] two thiophene-thiophene that contains of the present invention.Show of the present invention containing also [3,4-b] two thiophene-thiophene cough up and two (diazosulfide) multipolymer owing to coughing up also two (diazosulfide) conjugate unit containing new thiophene, its absorption spectrum generation red shift, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, ratio and charge collection efficiency that current carrier arrives electrode can be improved, thus raising effciency of energy transfer, by to the improvement of device architecture or modification, higher effciency of energy transfer can be obtained.
Embodiment 8
The copolymer p 1 prepared with embodiment 1 is for luminescent layer, prepare organic electroluminescence device, comprise the glass substrate 1 stacked gradually, transparent anode 2, anode buffer layer 3, luminescent layer 4, cathode buffer layer 5 and negative electrode 6, the structure of device is specially: glass substrate/transparent anode/anode buffer layer/luminescent layer/cathode buffer layer/negative electrode, see Fig. 2, but the structure of practical devices is not limited thereto.Wherein, each layer material and thickness are: transparent anode 2 for square resistance be the tin indium oxide (ITO) (thickness is 150nm) of 10 Ω/mouth, the material of anode buffer layer 3 is poly-(3, 4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) matrix material (PEDOT:PSS, commodity are called CLEVIOSPVPAl4083), thickness is 30nm, the material of luminescent layer 4 is copolymer p 1 (thickness is 90nm) prepared by the embodiment of the present invention 1, the material of cathode buffer layer 5 is LiF (thickness is 1.5nm), the material of negative electrode 6 is metal A l (thickness is 150nm).
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 11.9cd/A, and high-high brightness is 1148cd/m 2.
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. coughing up and two (diazosulfide) multipolymer containing also [3,4-b] two thiophene-thiophene for one kind, it is characterized in that, for having the copolymer p of following general formula:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for the integer that H or F, n are between 1 ~ 100.
2. cough up and the preparation method of two (diazosulfide) multipolymer containing also [3,4-b] two thiophene-thiophene for one kind, it is characterized in that, comprise following operation steps:
There is provided compd A and compd B, the structural formula of compd A and B is respectively:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3for H or C 1~ C 20alkyl, R 4for H or F;
In atmosphere of inert gases, described compd A and compd B are dissolved in organic solvent by 1:1.5 ~ 1.5:1 in molar ratio, add catalyzer, Stille coupling reaction is carried out 6 ~ 100 hours at 50 DEG C ~ 120 DEG C, obtain containing also [3 after separation and purification, 4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer, describedly to cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer is the copolymer p with following general formula:
In formula, n is the integer between 1 ~ 100.
3. also [3, the 4-b] two thiophene-thiophene that contains as claimed in claim 2 is coughed up and the preparation method of two (diazosulfide) multipolymer, and it is characterized in that, the preparation method of described compd A comprises following operation steps:
(1) 4-oil of mirbane-1,2-diamines and thionyl chloride and pyridine react, and be separated 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 diazosulfides and Hydrogen bromide and bromine generation bromination reaction, obtain 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide, reaction formula is:
Described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides and hydrobromic molecular volume are than being 4:1mol/L, 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) bromo-for 4,7-bis-5-nitro-2,1,3 diazosulfide, under copper powder catalysis, linked reaction is occurred, obtain 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides, reaction formula is:
Described 4,7-bis-bromo-5-nitro-2,1,3 diazosulfides: the mol ratio of copper powder is 0.2:1, and described temperature of reaction is 120 DEG C, and the reaction times is 3 hours;
(4) 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides is reduced to after amino through tindichloride, carries out diazotization reaction, then react with potassiumiodide under hydrochloric acid existent condition with Sodium Nitrite, obtain 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction formula is:
Described 4,4 '-two 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, and the time is 10h; Described 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: in hydrochloric acid, the mol ratio of hydrogenchloride is 0.92:1,4,4 '-two 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 less than 5 DEG C, and the time is 30min; Described 4,4 '-two 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 such 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 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides and n-Butyl Lithium react, and then at room temperature react with Compound C, obtain compd A, reaction formula is:
Described n-Butyl Lithium and 4,4 '-two bromo-6,6 '-two iodo-2,1, the mol ratio of 3 diazosulfides is x, 2≤x < 4, described Compound C and 4,4 '-two bromo-6,6 '-two iodo-2, the mol ratio of 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. also [3, the 4-b] two thiophene-thiophene that contains as claimed in claim 2 is coughed up and the preparation method of two (diazosulfide) multipolymer, and it is characterized in that, the preparation method of compd B comprises following operation steps:
Compound D is provided, wherein, R 3for H or C 1~ C 20alkyl, R 4for H or F:
Under protection of inert gas, Compound D is added in tetrahydrofuran (THF), be cooled to-78 DEG C; n-Butyl Lithium is added under-78 DEG C of conditions; Compound D: the mol ratio of n-Butyl Lithium is 1:2, and stirring reaction 1 ~ 2h, adds tributyltin chloride under-78 DEG C of conditions; Compound D: the mol ratio of tributyltin chloride is 1:2; react 1 hour at-78 DEG C, be then warming up to room temperature, react 6 hours; obtain compd B after separation, reaction formula is:
5. as claimed in claim 2 containing also [3,4-b] two thiophene-thiophene coughs up and the preparation method of two (diazosulfide) multipolymer, it is characterized in that, described catalyzer is three (dibenzalacetone) two palladium, two (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladiums.
6. also [3,4-b] two thiophene-thiophene as claimed in claim 2 is coughed up and the preparation method of two (diazosulfide) multipolymer, and it is characterized in that, the mole dosage of described catalyzer is 0.5% ~ 20% of compd A mole dosage.
7. also [3,4-b] two thiophene-thiophene as claimed in claim 2 is coughed up and the preparation method of two (diazosulfide) multipolymer, and it is characterized in that, described organic solvent is the one in tetrahydrofuran (THF), glycol dimethyl ether, Benzene and Toluene.
8. as claimed in claim 2 containing also [3, 4-b] two thiophene-thiophene coughs up and the preparation method of two (diazosulfide) multipolymer, it is characterized in that, being operating as of described separation and purification: after reaction, deionized water is added and toluene extracts in reaction solution, get organic phase, add after underpressure distillation in dehydrated alcohol, separate out precipitation, suction filtration, pressed powder is obtained after oven dry, after pressed powder being dissolved with chloroform, take toluene as elutriant, be separated with silica gel column chromatography, methyl alcohol sedimentation is used after chromatographic solution underpressure distillation, suction filtration, gained solid acetone extracts three days in apparatus,Soxhlet's, use methyl alcohol sedimentation again, suction filtration, vacuum filtration spends the night, obtain containing also [3, 4-b] two thiophene-thiophene coughs up and two (diazosulfide) multipolymer.
9. as claimed in claim 1 containing also [3,4-b] two thiophene-thiophene coughs up and the application of two (diazosulfide) multipolymer, it is characterized in that, described cough up containing also [3,4-b] two thiophene-thiophene and two (diazosulfide) multipolymer for the preparation of polymer solar cell device or organic electroluminescence device.
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