CN103833973A - Copolymer containing dithieno (3,2-b:2',3'-d) thiophene-silole (2,3-b:3',2'-d) (diazosulfide) as well as preparation method and application of copolymer - Google Patents

Copolymer containing dithieno (3,2-b:2',3'-d) thiophene-silole (2,3-b:3',2'-d) (diazosulfide) as well as preparation method and application of copolymer Download PDF

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CN103833973A
CN103833973A CN201210489179.2A CN201210489179A CN103833973A CN 103833973 A CN103833973 A CN 103833973A CN 201210489179 A CN201210489179 A CN 201210489179A CN 103833973 A CN103833973 A CN 103833973A
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thiophene
diazosulfide
bis
reaction
multipolymer
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CN103833973B (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 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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Abstract

The invention provides a copolymer containing dithieno (3,2-b:2',3'-d) thiophene-silole (2,3-b:3',2'-d) (diazosulfide) as well as a preparation method and an application of the copolymer. The copolymer provided by the invention is a copolymer P which has the general formula shown in the specification, wherein in the formula, R1 and R2 represent alkyl groups of C1 to C20; R3 and R4 represent H or alkyl groups of C1 to C20; n represents an integer between 1 and 100. The copolymer contains a new silole (2,3-b:3',2'-d) (diazosulfide) conjugation unit which has a high matching degree with solar spectrum and is of a plane conjugation structure at the same time, so that the charge carrier migration rate is high. Thus, the energy conversion efficiency is improved. A preparation method of the copolymer is simple and controllable. As a result, the copolymer provided by the invention has good application prospects in the fields of polymer solar cells, organic electroluminescent devices and other photoelectric materials.

Description

Containing also three thiophene-thiophene coughs up and two (diazosulfide) multipolymers and preparation and application
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of also three thiophene-thiophene that contains and cough up also two (diazosulfide) multipolymer and preparation method thereof and application.
Background technology
The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell is because complex manufacturing, cost are high at present, and application is restricted.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.
At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.And the absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, it is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor, improve absorbing sun power.
For photoelectric material contain and the conjugated polymers of three thiophene units and diazosulfide unit appears in the newspapers, but the effciency of energy transfer obtaining is in actual applications still lower.Therefore, develop new polymer materials, improve the effciency of energy transfer of photoelectric material for the great significance of organic solar batteries.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of also three thiophene-thiophene that contains and coughs up and two (diazosulfide) multipolymer.
The present invention also aims to provide containing and three thiophene-thiophene is coughed up and preparation method and the application of two (diazosulfide) multipolymer.
First aspect, the invention provides a kind of also three thiophene-thiophene that contains and coughs up and two (diazosulfide) multipolymer, for thering is the copolymer p of following general formula:
Figure BDA00002472477400021
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H or C 1~ C 20alkyl, n is the integer between 1～100.
Provided by the invention containing and three thiophene-thiophene is coughed up and the structure of two (diazosulfide) multipolymer in contain that new thiophene is coughed up and two (diazosulfide) unit, diazosulfide unit is common functional unit, there is excellent reduction reversibility, approach with the work content value of the metallic cathode such as magnesium, aluminium, belong to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, it is the good body unit that is subject to, there is good electronic transport property, can also regulate the energy gap of material, and thiophene is coughed up in structural unit and is existed simultaneously
Figure BDA00002472477400022
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 benzene 1,4-Dithiapentalene-thiophene cough up and two (diazosulfide) multipolymer in the new thiophene that contains cough up and two (diazosulfide) copolymer unit combines the constitutional features of above two kinds of unit, there is narrower band gap and stronger conjugated nature, make multipolymer there is excellent electronic transmission performance, can be applicable to the fields such as organic solar batteries.
Simultaneously, thiophene is five-membered ring structure, there is moderate band gap, wider spectral response, thermostability and film forming properties preferably, therefore, thiophene-based organic photoelectrical material is the up-and-coming material of a class, application in fields such as organic solar batteries has obtained broad research, and also three thiophene units have three five-membered ring structures, there is narrow band gap and strong conjugated nature, at present in the photoelectric material such as widespread use and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
The present invention on the basis of above two kinds of unit, obtain having novel planar conjugated structure containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer, there is excellent carrier mobility ability and configuration flexibility, have a extensive future.
