CN103833973B - Containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymers and preparation thereof and application - Google Patents
Containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymers and preparation thereof and application Download PDFInfo
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- 0 CC1=Cc([n-]c2cc(*)c(*N=C3)c3c22)c2C2=C=CN*=C12 Chemical compound CC1=Cc([n-]c2cc(*)c(*N=C3)c3c22)c2C2=C=CN*=C12 0.000 description 5
- GWUPTJYUMDTXJV-UHFFFAOYSA-N Nc(c(N)c1C2CC2)ccc1[N+]([O-])=O Chemical compound Nc(c(N)c1C2CC2)ccc1[N+]([O-])=O GWUPTJYUMDTXJV-UHFFFAOYSA-N 0.000 description 1
- FSFGPEZTQUIDBZ-UHFFFAOYSA-N [O-][N+](C1=CC2=NSNC2C=C1)=O Chemical compound [O-][N+](C1=CC2=NSNC2C=C1)=O FSFGPEZTQUIDBZ-UHFFFAOYSA-N 0.000 description 1
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The present invention provides containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymers and preparation thereof and application, described containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is the copolymer p with below formula, in formula, R1, R2For C1~C20Alkyl, R3, R4For H or C1~C20Alkyl, n is the integer between 1～100.The present invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer contains new thiophene and coughs up also two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it it is planar conjugate structure simultaneously, carrier mobility speed is high, energy conversion efficiency is made to be improved, and preparation method is simply controlled, there is good application prospect in the field of photovoltaic materials such as polymer solar battery, organic electroluminescence device.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer and preparation method thereof and application.
Background technology
The solaode that preparation cost is low, usefulness is high is always up study hotspot and the difficult point of photovoltaic art.Business-like silicon solar cell is due to complex manufacturing, cost height at present, and application is restricted.In order to reduce cost, expansive approach scope, people always search for novel solar cell material for a long time.Polymer solar battery has superior market prospect because the mode large area such as low in raw material price, light weight, flexibility, production technology simple, available coating, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.SSariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) upper report conjugated polymer and C60Between Photo-induced electron transfer phenomenon after, people have put into big quantity research in polymer solar battery, and achieve development at full speed.
The energy conversion efficiency of current polymer solar battery is still low than silicon solar cell, and one of reason is due to the carrier mobility of polymer several orders of magnitude lower than the mobility of inorganic monocrystalline material.And the absorption spectrum of currently used conjugated polymer light cell material and solar spectrum can not be well matched with, it it is another major reason causing energy transfer efficiency low.For improving the performance of polymer solar battery further, the pole narrow band gap polymer with relatively wide absorption spectrum can be adopted to do donor and receptor, improve absorbing solar energy.
The conjugated polymer containing also three thiophene units and diazosulfide unit for photoelectric material appears in the newspapers, but the energy conversion efficiency obtained in actual applications is still relatively low.Therefore, develop new polymeric material, improve the energy conversion efficiency great significance for organic solar batteries of photoelectric material.
Summary of the invention
For solving the problems referred to above, it is desirable to provide one is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene.
The present invention also aims to provide containing and three thiophene-thiophene is coughed up and the preparation method of two (diazosulfide) copolymer and application.
First aspect, the invention provides a kind of containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer, for having the copolymer p of below formula:
In formula, R1, R2For C1~C20Alkyl, R3, R4For H or C1~C20Alkyl, n is the integer between 1～100.
Provided by the invention containing and three thiophene-thiophene is coughed up and coughs up also two (diazosulfide) unit containing new thiophene in the structure of two (diazosulfide) copolymer, diazosulfide unit is common functional unit, there is the reduction reversibility of excellence, close with the work function value of the metallic cathode such as magnesium, aluminum, belong to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, it is excellent in body unit, there is good electronic transport property, the energy gap of material can also be regulated simultaneously, and thiophene is coughed up in construction unit and existedConjugation so that the minimum occupied orbital energy level (LUMO) that thiophene coughs up unit is relatively low so that it is have good electron affinity and electron mobility simultaneously.The new thiophene coughed up containing benzene 1,4-Dithiapentalene-thiophene and contain in two (diazosulfide) copolymer of the present invention is coughed up and two (diazosulfide) copolymer unit combines the architectural feature of both the above unit, there is narrower band gap and stronger conjugated nature, make copolymer have the electronic transmission performance of excellence, 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, good heat stability and filming performance, therefore, thiophene-based organic photoelectrical material is a up-and-coming material of class, application in fields such as organic solar batteries has been widely studied, and also three thiophene units have three five-membered ring structures, there is narrow band gap and strong conjugated nature, in the photoelectric material such as extensive use at present and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
The present invention obtain having on the basis of both the above unit novel planar conjugated structure containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer, there is carrier mobility ability and the configuration flexibility of excellence, have a extensive future.
Second aspect, the invention provides containing and three thiophene-thiophene is coughed up and the preparation method of two (diazosulfide) copolymer, including following operating procedure:
Thering is provided compound A and compound B, the structural formula of compound A and B is respectively as follows:
In formula, R1, R2For C1~C20Alkyl, R3, R4For H or C1~C20Alkyl；
In atmosphere of inert gases, described compound A and compound B is dissolved in organic solvent by 1:1.5 ~ 1.5:1 in molar ratio, add catalyst, Stille coupled reaction is carried out 6 ~ 100 hours at 50 DEG C ~ 120 DEG C, separate and obtain after purification containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer, described containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is the copolymer p with below formula:
In formula, n is the integer between 1 ~ 100.
