CN103772656A - Benzodithiophene-benzodi(benzothiadiazole) containing copolymer, preparation and application thereof - Google Patents
Benzodithiophene-benzodi(benzothiadiazole) containing copolymer, preparation and application thereof Download PDFInfo
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- 0 *[N+](c(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O)[O-] Chemical compound *[N+](c(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O)[O-] 0.000 description 2
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Abstract
The invention provides a benzodithiophene-benzodi(benzothiadiazole) containing copolymer, preparation and application thereof. The benzodithiophene-benzodi(benzothiadiazole) containing copolymer is a compound P with a general formula shown as the specification, wherein R1 and R2 are alkyl of C1-C20, R3 and R4 are alkyl of C1-C20, alkoxy of C6-C16 or a thiophene derivative group, which has an alkyl side chain of C16, and n is an integer ranging from 1 to 100. The benzodithiophene-benzodi(benzothiadiazole) containing copolymer contains a new benzodi(benzothiadiazole) conjugated unit, the absorption spectrum of the copolymer undergoes red shift and has a high matching degree with a solar spectrum. Meanwhile, with a planar conjugated structure, the copolymer provided by the invention has the advantages of high charge carrier migration rate and high energy conversion efficiency, simple and controllable preparation method, and has good application prospects in polymer solar cells, organic light-emitting devices and other photoelectric material fields.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer and preparation and application thereof.
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, and one of reason is that the carrier mobility of polymkeric substance is than low several orders of magnitude of the mobility of inorganic monocrystal material.And the absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, it is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor, improve absorbing sun power.
The conjugated polymers that contains thiophene unit and diazosulfide unit for photoelectric material appears in the newspapers, but the effciency of energy transfer obtaining is in actual applications still lower, therefore, develop new polymer materials, improve the effciency of energy transfer of photoelectric material for the great significance of organic solar batteries.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
The present invention also aims to provide above-mentioned preparation method and application containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
First aspect, the invention provides a kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, for having the compound P of following general formula:
In formula, R
1, R
2for C
1~ C
20alkyl, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r' is C
16alkyl, n is the integer between 1 ~ 100.R
1, R
2, R
3, R
4can also be other Hete rocyclic derivatives groups, comprise the group from the heterocycles such as thiophene, diazosulfide, pyrazine, pyrroles, quinoxaline and derivative thereof.
Contain new benzo two (diazosulfide) conjugate unit of the present invention containing in benzene 1,4-Dithiapentalene-benzo two (diazosulfide) copolymer structure, diazosulfide unit is common functional unit, there is excellent reduction reversibility, with magnesium, the work content value of the metallic cathodes such as aluminium approaches, 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 simultaneously, new benzo two (diazosulfide) unit also has identity function, and correlation function is further improved.Contain thiophene five-membered ring structure unit simultaneously of the present invention containing in benzene 1,4-Dithiapentalene-benzo two (diazosulfide) copolymer structure, thiophene unit has moderate band gap, wider spectral response, thermostability and film forming properties, be widely used in organic photoelectrical material field preferably.New conjugate planes structure that what the present invention obtained on the basis of above two kinds of unit have containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, there is excellent carrier mobility ability and configuration flexibility, have a extensive future.
Contain in benzene 1,4-Dithiapentalene-benzo two (diazosulfide) copolymer structure of the present invention, substituting group is used for modifying agent structure, for example conventionally can on benzo two thiophene units, introduce heterocycle, many aromatic rings or fragrant heterocycle molecule, can increase the density of benzene 1,4-Dithiapentalene skeleton electrons cloud, improve carrier transmission performance, stability or film-forming properties, or regulate the processing characteristics such as dissolving and film forming properties of multipolymer by alkyl substituent carbonatoms.
Second aspect, the invention provides a kind of preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, comprises following operation steps:
Compd A and compd B are provided, and the structural formula of compd A and B is respectively:
In formula, R
1, R
2for C
1~ C
20alkyl, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r ' is C
16alkyl;
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 ℃ ~ 120 ℃, carry out Stille coupling reaction 6 ~ 108 hours, after separation and purification, obtain containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, described is the compound P with following general formula containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer:
In formula, n is the integer between 1 ~ 100.