Second aspect, the invention provides containing and three thiophene-thiophene is coughed up and the preparation method of two (diazosulfide) multipolymer, comprises following operation steps:
Compd A and compd B are provided, and the structural formula of compd A and B is respectively:
Figure BDA00002472477400031
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H or C 1~ C 20alkyl;
In atmosphere of inert gases, 1:1.5 ~ 1.5:1 is dissolved in described compd A and compd B in organic solvent in molar ratio, add catalyzer, at 50 DEG C ~ 120 DEG C, carry out Stille coupling reaction 6 ~ 100 hours, after separation and purification, obtain containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer, described containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer is the copolymer p with following general formula:
Figure BDA00002472477400041
In formula, n is the integer between 1 ~ 100.
The reaction formula of Stille coupling reaction is:
Figure BDA00002472477400042
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, 0.5% ~ 20% of the amount of substance that the mole dosage of described catalyzer is 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, described preparation method's operating process is: compd A is mixed with compd B and organic solvent, vacuumize deoxygenation and be filled with rare gas element, add catalyzer, be heated to 50 ~ 120 DEG C, reaction times is 6 ~ 100 hours, and reaction finishes, and obtains containing also three thiophene-thiophene and cough up and two (diazosulfide) multipolymer after separation and purification.
Preferably, being operating as of described separation and purification: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, taking toluene as elutriant, separate with silica gel column chromatography, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtaining containing also three 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 reacts with thionyl chloride and pyridine, separate obtain 5-nitro-2,1,3 diazosulfide, reaction formula is:
Figure BDA00002472477400051
Preferably, described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/L, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 DEG C, and the time is 24h.
(2), 5-nitro-2,1,3 diazosulfide and Hydrogen bromide and bromine generation bromination reaction, obtain the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide, reaction formula is:
Figure BDA00002472477400052
Preferably, described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides are 4:1mol/L with hydrobromic molecular volume ratio, described 5-nitro-2,1,3 diazosulfides: the molecular volume of bromine is than being 5.3:1mol/L, and described temperature of reaction is 127 DEG C, and the reaction times is 4h.
(3), 4, the bromo-5-of 7-bis-nitro-2, under copper powder catalysis, there is linked reaction in 1,3 diazosulfide, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:
Figure BDA00002472477400061
Preferably, described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 DEG C, the reaction times is 3 hours.
(4), 4,4 '-bis-bromo-6, the nitro in 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides is through tindichloride (SnCl 2) be reduced to after amino, under the condition existing at hydrochloric acid, carry out diazotization reaction with Sodium Nitrite, then react with potassiumiodide, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:
Figure BDA00002472477400062
Preferably, described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1:10, the temperature of described reduction reaction is 100 DEG C, the time is 10h; Described 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: the mol ratio of the hydrogenchloride (HCl) in hydrochloric acid is 0.92:1,4,4 '-bis-is bromo-6,6 '-dinitrobenzene- Lian 2,1,3 diazosulfides: the mol ratio of Sodium Nitrite is 0.53:1, the temperature of described diazotization reaction is below 5 DEG C, the time is 30min; Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of potassiumiodide is 0.054:1, the described time of reacting with potassiumiodide is 12h.
(5), provide suc as formula the Compound C shown in C, wherein, R 1, R 2for C 1~ C 20alkyl;
Figure BDA00002472477400063
In dimethyl formamide (DMF) solvent and under oxygen free condition, at-90 DEG C, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides react with n-Butyl Lithium, then at room temperature react with Compound C, obtain compd A, and reaction formula is:
Figure BDA00002472477400071
Preferably, described n-Butyl Lithium and 4, the mol ratio of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is x, 2≤x ﹤ 4, described Compound C and 4, the mol ratio of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is 2:1.Preferably, the described time of reacting with n-Butyl Lithium is 2h, and the described time of reacting with Compound C is 10h.
In an embodiment, for convenience of statement, compd A is used respectively compd A 1, A2, and the expressions such as A3, Compound C is used respectively Compound C 1, C2, the expressions such as C3, name is all as the criterion with the title in each embodiment.
The preparation method of described compd B comprises following operation steps:
Compound D is provided, wherein, R 3, R 4for H or C 1~ C 20alkyl:
Under protection of inert gas, Compound D is added in tetrahydrofuran (THF) (THF), be cooled to-78 DEG C; under-78 DEG C of conditions, add n-Butyl Lithium; Compound D: the mol ratio of n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2h adds tributyltin chloride (SnBu under-78 DEG C of conditions 3cl), Compound D: the mol ratio of tributyltin chloride is 1:2 is reacted 1 hour at-78 DEG C, is then warming up to room temperature, reacts 6 hours, obtains compd B after separation, and reaction formula is:
Figure BDA00002472477400081
Preferably, described rare gas element is nitrogen or argon gas.