The reaction equation of Stille coupled reaction is:
Preferably, described catalyst is organic palladium catalyst, is three (dibenzalacetone) two palladium (Pd2(dba)3), tetrakis triphenylphosphine palladium (Pd (PPh3)4) or two (triphenylphosphine) palladium chloride (Pd (PPh3)2Cl2).It is highly preferred that described catalyst is two (triphenylphosphine) palladium chloride (Pd (PPh3)2Cl2).
Preferably, the mole dosage of described catalyst is the 0.5% ~ 20% of the amount of substance of compound A.
Preferably, described noble gas is nitrogen or argon.
Preferably, described organic solvent is the one in oxolane, glycol dimethyl ether, benzene and toluene.Described solvent is enough.
Preferably, the operating process of described preparation method is: mixed with compound B and organic solvent by compound A, evacuation deoxygenation is also filled with noble gas, add catalyst, it is heated to 50 ~ 120 DEG C, response time is 6 ~ 100 hours, and reaction terminates, and obtains containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer after separating purification.
Preferably, the operation of described separation purification is: after reaction, in reactant liquor, add deionized water and toluene extracts, take organic facies, add after decompression distillation in dehydrated alcohol, precipitate out precipitation, sucking filtration, pressed powder is obtained after drying, after pressed powder being dissolved with chloroform, with toluene for eluent, it is easily separated with silica gel column chromatography, settle with methanol after chromatographic solution decompression distillation, sucking filtration, gained solid acetone extracts three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum filtration is overnight, obtain containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer.
The preparation method of described compound A includes following operating procedure:
(1), 4-Nitrobenzol-1,2-diamidogen reacts with thionyl chloride and pyridine, separate obtain 5-nitro-2,1,3 diazosulfide, reaction equation is:
Preferably, described 4-Nitrobenzol-1,2-diamidogen: the molal volume of thionyl chloride is 50:1 than the volume ratio for 1.5:1mol/L, described thionyl chloride and pyridine, and the temperature of described reaction is 80 ~ 90 DEG C, and the time is 24h.
(2), 5-nitro-2,1,3 diazosulfide and hydrobromic acid and bromine generation bromination reaction, obtain 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide, reaction equation is:
Preferably, described hydrobromic mass fraction is 40%, 5-nitro-2,1,3 diazosulfides and hydrobromic molal volume than for 4:1mol/L, described 5-nitro-2,1,3 diazosulfides: the molal volume of bromine is than for 5.3:1mol/L, and described reaction temperature is 127 DEG C, and the response time is 4h.
(3), 4,7-bis-bromo-5-nitro-2, there is coupling reaction in 1,3 diazosulfide, obtain 4 under copper powder catalysis, 4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide, reaction equation is:
Preferably, described 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described reaction temperature is 120 DEG C, and the response time is 3 hours.
(4), 4,4 '-two bromo-6, the nitro in 6 '-dinitro-Lian 2,1,3 diazosulfide is through stannum dichloride (SnCl2) be reduced to amino after, under hydrochloric acid existent condition, carry out diazo-reaction with sodium nitrite, then react with potassium iodide, obtain 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction equation is:
Preferably, described 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide: the mol ratio of stannum dichloride 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 '-dinitro-Lian 2,1,3 diazosulfides: the mol ratio of the hydrogen chloride (HCl) in hydrochloric acid is 0.92:1,4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfides: the mol ratio of sodium nitrite is 0.53:1, the temperature of described diazo-reaction is less than 5 DEG C, and the time is 30min；Described 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide: the mol ratio of potassium iodide is 0.054:1, the described time reacted with potassium iodide is 12h.
(5), the compound C as shown in formula C is provided, wherein, R1, R2For C1~C20Alkyl；
In dimethylformamide (DMF) solvent and under oxygen free condition, 4,4 '-two bromo-6 at-90 DEG C, 6 '-two iodo-2,1,3 diazosulfides react with n-BuLi, then at room temperature react with compound C, obtain compound A, and reaction equation is:
Preferably, described n-BuLi and 4, the mol ratio of 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides is x, 2≤x 4, described compound C and 4, and the mol ratio of 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides is 2:1.Preferably, the described time reacted with n-BuLi is 2h, and described is 10h with the compound C time reacted.
In an embodiment, for convenience of statement, compound A uses compound A1, A2, A3 etc. to represent respectively, and compound C uses compound C1 respectively, C2, and C3 etc. represents, name is all as the criterion with the title in each embodiment.
The preparation method of described compound B includes following operating procedure:
Compound D is provided, wherein, R3, R4For H or C1~C20Alkyl:
Under inert gas shielding, compound D is added in oxolane (THF), is cooled to-78 DEG C; n-BuLi is added under-78 DEG C of conditions; compound D: the mol ratio of n-BuLi is 1:2, stirring reaction 1 ~ 2h, adds tributyltin chloride (SnBu under-78 DEG C of conditions3Cl), compound D: the mol ratio of tributyltin chloride is 1:2, react 1 hour at-78 DEG C, then heat to room temperature, react 6 hours, after separation, obtain compound B, reaction equation is:
Preferably, described noble gas is nitrogen or argon.