The reaction formula of described Stile coupling reaction is:
Preferably, described catalyzer is organic palladium catalyzer, is three (dibenzalacetone) two palladium (Pd
2(dba)
3), tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) or bi triphenyl phosphorus palladium chloride (Pd (PPh
3)
2cl
2).
Preferably, the mole dosage of described catalyzer is compd B 0.5% ~ 20%.More preferably, the mole dosage of described catalyzer is compd B 2% ~ 3.5%.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described organic solvent is tetrahydrofuran (THF) (THF), glycol dimethyl ether (DME), dioxane or toluene, and solvent is enough.
Preferably, the operating process of described Stile coupling reaction 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 ℃, reaction times is 6 ~ 108 hours, and reaction finishes rear separating-purifying, obtains containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
Preferably, being operating as of described separation and purification: after reaction finishes, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, splash in dehydrated alcohol, separate out precipitation, suction filtration, dry, obtain pressed powder, after pressed powder being dissolved with chloroform, take toluene or sherwood oil as elutriant, carry out column chromatography for separation with neutral alumina chromatography column or silica gel column chromatography, after the underpressure distillation of gained chromatographic solution, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
Described compd A (in embodiment below, for convenience of statement, use respectively A1, A2, A3, A4, A5, A6, A7 etc. represent, name and are as the criterion with the title in each embodiment) can buy, its preparation method comprises following operation steps:
Provide structural formula suc as formula the Compound C shown in C (in embodiment below, for convenience of statement, use respectively C1, C2, C3, C4, C5 etc. represent, name is as the criterion with the title in each embodiment), wherein, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r' is C
16alkyl:
In inert atmosphere, after being mixed with tetrahydrofuran (THF), Compound C is cooled to-78 ℃, add n-Butyl Lithium (n-BuLi), the ratio of the amount of substance of Compound C and n-Butyl Lithium (n-BuLi) is 1:2, after reaction 1h, adds tributyltin chloride (SnBu
3cl), tributyltin chloride (SnBu
3cl) be 2:1 with the ratio of the amount of substance of Compound C, then be warming up to room temperature after reacting 1h, react 6 hours, separate and obtain compd A.
Reaction formula is:
Preferably, described inert atmosphere is nitrogen or argon gas.
The preparation method of described compd B (in embodiment below, for convenience of statement, use respectively B1, B2, B3 represents, name is as the criterion with the title in each embodiment) 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:
Preferably, described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/mL, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 ℃, and the time is 24h.
(2) 5-nitro-2,1,3 diazosulfide and Hydrogen bromide and bromine generation bromination reaction, obtain the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide, reaction formula is:
Preferably, described hydrobromic massfraction is 40%, 5-nitro-2,1,3 diazosulfides are 4:1mol/L with hydrobromic molecular volume ratio, described 5-nitro-2,1,3 diazosulfides: the molecular volume of bromine is than being 5.3:1mol/L, and described temperature of reaction is 127 ℃, and the reaction times is 4h.
The bromo-5-of (3) 4,7-bis-nitro-2, under copper powder catalysis, there is linked reaction in 1,3 diazosulfide, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:
Preferably, described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 ℃, the reaction times is 3 hours.
(4) 4,4 '-bis-is bromo-6, and the nitro in 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides is through tindichloride (SnCl
2) be reduced to after amino, under the condition existing at hydrochloric acid, carry out diazotization reaction with Sodium Nitrite, then react with potassiumiodide, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:
Preferably, described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1:10, the temperature of described reduction reaction is 100 ℃, the time is 10h; Described 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides: the mol ratio of hydrogenchloride in hydrochloric acid (HCl) 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 ℃, 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 Compound D (in embodiment below, for convenience of statement, use respectively D1, D2, D3 represents, name is as the criterion with the title in each embodiment), wherein, R
1, R
2for C
1~ C
20alkyl:
In solvent dimethylformamide and under oxygen free condition, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides and Compound C are at tributylamine (Bu
3and palladium (Pd (OAc) N)
2) catalysis under there is ring closure reaction, obtain compd B, reaction formula is:
Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides: the mol ratio of Compound D is 1:2, and the temperature of described reaction is 130 ℃, and the time is 4h, Compound D: tributylamine: the mol ratio of palladium is 20:20:1.
The third aspect, the invention provides a kind of application containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, be describedly applied to and prepare polymer solar cell device or organic electroluminescence device containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.Described benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer that contains is as described in first aspect present invention.