In an embodiment, for convenience of statement, compd B is used respectively the expressions such as compound B-11, B2, B3, B4, and Compound D is used respectively Compound D 1, D2, and D3, the expressions such as D4, name is all as the criterion with the title in each embodiment.
The third aspect, the invention provides containing and three thiophene-thiophene is coughed up and the application of two (diazosulfide) multipolymer, containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer for the preparation of polymer solar cell device and organic electroluminescence device.Described containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer as described in first aspect.
One provided by the invention contains and three thiophene-thiophene is coughed up also two (diazosulfide) multipolymer and preparation method thereof and application, has following beneficial effect:
1, of the present invention containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer in, thiophene is coughed up and two (diazosulfide) unit has the advantages such as simple in structure, symmetrical, electron delocalization performance is good, and be two dimensional structure, it is a kind of very excellent donor material, with and three thiophene units be combined formation and there is the copolymer material of donor-receiver structure, can improve on the one hand the stability of material, can reduce on the other hand the band gap of material, thereby expand sunlight absorption region, improve electricity conversion;
2, provided by the invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer contains new thiophene and 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, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and can be by introducing solvability and the molecular weight of alkyl raising multipolymer, be conducive to film forming processing, and preparation method is simply ripe;
3, reaction conditions gentleness, be easy to control, and productive rate is high.
Brief description of the drawings
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.
The involved in the present invention also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, for thering is the copolymer p of following general formula:
Figure BDA00002472477400091
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H or C 1~ C 20alkyl, n is the integer between 1～100.
Embodiment 1
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, i.e. poly-{ also [3,2-b:4 of 3,5-dioctyl, 5-b '] three thiophene-6,6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfides) } (n=53), be designated as copolymer p 1, structural formula is as follows:
Preparation method comprises the following steps:
(1), 4,9-bis-is bromo-6,7-dioctyl-benzo [2,1-e:3,4-e] two (diazosulfide) preparation method (A1) comprises following operation steps:
(1) prepare compound 5-nitro-2,1,3 diazosulfide, reaction formula is:
In there-necked flask, add 4-oil of mirbane-1,2-diamines (22.95g, 0.15mol) and 100mL thionyl chloride, stir and slowly drip 2mL pyridine, after heating in 80 ~ 90 DEG C of back flow reaction 24h, stopped reaction, being heated to 80 DEG C revolves and steams after excessive thionyl chloride, reaction product is cooled to room temperature, in the large water gaging of impouring, stirs, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
(2) prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide, reaction formula is:
Figure BDA00002472477400111
In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and the massfraction Hydrogen bromide 15mL that is 40%, be warming up to 127 DEG C of backflows, in 30min, slowly drip bromine 11.3mL the 4h that refluxes, heat filtering, refilters after filtrate is cooling, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide 10.2g, productive rate 50%.
(3) prepare 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:
Figure BDA00002472477400112
In there-necked flask, add 4, the bromo-5-of 7-bis-nitro-2, 1, 3 diazosulfide (10.2g, 30mmol), the copper powder of 9.5g and 90mL N, dinethylformamide (DMF), be 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 is used 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 '-bis-bromo-6, 6 '-dinitrobenzene- Lian 2, 1, 3 diazosulfide 4.7g, productive rate 30.2%.