In an embodiment, for convenience of statement, compound B uses compound B-11, B2, B3 respectively, and B4 etc. represents, compound D uses compound D1 respectively, D2, D3, and D4 etc. represents, 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) copolymer, cough up containing also three thiophene-thiophene and two (diazosulfide) copolymer is used for preparing polymer solar cell device and organic electroluminescence device.Described containing and three thiophene-thiophene cough up and two (diazosulfide) copolymer as described in relation to the first aspect.
One provided by the invention coughs up also two (diazosulfide) copolymer and preparation method thereof and application containing also three thiophene-thiophene, has the advantages that
1, the present invention containing and three thiophene-thiophene cough up and two (diazosulfide) copolymer in, thiophene is coughed up and two (diazosulfide) unit has the advantages such as simple in construction, symmetry, electron delocalization performance be good, and be planar structure, it it is a kind of very excellent donor material, be combined with also three thiophene units and form the copolymer material with 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 expanding sunlight absorption region, improve electricity conversion；
2, provided by the invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer contains new thiophene and coughs up also two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it it is planar conjugate structure simultaneously, carrier mobility speed is high, carrier can be improved and arrive ratio and the charge collection efficiency of electrode, thus improving energy conversion efficiency, and can pass through to introduce alkyl and improve dissolubility and the molecular weight of copolymer, be conducive to film forming to process, and preparation method is simply ripe；
3, reaction condition is gentle, it is easy to control, and productivity 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.
Detailed description of the invention
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 making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Involved in the present invention coughs up and two (diazosulfide) copolymer containing also three thiophene-thiophene, for having the copolymer p of below formula:
In formula, R1, R2For C1~C20Alkyl, R3, R4For H or C1~C20Alkyl, n is the integer between 1～100.
Embodiment 1
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely { 3 are gathered, 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) } (n=53), and it being 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) includes following operating procedure:
(1) preparing compound 5-nitro-2,1,3 diazosulfide, reaction equation is:
There-necked flask adds 4-Nitrobenzol-1,2-diamidogen (22.95g, 0.15mol) and 100mL thionyl chloride, stirring slowly dropping 2mL pyridine, in 80 ~ 90 DEG C of back flow reaction 24h, stopped reaction after heating, after heating steams excessive thionyl chloride to 80 DEG C of rotations, product being cooled to room temperature, is poured in a large amount of water, stirring, filtration, washing final vacuum dry, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productivity 80%.
(2) preparing bromo-5-nitro-2 of compound 4,7-bis-, 1,3 diazosulfide, reaction equation is:
There-necked flask adds 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and the hydrobromic acid 15mL that mass fraction is 40%, it is warming up to 127 DEG C of backflows, in 30min, slowly drips bromine 11.3mL the 4h that refluxes, heat filtering, refilters after filtrate cooling, and solid is with substantial amounts of water washing and dries, with glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, product 4 is obtained, the bromo-5-nitro-2 of 7-bis-, 1,3 diazosulfide 10.2g, productivity 50%.
(3) 4 are prepared, 4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide, reaction equation is:
4 are added in there-necked flask, the bromo-5-nitro-2 of 7-bis-, 1, 3 diazosulfide (10.2g, 30mmol), the copper powder of 9.5g and 90mLN, dinethylformamide (DMF), heat after reacting 3 hours to 120 DEG C, stopped reaction, it is 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 dries, filter, rotation is evaporated, use dehydrated alcohol recrystallization, obtain product 4, 4 '-two bromo-6, 6 '-dinitro-Lian 2, 1, 3 diazosulfide 4.7g, productivity 30.2%.
(4) 4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction equation is:
In there-necked flask, add 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide (10.3g, 20mmol), add the 300mL tetrahydrofuran THF dried, add 40g stannum dichloride (SnCl2) (200mmol), it is warming up to 100 DEG C, it is heated to reflux 10h, stopped reaction, cooling, adjusting pH value to 8.0 with sodium hydroxide solution, absolute ether extracts, and gained organic layer is steamed in rotation, obtain solid crude product, being 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 controls below 5 DEG C, solution is yellow, after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassium iodide adds 100mL water and obtains liquor kalii iodide), is stirred vigorously, reacts 12h.Stopped reaction, adjusts pH value to 7.0 with sodium hydroxide solution, extracts with absolute ether, organic layer is washed, and anhydrous magnesium sulfate dries, and filters, rotation is evaporated filtrate, carries out silica gel column chromatography separation with petroleum ether for eluent, then carries out recrystallization with methanol, obtain 4.1g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, productivity is 30%.