One provided by the invention, containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer and preparation method thereof and application, has following beneficial effect:
There is no at present bibliographical information and related application openly containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, it is a kind of new photoelectric material, effciency of energy transfer is high, and can utilize Stile reaction preparation, preparation method is simple and ripe, and productive rate is high, mild condition, product is easy to control, and makes its having a extensive future in field of photovoltaic materials such as polymer solar batteries.
Accompanying drawing explanation
Fig. 1 is the structural representation of the polymer solar cell device in embodiment 8.
Fig. 2 is the structural representation of the organic electroluminescence device in embodiment 9.
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 present invention relates to containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, for thering is the compound P of following general formula:
In formula, R
1, R
2for C
1~ C
20alkyl, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r ' is C
16alkyl, n is the integer between 1 ~ 100.
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, gather { 4,8-(dioctyl) oxygen base-benzo [1,2-b:4,5-b'] two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=55), be designated as copolymer p 1, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) preparation method (B1) comprises following operation steps:
(1) prepare compound 5-nitro-2,1,3 diazosulfide:
In there-necked flask, add 4-oil of mirbane-1,2-diamines (22.95g, 0.15mol) and 100mL thionyl chloride (SOCl
2), stir and slowly drip 2mL pyridine, under room temperature, 2-amino-5-N-methyl-p-nitroaniline does not all dissolve, and solution is orange, and after heating, in 80 ~ 90 ℃ of back flow reaction 24h, stopped reaction, is heated to 80 ℃ and revolves and steam excessive thionyl chloride (SOCl
2) after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
(2) prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide:
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 ℃ of backflows, in 30min, slowly drip bromine 11.3mL back flow reaction 4h, 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:
In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g and the N of 90mL, dinethylformamide (DMF), is heated to 120 ℃ of reactions after 3 hours, stopped reaction, be cooled to room temperature, add 90mL toluene, stir 30 minutes, filter, filtrate, with saturated nacl aqueous solution and water washing, merges organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, use dehydrated alcohol recrystallization, obtain product 4,4 '-bis-is 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:
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), the tetrahydrofuran (THF) (THF) that 300mL is dry and 40g tindichloride (SnCl
2) (200mmol), be warming up to 100 ℃, 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 ℃, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g is that 0.373mol potassiumiodide adds 100mL water dissolution to obtain liquor kalii iodide) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, carry out silica gel column chromatography separation take sherwood oil as elutriant, then carry out recrystallizing methanol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
(5) provide Compound D 1,2,6,13,17-tetramethyl--9-octadecyne;
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides (3.4g, 5mmol), add Compound D 1(3.07g, 10mmol), 25mL DMF, passes into nitrogen gas stirring 20min, adds Tributylamine (Bu
3n) (0.907g, 10mmol), palladium (Pd (OAc)
2) (115mg, 0.5mmol), be warming up to 130 ℃, heating 4h, cooling, after washing, with dichloromethane extraction, obtain organic layer, add anhydrous sodium sulfate drying, filter, underpressure distillation, take volume ratio as 8:1 n-hexane/ethyl acetate mixed solvent is as elutriant, separates distilling rear surplus materials with silica gel column chromatography, after dry, obtain 2.4g 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) (B1), productive rate 70%, reaction formula is:
1HNMR（CDCl
3）δ（TMS，ppm）：8.32（d，2H），3.08（dd，4H），1.83（d，2H），1.60-1.64（m，6H），1.22-1.27（m，12H）,1.08-1.10（m，18H）；
13CNMR（CDCl
3）δ（TMS，ppm）：134.0,131.8,130.2,129.9,124.9,123.6,130.0,41.0,39.7,38.0,32.6,28.5,25.6,24.2,23.0,21.0。
(2), poly-{ 4,8-(dioctyl) oxygen base-benzo [1,2-b:4,5-b'], two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P1) is as follows:
Provide structural formula suc as formula the compd A 1 shown in A1,4,8-(dioctyl) oxygen base-2,7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene, buy from Shenzhen Rui Xun photoelectric material Science and Technology Ltd.;
Under nitrogen protection; in round-bottomed flask, add structural formula suc as formula the compd A 1 (205mg shown in A1; compound B-11 (the 146.6mg that 0.2mmol), prepared by step (); 0.2mmol) with tetrahydrofuran solvent 40mL; vacuumize deoxygenation and be filled with nitrogen; then add (5mg, 0.007mmol) Pd (PPh
3)
2cl
2, be heated to 90 ℃ of reaction 72h.After reaction, 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, carry out column chromatography for separation take toluene as elutriant with neutral alumina chromatography column, organic solvent is removed in decompression, 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 { 4, 8-(dioctyl) oxygen base-benzo [1, 2-b:4, 5-b'] two thiophene-6, 7-bis-(3, 7-dimethyl octyl group)-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P1), reaction formula is as follows:
By gained poly-{ 4,8-(dioctyl) oxygen base-benzo [1,2-b:4,5-b'] two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (P1) carry out GPC test, record number-average molecular weight Mn=55990, n=55, polymkeric substance monodispersity coefficient is 1.9.