(4) prepare 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:
Figure BDA00002472477400113
In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran THF that 300mL is dry, add 40g tindichloride (SnCl 2) (200mmol), be warming up to 100 DEG C, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtain solid crude product, be put in there-necked flask, add the hydrochloric acid (amount of substance of HCl is 21.7mmol) of 58mL, in 30 minutes, the amount of substance of agitation and dropping sodium nitrite solution 20mL(Sodium Nitrite is 37.7mmol), temperature is controlled at below 5 DEG C, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide adds 100mL water to obtain liquor kalii iodide) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, carry out silica gel column chromatography separation taking sherwood oil as elutriant, then carry out recrystallization with methyl alcohol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
(5) provide structural formula suc as formula the Compound C 1 shown in C1, i.e. dioctyl dichlorosilane;
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50mL DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.015mol) of 6.0mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, and stirring reaction 2 hours at-90 DEG C, adds 4.73mL Compound C 1(10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, carry out silica gel column chromatography separation taking sherwood oil as elutriant to distilling rear surplus materials, obtain 4.43g product 4,8-bis-is bromo-6, and 6-dioctyl thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A1), productive rate 65%, reaction formula is:
Figure BDA00002472477400131
The structured testing data of compd A 1 are as follows:
1HNMR（CDCl 3）δ（TMS，ppm）：8.08（d，2H），1.30-1.42（m，28H），0.93（d，6H）；
13CNMR（CDCl 3）δ（TMS，ppm）：160.3，155.8，140.0，136.3，134.2，114.5，33.0，31.8，29.5，24.0，22.6，14.2，13.6。
(2), 3,5-dioctyl-2,6-bis-(tributyl tin) the also preparation method of [3,2-b:4,5-b '] three thiophene (B1) comprises the following steps:
Compound D 1 is provided, 3,5-dioctyl-2,6-dibromo is [3,2-b:4,5-b '] three thiophene also;
Under the protection of nitrogen, in there-necked flask, add Compound D 1 (5.79g, 0.01mol) with 60mL tetrahydrofuran (THF), under-78 DEG C of conditions, slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe, 0.02mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, rise to stirring at room temperature reaction 6 hours, in there-necked flask, add saturated sodium-chloride water solution 30mL termination reaction, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate to be dried, after suction filtration by filtrate collection and revolve and evaporate ether, obtain crude product, with sherwood oil be elutriant, crude product is carried out to separating-purifying with neutral alumina chromatography column, obtain product 3, 5-dioctyl-2, 6-bis-(tributyl tin) also [3, 2-b:4, 5-b '] three thiophene (B1), productive rate 68%, reaction formula is:
Figure BDA00002472477400132
(3) (P1), reaction formula is, to gather { 3,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, and 6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) }:
Figure BDA00002472477400141
Under nitrogen protection; compound B-11 (the 199.8mg that adds step (two) to prepare in round-bottomed flask; compd A 1 (the 136.2mg that 0.2mmol), step () prepares; 0.2mmol) with tetrahydrofuran (THF) 40mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 2cl 2(5mg, 7.12 × 10 -3mmol), be heated to 90 DEG C of reaction 72h.
After reaction finishes, add deionized water and toluene to extract to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, splash in 400mL dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, carry out silica gel column chromatography separation taking toluene as elutriant, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3, 5-dioctyl also [3, 2-b:4, 5-b '] three thiophene-6, 6 dioctyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P1).
{ 3,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also by poly-gained, 6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P1) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=51410, n=53, polymkeric substance monodispersity coefficient is 2.4.
Embodiment 2
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, gather { 3,5-bis-(NSC 62789 base) also [3,2-b:4,5-b '] three thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfides) } (n=29), be designated as copolymer p 2, structural formula is as follows:
Preparation method comprises the following steps:
(1), 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) preparation method (A2) and is comprised following operation steps:
Prepare 4 according to (1) of embodiment 1 step ()-(4) step, 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
Provide structural formula suc as formula the Compound C 2 shown in C2, i.e. dimethyldichlorosilane(DMCS).
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50mL DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.01mol) of 4.0mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, and at-90 DEG C, stirring reaction 2 hours, adds 10mmol Compound C 2, rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, carry out silica gel column chromatography separation taking sherwood oil as elutriant to distilling rear surplus materials, obtain 3.38g product 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A2), productive rate 70%, reaction formula is:
Figure BDA00002472477400152
The structured testing data of compd A 2 are as follows:
1HNMR（CDCl 3）δ（TMS，ppm）：8.08（d，2H），0.68（d，6H）；
13CNMR（CDCl 3）δ（TMS，ppm）：160.3，155.8，140.0，136.3，134.2，114.5，-1.8。
(2), 3,5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) the also preparation method of [3,2-b:4,5-b '] three thiophene (B2) comprises the following steps:
Provide structural formula suc as formula the Compound D 2 shown in D2,3,5-bis-(NSC 62789 base)-2,6-dibromo is [3,2-b:4,5-b '] three thiophene also;
Under the protection of nitrogen, in there-necked flask, add Compound D 2 (9.15g, 0.01mol), add the tetrahydrofuran (THF) of 90mL, under-78 DEG C of conditions, slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe, 0.02mol), continue stirring reaction 1h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, be warming up under room temperature stirring reaction 6 hours, reacted reaction solution adds termination reaction in 30mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulphate layer is dry, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, with sherwood oil be elutriant, crude product is carried out to neutral alumina column chromatography for separation, obtain 3, 5-bis-(NSC 62789 base)-2, 6-bis-(tributyl tin) also [3, 2-b:4, 5-b '] three thiophene (B2), productive rate 74%, reaction formula is:
Figure BDA00002472477400161
(3), poly-{ 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6 also, and 6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P2) comprises the following steps:
Under argon shield; to the compd B 2 (267mg that add step (two) to prepare in round-bottomed flask; compd A 2 (the 136.2mg that 0.2mmol), prepared by step (); 0.2mmol) with glycol dimethyl ether 40mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 4(5mg, 4.33 × 10 -3mmol), be heated to 70 DEG C of reaction 36h.