(5) structural formula such as the compound C1 shown in formula C1, i.e. dioctyl dichlorosilane are provided;
There-necked flask adds 4,4 '-two bromo-6,6 '-two iodo-2,1,3 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-BuLi, within 0.5 hour, drip off, control temperature and be-90 DEG C, stirring reaction 2 hours at-90 DEG C, add 4.73mL compound C1(10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, extracts with absolute ether after reactant liquor is washed, obtains organic layer, add anhydrous sodium sulfate to dry, filter, decompression distillation, for eluent, surplus materials after distillation is carried out silica gel column chromatography separation with petroleum ether, 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), productivity 65%, reaction equation is:
The structured testing data of compound A1 are as follows:
1HNMR(CDCl3) δ (TMS, ppm): 8.08(d, 2H), 1.30-1.42(m, 28H), 0.93(d, 6H)；
13CNMR(CDCl3) 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, the preparation method of 6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (B1) comprises the following steps:
Thering is provided compound D1, i.e. 3,5-dioctyl-2,6-dibromo is [3,2-b:4,5-b '] three thiophene also；
Under the protection of nitrogen, compound D1 (5.79g is added in there-necked flask, 0.01mol) with 60mL oxolane, slowly inject the hexane solution (2.5M of 8.0mL n-BuLi 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), rise to after reacting 1 hour and reaction 6 hour is stirred at room temperature, in there-necked flask, add saturated sodium-chloride water solution 30mL terminate reaction, extract with absolute ether, obtain organic layer, add anhydrous sodium sulfate to be dried, after sucking filtration, filtrate collection rotation are evaporated ether, obtain crude product, it is eluent with petroleum ether, with neutral alumina chromatographic column, crude product is easily separated purification, obtain product 3, 5-dioctyl-2, 6-bis-(tributyl tin) [3, 2-b:4, 5-b '] three thiophene (B1), productivity 68%, reaction equation is:
(3), gathering { 3,5-dioctyls are [3,2-b:4,5-b '] three thiophene-6 also, and 6 dioctyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (P1), reaction equation is:
Under nitrogen protection; round-bottomed flask adds the compound B-11 (199.8mg that step (two) prepares; 0.2mmol), the compound A1 (136.2mg that step () prepares; 0.2mmol) with oxolane 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd (PPh3)2Cl2(5mg, 7.12 × 10-3Mmol), 90 DEG C of reaction 72h it are heated to.
After reaction terminates, add deionized water to round-bottomed flask and toluene extracts, take out organic facies, decompression is distilled to about 5mL, it is added dropwise in 400mL dehydrated alcohol and is stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, pressed powder chloroform is dissolved, silica gel column chromatography separation is carried out for eluent with toluene, chromatographic solution decompression is distilled off organic solvent, settle with methanol, sucking filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, 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).
By gained poly-{ 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) carry out gel chromatography (GPC) test, recording number-average molecular weight Mn=51410, n=53, polymer monodispersity coefficient is 2.4.
Embodiment 2
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely { 3 are gathered, 5-bis-(AI3-28404 base) [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), and it being 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 the preparation method of [3,2-e:4,5-e] two (diazosulfide) (A2) and is included following operating procedure:
4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides according to (1)-(4) step of embodiment 1 step ().
Structural formula such as the compound C2 shown in formula C2, i.e. dimethyldichlorosilane are provided.
There-necked flask adds 4,4 '-two bromo-6,6 '-two iodo-2,1,3 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-BuLi, within 0.5 hour, drip off, control temperature and be-90 DEG C, stirring reaction 2 hours at-90 DEG C, add 10mmol compound C2, rise to room temperature, stirring reaction 10 hours.Stopped reaction, extracts with absolute ether after reactant liquor is washed, obtains organic layer, add anhydrous sodium sulfate to dry, filter, decompression distillation, for eluent, surplus materials after distillation is carried out silica gel column chromatography separation with petroleum ether, obtaining 3.38g product 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) (A2), productivity 70%, reaction equation is:
The structured testing data of compound A2 are as follows:
1HNMR(CDCl3) δ (TMS, ppm): 8.08(d, 2H), 0.68(d, 6H)；
13CNMR(CDCl3) δ (TMS, ppm): 160.3,155.8,140.0,136.3,134.2,114.5 ,-1.8.
(2), the preparation method of 3,5-bis-(AI3-28404 base)-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (B2) comprises the following steps:
The structural formula such as compound D2 shown in formula D2, i.e. 3,5-bis-(AI3-28404 base)-2,6-dibromo also [3,2-b:4,5-b '] three thiophene are provided；
Under the protection of nitrogen, compound D2 (9.15g is added in there-necked flask, 0.01mol), add the oxolane of 90mL, slowly inject the hexane solution (2.5M of 8.0mL n-BuLi 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), it is warming up under room temperature after reacting 1 hour stirring reaction 6 hours, reacted reactant liquor adds termination reaction in 30mL saturated sodium-chloride water solution, extract with absolute ether, anhydrous sodium sulfate layer dries, after sucking filtration, filtrate collection rotation are evaporated absolute ether, obtain crude product, it is eluent with petroleum ether, crude product is carried out neutral alumina column chromatography for separation, obtain 3, 5-bis-(AI3-28404 base)-2, 6-bis-(tributyl tin) [3, 2-b:4, 5-b '] three thiophene (B2), productivity 74%, reaction equation is:
(3), preparation method poly-{ 3,5-bis-(AI3-28404 bases) [3,2-b:4,5-b '] three thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (P2) comprises the following steps:
Under argon shield; compound B2 (267mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compound A2 (136.2mg that prepared by step (); 0.2mmol) with glycol dimethyl ether 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd (PPh3)4(5mg, 4.33 × 10-3Mmol), 70 DEG C of reaction 36h it are heated to.
After reaction, in round-bottomed flask, add deionized water and toluene extracts, take organic facies, decompression is distilled to about about 6mL, instilled in 500mL dehydrated alcohol and be stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, pressed powder chloroform is dissolved, it is that eluent carries out silica gel column chromatography separation with toluene, chromatographic solution decompression is distilled off organic solvent, sucking filtration after settling with methanol, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, gathered { 3, 5-bis-(AI3-28404 base) [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 equation is as follows:
To poly-{ 3,5-bis-(AI3-28404 base) [3,2-b:4,5-b '] three thiophene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfides) (P2) carry out gel chromatography (GPC) test, recording number-average molecular weight Mn=32190, n=29, monodispersity coefficient is 2.7.