After reaction, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 6mL left and right, splashed in 500mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, chromatographic solution underpressure distillation is removed to organic solvent, with suction filtration after methyl alcohol sedimentation, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3, 5-bis-(NSC 62789 base) also [3, 2-b:4, 5-b '] three thiophene-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P2), reaction formula is as follows:
Figure BDA00002472477400171
To poly-{ 3,5-bis-(NSC 62789 base) also [3,2-b:4,5-b '] three thiophene-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfides) } (P2) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=32190, n=29, monodispersity coefficient is 2.7.
Embodiment 3
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, gather { 3,5-dioctyl also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) } (n=65), be designated as copolymer p 3, structural formula is as follows:
Figure BDA00002472477400181
Preparation method comprises the following steps:
(1), 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) preparation method (A3) and is comprised following operation steps:
Prepare 4 according to (1) of embodiment 1 step ()-(4) step, 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.
Provide structural formula suc as formula the Compound C 3 shown in C3, i.e. two (NSC 62789 base) dichlorosilane.
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 50mL DMF, pass into nitrogen gas stirring 20min, slowly drip the hexane solution (2.5M, 0.02) of 8.0mL n-Butyl Lithium, within 0.5 hour, drip off, controlling temperature is-90 DEG C, and stirring reaction 2 hours at-90 DEG C, adds 4.93mL Compound C 3(10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, with anhydrous diethyl ether extraction, obtains organic layer after reaction solution is washed, add anhydrous sodium sulfate drying, filter underpressure distillation, normal hexane/methylene dichloride mixed solvent taking volume ratio as 10:1 carries out silica gel column chromatography separation to distilling rear surplus materials as elutriant, obtain 2.79g product 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (A3), productive rate 55%, reaction formula is:
Figure BDA00002472477400182
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), preparation 3,5-dioctyl-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene (B1) also: concrete operations are with embodiment 1 step (two).
(3) poly-{ 3,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, and 6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P3) comprises the following steps:
Under nitrogen protection; to the compound B-11 (199.8mg, 0.2mmol) that adds in round-bottomed flask step (two) to prepare, compound A-13 (203.4mg, 0.2mmol) and toluene 40mL prepared by step (); vacuumize deoxygenation and be filled with nitrogen, then add Pd 2(dba) 3(5mg, 5.45 × 10 -3mmol), be heated to 80 DEG C of reaction 48h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3, 5-dioctyl also [3, 2-b:4, 5-b '] three 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:
Figure BDA00002472477400191
To poly-{ 3,5-dioctyl also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfides) } (P3) carry out gel chromatography (GPC) test, record number-average molecular weight Mn=84890, n=65, monodispersity coefficient is 3.1.
Embodiment 4
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, poly-{ also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } (n=35), be designated as copolymer p 4, structural formula is as follows:
Figure BDA00002472477400201
(1), preparation 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step in embodiment 3 (one).
(2), 2,6-bis-(tributyl tin) the also preparation method of [3,2-b:4,5-b '] three thiophene (B3) comprises the following steps:
Provide structural formula suc as formula the compound d3 shown in D3,2,6-dibromo is [3,2-b:4,5-b '] three thiophene also;
Under the protection of nitrogen, in there-necked flask, add compound d3 (3.54g, 0.01mol) with 40mL tetrahydrofuran (THF), under-78 DEG C of conditions, slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe, 0.02mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, rise to stirring at room temperature reaction 6 hours, in there-necked flask, add saturated sodium-chloride water solution 30mL termination reaction, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate to be dried, after suction filtration by filtrate collection and revolve and evaporate ether, obtain crude product, with sherwood oil be elutriant, crude product is carried out to separating-purifying with neutral alumina chromatography column, obtain product 2, 6-bis-(tributyl tin) also [3, 2-b:4, 5-b '] three thiophene (B3), productive rate 58%, reaction formula is as follows:
(3), poly-{ also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P4) comprises following operation steps:
Under nitrogen protection; compd B 3 (the 154.8mg that add step (two) to prepare in round-bottomed flask; compound A-13 (the 203.4mg that 0.2mmol), prepared by step (); 0.2mmol) with benzene 40mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 2cl 2(28.08mg, 0.04mmol), is heated to 90 DEG C of reaction 72h.