Embodiment 3
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely { 3 are gathered, 5-dioctyl also [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) } (n=65), and it being designated as copolymer p 3, structural formula is as follows:
Preparation method comprises the following steps:
(1), 6,6-bis-(AI3-28404 base)-4,8-dibromo thiophene is coughed up also the preparation method of [3,2-e:4,5-e] two (diazosulfide) (A3) and is included following operating procedure:
4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides according to (1)-(4) step of embodiment 1 step ().
The structural formula such as compound C3 shown in formula C3, i.e. two (AI3-28404 base) dichlorosilane are provided.
There-necked flask adds 4,4 '-two bromo-6,6 '-two iodo-2,1,3 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-BuLi, within 0.5 hour, drip off, control temperature and be-90 DEG C, stirring reaction 2 hours at-90 DEG C, add 4.93mL compound C3(10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, extracts with absolute ether after reactant liquor is washed, obtains organic layer, add anhydrous sodium sulfate to dry, filter, decompression distillation, for eluent, surplus materials after distillation is carried out silica gel column chromatography separation with normal hexane/dichloromethane mixed solvent that volume ratio is 10:1, obtain 2.79g product 6,6-bis-(AI3-28404 base)-4,8-dibromo thiophene and cough up also [3,2-e:4,5-e] two (diazosulfide) (A3), productivity 55%, reaction equation is:
The structured testing data of compound A-13 are as follows:
1HNMR(CDCl3) δ (TMS, ppm): 8.08(d, 2H), 1.47(d, 4H), 1.27-1.35(m, 72H) 0.95(d, 6H)；
13CNMR(CDCl3) δ (TMS, ppm): 160.3,155.8,140.0,136.3,134.2,114.5,33.0,31.8,29.6,29.3,24.0,22.9,14.0,13.7.
(2), 3,5-dioctyl-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (B1) are prepared: concrete operations are with embodiment 1 step (two).
(3) preparation method poly-{ 3,5-dioctyls are [3,2-b:4,5-b '] three thiophene-6 also, and 6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (P3) comprises the following steps:
Under nitrogen protection; in round-bottomed flask, add step (two) compound B-11 (199.8mg, 0.2mmol) prepared, compound A-13 (203.4mg, 0.2mmol) prepared by step () and toluene 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd2(dba)3(5mg, 5.45 × 10-3Mmol), 80 DEG C of reaction 48h it are heated to.
After reaction terminates, in round-bottomed flask, add deionized water and toluene extracts, take organic facies, decompression is distilled to about about 5mL, it is added dropwise in 400mL dehydrated alcohol and is stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, pressed powder chloroform is dissolved, it is that eluent carries out silica gel column chromatography separation with toluene, chromatographic solution decompression is distilled off organic solvent, settle with methanol, sucking filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, gathered { 3, 5-dioctyl also [3, 2-b:4, 5-b '] three thiophene-6, 6 two (AI3-28404 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P3), reaction equation is as follows:
To poly-{ 3,5-dioctyl also [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) (P3) carry out gel chromatography (GPC) test, recording number-average molecular weight Mn=84890, n=65, monodispersity coefficient is 3.1.
Embodiment 4
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely gather and [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (n=35), being designated as copolymer p 4, structural formula is as follows:
(1), preparation 6,6-bis-(AI3-28404 base)-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step () in embodiment 3.
(2), the preparation method of 2,6-bis-(tributyl tins) [3,2-b:4,5-b '] three thiophene (B3) comprises the following steps:
The structural formula such as compound d3 shown in formula D3, i.e. 2,6-dibromos also [3,2-b:4,5-b '] three thiophene are provided；
Under the protection of nitrogen, compound d3 (3.54g is added in there-necked flask, 0.01mol) with 40mL oxolane, slowly inject the hexane solution (2.5M of 8.0mL n-BuLi 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), rise to after reacting 1 hour and reaction 6 hour is stirred at room temperature, in there-necked flask, add saturated sodium-chloride water solution 30mL terminate reaction, extract with absolute ether, obtain organic layer, add anhydrous sodium sulfate to be dried, after sucking filtration, filtrate collection rotation are evaporated ether, obtain crude product, it is eluent with petroleum ether, with neutral alumina chromatographic column, crude product is easily separated purification, obtain product 2, 6-bis-(tributyl tin) [3, 2-b:4, 5-b '] three thiophene (B3), productivity 58%, reaction equation is as follows:
(3) preparation method of, poly-{ and [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } (P4) includes following operating procedure:
Under nitrogen protection; round-bottomed flask adds compound B3 (154.8mg prepared by step (two); 0.2mmol), compound A-13 (203.4mg prepared by step (); 0.2mmol) with benzene 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd (PPh3)2Cl2(28.08mg, 0.04mmol), is heated to 90 DEG C of reaction 72h.
After reaction terminates, add deionized water to round-bottomed flask and toluene extracts, take out organic facies, decompression is distilled to about 5mL, it is added dropwise in 400mL dehydrated alcohol and is stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, dissolve with chloroform, it is that eluent carries out silica gel column chromatography separation with toluene, chromatographic solution decompression is distilled off organic solvent, settle with methanol, sucking filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, obtain product poly-{ and [3, 2-b:4, 5-b '] three thiophene-6, 6 two (AI3-28404 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P4), reaction equation is:
Gained is gathered and [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs 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
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely { 3 are gathered, 5-bis-(AI3-28404 base) [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfides) } (n=100), and it being designated as copolymer p 5, structural formula is as follows:
(1), preparation 6,6-bis-(AI3-28404 base)-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) (A3):
Concrete operations are with the step () in embodiment 3.
(2), preparation 3,5-bis-(AI3-28404 base)-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (B2):
Concrete operations are with the step (two) in embodiment 2.
(3), poly-{ 3,5-bis-(AI3-28404 bases) [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) } preparation method of (P5) includes following operating procedure:
Under nitrogen protection; round-bottomed flask adds compound B2 (400.5mg prepared by step (two); 0.3mmol), compound A-13 (203.4mg prepared by step (); 0.2mmol) with oxolane 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd (PPh3)2Cl2(28.04mg, 3.99 × 10-2Mmol), 120 DEG C of reaction 100h it are heated to.
After reaction terminates, add deionized water to round-bottomed flask and toluene extracts, take out organic facies, decompression is distilled to about 5mL, it is added dropwise in 400mL dehydrated alcohol and is stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, dissolve with chloroform, it is that eluent carries out silica gel column chromatography separation with toluene, chromatographic solution decompression is distilled off organic solvent, settle with methanol, sucking filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, obtain product poly-{ 3, 5-bis-(AI3-28404 base) [3, 2-b:4, 5-b '] three thiophene-6, 6 two (AI3-28404 base) thiophene coughs up also [3, 2-e:4, 5-e] two (diazosulfides) } (P5), reaction equation is:
By gained poly-{ 3,5-bis-(AI3-28404 base) [3,2-b:4,5-b '] three thiophene-6,6 two (AI3-28404 base) thiophene coughs 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
One is coughed up and two (diazosulfide) copolymer containing also three thiophene-thiophene, namely { 3 are gathered, 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) } (n=1), and it being designated as copolymer p 6, structural formula is as follows:
Preparation method comprises the following steps:
(1), preparing 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) (A2) concrete operations with the step () in embodiment 2.
(2), 3,5-dimethyl-2, the preparation method of 6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (B4) comprises the following steps:
There is provided the structural formula such as compound D4 shown in formula D4, i.e. 3,5-dimethyl-2,6-dibromo is [3,2-b:4,5-b '] three thiophene also；
Under the protection of nitrogen, compound D4 (3.82g is added in there-necked flask, 0.01mol) with 40mL oxolane, slowly inject the hexane solution (2.5M of 8.0mL n-BuLi 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), rise to after reacting 1 hour and reaction 6 hour is stirred at room temperature, in there-necked flask, add saturated sodium-chloride water solution 30mL terminate reaction, extract with absolute ether, obtain organic layer, add anhydrous sodium sulfate to be dried, after sucking filtration, filtrate collection rotation are evaporated ether, obtain crude product, it is eluent with petroleum ether, with neutral alumina chromatographic column, crude product is easily separated purification, obtain product 3, 5-dimethyl-2, 6-bis-(tributyl tin) [3, 2-b:4, 5-b '] three thiophene (B4), productivity 60%, reaction equation is as follows:
(3) preparation method poly-{ 3,5-dimethyl are [3,2-b:4,5-b '] three thiophene-6 also, and 6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (P6) comprises the following steps:
Under nitrogen protection; compound B4 (160.4mg prepared by step (two) is added in round-bottomed flask; 0.2mmol), the compound A2 (145.2mg that prepared by step (); 0.3mmol) with tetrahydrofuran solvent 40mL; evacuation deoxygenation is also filled with nitrogen, is subsequently adding Pd (PPh3)2Cl2(1.052mg, 0.0015mmol), is heated to 50 DEG C of reaction 6h.
After reaction terminates, in round-bottomed flask, add deionized water and toluene extracts, take organic facies, decompression is distilled to about about 5mL, it is added dropwise in 400mL dehydrated alcohol and is stirred continuously, solid precipitation is had to precipitate out, sucking filtration, pressed powder is obtained after drying, pressed powder chloroform is dissolved, it is that eluent carries out silica gel column chromatography separation with toluene, chromatographic solution decompression is distilled off organic solvent, settle with methanol, sucking filtration, gained solid uses acetone extraction three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum pump sucking filtration is overnight, 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 equation is as follows:
Poly-{ 3,5-dimethyl are [3,2-b:4,5-b '] three thiophene-6 also, and 6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) } (P6) is carried out gel chromatography (GPC) test, records number-average molecular weight Mn=577, n=1.
Embodiment 7
With the embodiment of the present invention prepare containing and three thiophene-thiophene cough up and two (diazosulfide) copolymer for active layer, prepare polymer solar cell device, including the substrate of glass 1 stacked gradually, anode 2, middle auxiliary layer 3, active layer 4 and negative electrode 5, this device architecture specifically can be briefly described as: substrate of glass/anode/centre auxiliary layer/active layer/negative electrode, sees Fig. 1.Wherein, anode 2 is tin indium oxide (ITO) that square resistance is 10 Ω/, the material of middle auxiliary layer 3 is poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) composite, being expressed as PEDOT:PSS(trade name is CLEVIOSPVPAl4083)；The material of active layer 4 includes electron donor material and electron acceptor material, electron donor material be the embodiment of the present invention prepare containing and three thiophene-thiophene cough up and two (diazosulfide) copolymer, electron acceptor material is [6,6] phenyl-C61-methyl butyrate (PCBM)；The material of negative electrode 5 is aluminum.