After reaction finishes, add deionized water and toluene to extract to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, splash in 400mL dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, dissolve with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain product poly-{ also [3, 2-b:4, 5-b '] three thiophene-6, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P4), reaction formula is:
Figure BDA00002472477400212
By poly-gained { also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P4) carry out gel chromatography (GPC) test, number-average molecular weight=37870, n=35, monodispersity coefficient is 3.5.
Embodiment 5
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, gather { 3,5-bis-(NSC 62789 base) also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) } (n=100), be designated as copolymer p 5, structural formula is as follows:
Figure BDA00002472477400221
(1), preparation 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step in embodiment 3 (one).
(2), preparation 3,5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene (B2) also:
Concrete operations are with the step in embodiment 2 (two).
(3), poly-{ 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6 also, and 6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P5) comprises following operation steps:
Under nitrogen protection; compd B 2 (the 400.5mg that add step (two) to prepare in round-bottomed flask; compound A-13 (the 203.4mg that 0.3mmol), prepared by step (); 0.2mmol) with tetrahydrofuran (THF) 40mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 2cl 2(28.04mg, 3.99 × 10 -2mmol), be heated to 120 DEG C of reaction 100h.
After reaction finishes, add deionized water and toluene to extract to round-bottomed flask, take out organic phase, underpressure distillation is to about 5mL, splash in 400mL dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, dissolve with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain product poly-{ 3, 5-bis-(NSC 62789 base) also [3, 2-b:4, 5-b '] three thiophene-6, 6 two (NSC 62789 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P5), reaction formula is:
Figure BDA00002472477400231
By gained poly-{ 3,5-bis-(NSC 62789 base) also [3,2-b:4,5-b '] three thiophene-6,6 two (NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfides) } (P5) carry out gel chromatography (GPC) test, number-average molecular weight=164300, n=100, monodispersity coefficient is 5.8.
Embodiment 6
A kind of also three thiophene-thiophene that contains is coughed up and two (diazosulfide) multipolymer, i.e. poly-{ also [3,2-b:4 of 3,5-dimethyl, 5-b '] three thiophene-6,6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfides) } (n=1), be designated as copolymer p 6, structural formula is as follows:
Preparation method comprises the following steps:
(1), preparation 6,6-dimethyl-4,8-dibromo thiophene cough up also [3,2-e:4,5-e] two (diazosulfide) (A2) concrete operations with the step in embodiment 2 (one).
(2), 3,5-dimethyl-2,6-bis-(tributyl tin) the also preparation method of [3,2-b:4,5-b '] three thiophene (B4) comprises the following steps:
Provide structural formula suc as formula the Compound D 4 shown in D4,3,5-dimethyl-2,6-dibromo is [3,2-b:4,5-b '] three thiophene also;
Under the protection of nitrogen, in there-necked flask, add Compound D 4 (3.82g, 0.01mol) with 40mL tetrahydrofuran (THF), under-78 DEG C of conditions, slowly inject the hexane solution (2.5M of 8.0mL n-Butyl Lithium with syringe, 0.02mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe, 0.02mol), react and after 1 hour, rise to stirring at room temperature reaction 6 hours, in there-necked flask, add saturated sodium-chloride water solution 30mL termination reaction, extract with anhydrous diethyl ether, obtain organic layer, add anhydrous sodium sulphate to be dried, after suction filtration by filtrate collection and revolve and evaporate ether, obtain crude product, with sherwood oil be elutriant, crude product is carried out to separating-purifying with neutral alumina chromatography column, obtain product 3, 5-dimethyl-2, 6-bis-(tributyl tin) also [3, 2-b:4, 5-b '] three thiophene (B4), productive rate 60%, reaction formula is as follows:
Figure BDA00002472477400241
(3) poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6 also, and 6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } preparation method (P6) comprises the following steps:
Under nitrogen protection; to the compd B 4 (160.4mg that add step (two) to prepare in round-bottomed flask; compd A 2 (the 145.2mg that 0.2mmol), prepared by step (); 0.3mmol) with tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 2cl 2(1.052mg, 0.0015mmol), is heated to 50 DEG C of reaction 6h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, be that elutriant carries out silica gel column chromatography separation with toluene, organic solvent is removed in chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, gathered { 3, 5-dimethyl also [3, 2-b:4, 5-b '] three thiophene-6, 6 dimethyl thiophenes cough up also [3, 2-e:4, 5-e] two (diazosulfides) } (P6), reaction formula is as follows:
Figure BDA00002472477400251
Poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6 also, and 6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) } (P6) are carried out to gel chromatography (GPC) test, record number-average molecular weight Mn=577, n=1.