Wherein, substrate of glass 1, as bottom, can choose ito glass, with ITO layer as anode 2, commercially available, and thickness is 1.1mm, after ultrasonic waves for cleaning, processes with oxygen plasma (oxygen-Plasma)；Then being coated with PEDOT:PSS on ito glass, obtain middle auxiliary layer 3, thickness is 110nm；Prepared by the 10mg embodiment of the present invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is dissolved in 0.4mL dimethylbenzene, obtain solution 1,8mgPCBM is dissolved in 0.4mL chlorobenzene and obtains solution 2, to be spun on middle auxiliary layer after solution 1 and solution 2 mix homogeneously, obtaining active layer 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.Containing the present invention containing and three thiophene-thiophene is coughed up and the preparation method of polymer solar cell device of two (diazosulfide) copolymer and structure are not limited to the present embodiment, it is possible to device is suitably modified or modifies.
Respectively using embodiment 1,2 and 3 preparation containing and three 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 layer, obtaining device 1,2 and 3, all preparation process all carry out in the glove box providing nitrogen inert atmosphere.
By the I-E characteristic of Keithley236 current/voltage source-measurement system and test polymer solar cell device, obtain performance data in Table 1.
Table 1 with the present invention containing and the performance data of three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is prepared for active layer polymer solar cell device
As seen from the data in Table 1, using the energy conversion efficiency containing the also polymer solar cell device that three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is prepared as active layer of the present invention for 0.92 ~ 1.25.Show the present invention containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is owing to coughing up and two (diazosulfide) conjugate unit containing new thiophene, its absorption spectrum generation red shift, high with the matching degree of solar spectrum, it it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve carrier and arrive ratio and the charge collection efficiency of electrode, thus improving energy conversion efficiency, by to the improvement of device architecture or modification, it is possible to obtain higher energy conversion efficiency.
Embodiment 8
With the copolymer p 1 of embodiment 1 preparation for luminescent layer, prepare organic electroluminescence device, including 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, particularly as follows: glass substrate/transparent anode/anode buffer layer/luminescent layer/cathode buffer layer/negative electrode, is shown in Fig. 2, but the structure of practical devices is not limited to this.Wherein, each layer material and thickness is: transparent anode 2 is tin indium oxide (ITO) (thickness is 150nm) that square resistance is 10 Ω/, the material of anode buffer layer 3 is poly-(3, 4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) composite (PEDOT:PSS, commodity are called CLEVIOSPVPAl4083), thickness is 30nm, the copolymer p 1(thickness that the material of luminescent layer 4 is the embodiment of the present invention 1 preparation is 90nm), the material of cathode buffer layer 5 is LiF(thickness is 1.5nm), the material of negative electrode 6 is metal Al(thickness is 150nm).
Measured system (Keithley2400Sourcemeter) by Keithley source and test the current versus brightness-voltage characteristic of above-mentioned organic electroluminescence device, with JY company of France its electroluminescent spectrum of SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 12.5cd/A, and high-high brightness is 1160cd/m2。
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 making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1. cough up and two (diazosulfide) copolymer containing also three thiophene-thiophene for one kind, it is characterised in that for having the copolymer p of below formula:
In formula, R1, R2For C1～C20Alkyl, R3, R4For H or C1～C20Alkyl, n is the integer between 1～100.
2. one kind containing and three thiophene-thiophene is coughed up and the preparation method of two (diazosulfide) copolymer, it is characterised in that include following operating procedure:
Thering is provided compound A and compound B, the structural formula of compound A and B is respectively as follows:
In formula, R1, R2For C1～C20Alkyl, R3, R4For H or C1～C20Alkyl；
In atmosphere of inert gases, described compound A and compound B is dissolved in organic solvent by 1:1.5～1.5:1 in molar ratio, add catalyst, Stille coupled reaction is carried out 6～100 hours at 50 DEG C～120 DEG C, separate and obtain after purification containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer, described containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer is the copolymer p with below formula:
In formula, n is the integer between 1～100.