Embodiment 7
Prepare taking the embodiment of the present invention containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer be active coating, prepare polymer solar cell device, comprise the substrate of glass 1 stacking gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, see Fig. 1.Wherein, the tin indium oxide (ITO) that anode 2 is 10 Ω/ for square resistance, the material of middle supplementary layer 3 is poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) matrix material, being expressed as PEDOT:PSS(trade name is CLEVIOS P VP Al 4083); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor material is that the also three thiophene-thiophene that contains prepared by the embodiment of the present invention is coughed 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 be chosen ito glass,, can buy as anode 2 with ITO layer, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen plasma (oxygen-Plasma) processing; Then on ito glass, apply PEDOT:PSS, supplementary layer 3 in the middle of obtaining, thickness is 110nm; Prepared by the 10mg embodiment of the present invention containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer be dissolved in 0.4mL dimethylbenzene, obtain solution 1,8mg PCBM is dissolved in 0.4mL chlorobenzene and obtains solution 2, in the middle of being spun on after solution 1 and solution 2 are mixed on supplementary layer, obtain active coating 4, thickness is 150nm; At vacuum condition (2 × 10 -3pa) lower AM aluminum metallization prepares negative electrode 5, and thickness is 120nm, obtains polymer solar cell device.Contain the present invention containing and three thiophene-thiophene is coughed up and preparation method and the structure of the polymer solar cell device of two (diazosulfide) multipolymer are not limited to the present embodiment, can device suitably be improved or be modified.
Respectively using embodiment 1,2 and 3 preparation containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer p 1, P2, P3 are prepared 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 that nitrogen inert atmosphere is provided.
By the I-E characteristic of Keithley236 current/voltage source-measuring system and test polymer solar cell device, obtain performance data in table 1.
Table 1 taking of the present invention containing and three thiophene-thiophene is coughed up and the performance data of the polymer solar cell device that two (diazosulfide) multipolymer is prepared as active coating
Figure BDA00002472477400261
Figure BDA00002472477400271
As seen from the data in Table 1, taking of the present invention containing and three thiophene-thiophene is coughed up and the energy conversion efficiency of the polymer solar cell device prepared as active coating of two (diazosulfide) multipolymer as 0.92 ~ 1.25.Show of the present invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer is coughed up and two (diazosulfide) conjugate unit owing to 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, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, by the improvement to device architecture or modification, can obtain higher effciency of energy transfer.
Embodiment 8
The copolymer p 1 of preparing taking embodiment 1 is luminescent layer, be prepared with organic electroluminescence devices, comprise the glass substrate 1 stacking 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 to this.Wherein, each layer of material and thickness are: the tin indium oxide (ITO) (thickness is 150nm) that transparent anode 2 is 10 Ω/ for square resistance, 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 CLEVIOS P VP Al 4083), thickness is 30nm, the material of luminescent layer 4 is that copolymer p 1(thickness prepared by the embodiment of the present invention 1 is 90nm), the material of cathode buffer layer 5 is that LiF(thickness is 1.5nm), the material of negative electrode 6 is that metal A l(thickness is 150nm).
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 12.5cd/A, and high-high brightness is 1160cd/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. contain also three thiophene-thiophene and cough up and two (diazosulfide) multipolymer, it is characterized in that, for thering is the copolymer p of following general formula:
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H or C 1~ C 20alkyl, n is the integer between 1～100.
2. contain also three thiophene-thiophene and cough up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, comprise following operation steps:
Compd A and compd B are provided, and the structural formula of compd A and B is respectively:
Figure FDA00002472477300012
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H or C 1~ C 20alkyl;
In atmosphere of inert gases, 1:1.5 ~ 1.5:1 is dissolved in described compd A and compd B in organic solvent in molar ratio, add catalyzer, at 50 DEG C ~ 120 DEG C, carry out Stille coupling reaction 6 ~ 100 hours, after separation and purification, obtain containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer, described containing and three thiophene-thiophene is coughed up and two (diazosulfide) multipolymer is the copolymer p with following general formula:
Figure FDA00002472477300021
In formula, n is the integer between 1 ~ 100.