3. as claimed in claim 2 containing the preparation method that also three thiophene-thiophene coughs up also two (diazosulfide) copolymer, it is characterised in that the preparation method of described compound A includes following operating procedure:
(1) 4-Nitrobenzol-1,2-diamidogen reacts with thionyl chloride and pyridine, separates and obtains 5-nitro-2,1,3 diazosulfide, and reaction equation is:
Described 4-Nitrobenzol-1,2-diamidogen: the molal volume of thionyl chloride is 50:1 than the volume ratio for 1.5mol:1L, described thionyl chloride and pyridine, and the temperature of described reaction is 80～90 DEG C, and the time is 24h；
(2) 5-nitro-2,1,3 diazosulfide and hydrobromic acid and bromine generation bromination reaction, obtain 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide, and reaction equation is:
Described hydrobromic mass fraction is 40%, 5-nitro-2,1,3 diazosulfides and hydrobromic molal volume than for 4mol:1L, described 5-nitro-2,1,3 diazosulfides: the molal volume of bromine is than for 5.3mol:1L, and described reaction temperature is 127 DEG C, and the response time is 4h；
(3) by 4,7-bis-bromo-5-nitro-2, there is coupling reaction in 1,3 diazosulfide, obtain 4 under copper powder catalysis, and 4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide, reaction equation is:
Described 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described reaction temperature is 120 DEG C, and the response time is 3 hours；
(4) 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1, nitro in 3 diazosulfides is reduced to after amino through stannum dichloride, carries out diazo-reaction with sodium nitrite, then react with potassium iodide under hydrochloric acid existent condition, obtain 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, reaction equation is:
Described 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide: the mol ratio of stannum dichloride 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 '-dinitro-Lian 2,1,3 diazosulfides: in hydrochloric acid, the mol ratio of hydrogen chloride is 0.92:1,4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfides: the mol ratio of sodium nitrite is 0.53:1, the temperature of described diazo-reaction is less than 5 DEG C, and the time is 30min；Described 4,4 '-two bromo-6,6 '-dinitro-Lian 2,1,3 diazosulfide: the mol ratio of potassium iodide is 0.054:1, the described time reacted with potassium iodide is 12h；
(5) the compound C as shown in formula C is provided, wherein, R1, R2For C1～C20Alkyl；
In solvent dimethylformamide and under oxygen free condition, 4,4 '-two bromo-6 at-90 DEG C, 6 '-two iodo-2,1,3 diazosulfides react with n-BuLi, then at room temperature react with compound C, obtain compound A, and reaction equation is:
Described n-BuLi 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, the mol ratio of 6 '-two iodo-2,1,3 diazosulfides is 2:1, the described time reacted with n-BuLi is 2h, and described is 10h with the compound C time reacted.
4. as claimed in claim 2 containing the preparation method that also three thiophene-thiophene coughs up also two (diazosulfide) copolymer, it is characterised in that the preparation method of compound B includes following operating procedure:
Compound D is provided, wherein, R3, R4For H or C1～C20Alkyl:
Under inert gas shielding, compound D is added in oxolane, is cooled to-78 DEG C; n-BuLi is added under-78 DEG C of conditions; compound D: the mol ratio of n-BuLi 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; react 1 hour at-78 DEG C, then heat to room temperature, react 6 hours; obtaining compound B after separation, reaction equation is:
5. as claimed in claim 2 containing the preparation method that also three thiophene-thiophene coughs up also two (diazosulfide) copolymer, it is characterized in that, described catalyst is three (dibenzalacetone) two palladium, two (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladiums.
6. as claimed in claim 2 containing the preparation method that also three thiophene thiophenes cough up also two (diazosulfide) copolymer, it is characterised in that the mole dosage of described catalyst is the 0.5%～20% of compound A mole dosage.
7. as claimed in claim 2 containing the preparation method that also three thiophene-thiophene coughs up also two (diazosulfide) copolymer, it is characterised in that described organic solvent is the one in oxolane, glycol dimethyl ether, benzene and toluene.
8. as claimed in claim 2 containing the preparation method that also three thiophene-thiophene coughs up also two (diazosulfide) copolymer, it is characterized in that, the operation of described separation purification is: after reaction, in reactant liquor, add deionized water and toluene extracts, take organic facies, add after decompression distillation in dehydrated alcohol, precipitate out precipitation, sucking filtration, pressed powder is obtained after drying, after pressed powder being dissolved with chloroform, with toluene for eluent, it is easily separated with silica gel column chromatography, settle with methanol after chromatographic solution decompression distillation, sucking filtration, gained solid acetone extracts three days in apparatus,Soxhlet's, again with methanol settles, sucking filtration, vacuum filtration is overnight, obtain containing and three thiophene-thiophene is coughed up and two (diazosulfide) copolymer.
9. cough up the application of also two (diazosulfide) copolymer containing also three thiophene-thiophene as claimed in claim 1, it is characterized in that, described containing and three thiophene-thiophene cough up and two (diazosulfide) copolymer is used for preparing polymer solar cell device or organic electroluminescence device.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010013628A (en) * | 2008-06-05 | 2010-01-21 | Sumitomo Chemical Co Ltd | Polymer compound and polymeric light-emitting device using same |
| WO2011144537A1 (en) * | 2010-05-21 | 2011-11-24 | Eni S.P.A. | Photoactive composition with a high mobility of the electronic holes |
| JP2012056990A (en) * | 2010-09-06 | 2012-03-22 | Kuraray Co Ltd | Conductive benzothiadiazole copolymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013628A (en) * | 2008-06-05 | 2010-01-21 | Sumitomo Chemical Co Ltd | Polymer compound and polymeric light-emitting device using same |
| WO2011144537A1 (en) * | 2010-05-21 | 2011-11-24 | Eni S.P.A. | Photoactive composition with a high mobility of the electronic holes |
| JP2012056990A (en) * | 2010-09-06 | 2012-03-22 | Kuraray Co Ltd | Conductive benzothiadiazole copolymer composition |
Non-Patent Citations (2)
| Title |
|---|
| Pd-Catalysed Direct Arylation Polymerisation for Synthesis of Low-Bandgap Conjugated Polymers and Photovoltaic Performance;Chang S W etal;《Macromolecular Rapid Communications》;20120731;第33卷(第22期);第1927-1932页 * |
| Synthetic Principles Directing Charge Transport in Low-Band-Gap Dithienosilole–Benzothiadiazole Copolymers;Beaujuge PM etal;《Journal of American Chemical Society》;20120518;第134卷(第21期);第8944–8957页 * |
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