3. the also three thiophene-thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the preparation method of described compd A comprises following operation steps:
(1) 4-oil of mirbane-1,2-diamines reacts with thionyl chloride and pyridine, and separate and obtain 5-nitro-2,1,3 diazosulfide, reaction formula is:
Figure FDA00002472477300022
Described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/L, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 DEG C, and the time is 24h;
(2) 5-nitro-2,1,3 diazosulfide and Hydrogen bromide and bromine generation bromination reaction, obtain the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide, reaction formula is:
Described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides are 4:1mol/L with hydrobromic molecular volume ratio, described 5-nitro-2,1,3 diazosulfides: the molecular volume of bromine is than being 5.3:1mol/L, and described temperature of reaction is 127 DEG C, and the reaction times is 4h;
(3) by bromo-4,7-bis-5-nitro-2, there is linked reaction in 1,3 diazosulfide under copper powder catalysis, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:
Figure FDA00002472477300031
Described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 DEG C, the reaction times is 3 hours;
(4) 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides, after tindichloride is reduced to amino, carries out diazotization reaction with Sodium Nitrite under the condition existing, then react with potassiumiodide at hydrochloric acid, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:
Figure FDA00002472477300032
Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1:10, the temperature of described reduction reaction is 100 DEG C, the time is 10h; Described 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: in hydrochloric acid, the mol ratio of hydrogenchloride is 0.92:1,4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: the mol ratio of Sodium Nitrite is 0.53:1, the temperature of described diazotization reaction is below 5 DEG C, the time is 30min; Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of potassiumiodide is 0.054:1, the described time of reacting with potassiumiodide is 12h;
(5) provide suc as formula the Compound C shown in C, wherein, R 1, R 2for C 1~ C 20alkyl;
Figure FDA00002472477300041
In solvent dimethylformamide and under oxygen free condition, at-90 DEG C, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides react with n-Butyl Lithium, then at room temperature react with Compound C, obtain compd A, and reaction formula is:
Figure FDA00002472477300042
Described n-Butyl Lithium and 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1, the mol ratio of 3 diazosulfides is x, 2≤x ﹤ 4, described Compound C and 4,4 '-bis-bromo-6, the mol ratio of 6 '-bis-iodo-2,1,3 diazosulfides is 2:1, the described time of reacting with n-Butyl Lithium is 2h, and the described time of reacting with Compound C is 10h.
4. the also three thiophene-thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the preparation method of compd B comprises following operation steps:
Compound D is provided, wherein, R 3, R 4for H or C 1~ C 20alkyl:
Figure FDA00002472477300043
Under protection of inert gas, Compound D is added in tetrahydrofuran (THF), be cooled to-78 DEG C; under-78 DEG C of conditions, add n-Butyl Lithium; Compound D: the mol ratio of n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2h adds tributyltin chloride under-78 DEG C of conditions; Compound D: the mol ratio of tributyltin chloride is 1:2; at-78 DEG C, react 1 hour, be then warming up to room temperature, react 6 hours; after separation, obtain compd B, reaction formula is:
Figure FDA00002472477300051
5. the also three thiophene-thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described catalyzer is three (dibenzalacetone) two palladiums, two (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladiums.
6. as claimed in claim 2 and three thiophene thiophenes are coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, the mole dosage of described catalyzer is 0.5% ~ 20% of compd A mole dosage.
7. as claimed in claim 2 and three thiophene fen-thiophenes are coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, described organic solvent is the one in tetrahydrofuran (THF), glycol dimethyl ether, benzene and toluene.
8. the also three thiophene-thiophene that contains as claimed in claim 2 is coughed up the also preparation method of two (diazosulfide) multipolymer, it is characterized in that, being operating as of described separation and purification: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, taking toluene as elutriant, separate with silica gel column chromatography, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtaining containing also three thiophene-thiophene coughs up and two (diazosulfide) multipolymer.
9. the also three thiophene-thiophene that contains as claimed in claim 1 is coughed up the also application of two (diazosulfide) multipolymer, it is characterized in that, described containing and three thiophene-thiophene cough up and two (diazosulfide) multipolymer for the preparation of polymer solar cell device or organic electroluminescence device.
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