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, poly-{ 4,8-dioctyl-benzo [1,2-b:4,5-b'] two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=50), be designated as copolymer p 2, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,8-dioctyl-2, the preparation method of 7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene (A2) is as follows:
Provide structural formula suc as formula Compound C 1 shown in C1,4,8-dioctyl-2, the bromo-benzo of 7-bis-[1,2-b:4,5-b'] two thiophene;
In round-bottomed flask, add Compound C 1(11.46g, 0.02mol) and 100mL THF, under nitrogen protection; be cooled to-78 ℃, drip the hexane solution 16.8mL (2.5M, 0.04mol) of n-Butyl Lithium; react 1 hour, add 11.2mL tributyltin chloride (SnBu
3cl) (0.04mol), react and be warming up to room temperature after 1 hour, reaction 6h, stopped reaction.After adding water, with anhydrous diethyl ether extraction, get organic layer, add after anhydrous magnesium sulfate drying, separate with neutral alumina chromatography column take sherwood oil as elutriant, after being dried, obtain 13g compd A 2, productive rate 65%, reaction formula is:
(2), 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) preparation method (B1) is with the step in embodiment 1 (one).
(3), poly-{ 4,8-dioctyl-benzo [1,2-b:4,5-b'], two thiophene-6,7-dioctyl-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P2) is as follows:
Under nitrogen protection; compd A 2 (248.3mg prepared by step (); compound B-11 (the 183.3mg that 0.25mmol), prepared by step (two); 0.25mmol) add in round-bottomed flask with DME 50mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh
3)
4(6.25mg, 0.0054mmol), is heated to 90 ℃ of reaction 72h.After reaction, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 6.5mL 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, take toluene as elutriant, separate with silica gel column chromatography, organic solvent is removed in decompression, 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 { 4, 8-dioctyl-benzo [1, 2-b:4, 5-b'] two thiophene-6, 7-dioctyl-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P2), reaction formula is as follows:
By poly-gained { 4,8-dioctyl-benzo [1,2-b:4,5-b'], two thiophene-6,7-dioctyl-benzo [2,1-e:3,4-e] two (diazosulfides) } (P2) carry out GPC test, record number-average molecular weight Mn=49300, n=50, monodispersity coefficient is 2.0.
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, i.e. poly-{ 4,8-bis-(5 '-hexadecyl-2 '-thienyl)-benzo [1,2-b:4,5-b'] two thiophene-benzo [1,2-b:4,5-b'], two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=85), be designated as copolymer p 3, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,8-bis-(5 '-hexadecyl-2 '-thienyl)-2, the preparation method of 7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene (A3) is as follows:
Provide structural formula suc as formula the Compound C 2 shown in C2,4,8-bis-(5 '-hexadecyl-2 '-thienyl)-2, the bromo-benzo of 7-bis-[1,2-b:4,5-b'] two thiophene;
In round-bottomed flask, add Compound C 2 (9.61g, 0.01mol) and 100mL THF, under nitrogen protection, be cooled to-78 ℃, drip the hexane solution 8.4mL (2.5M, 0.02mol) of n-Butyl Lithium, react 1 hour, add SnBu
3cl 5.60mL(0.02mol), then react after 1 hour and be warming up to room temperature, reaction 6h, stopped reaction.After adding water, with anhydrous diethyl ether extraction, get organic layer, add after anhydrous magnesium sulfate drying, take sherwood oil as elutriant, separate with neutral alumina chromatography column, after being dried, obtain 8g compound A-13, productive rate 57.9%, reaction formula is:
(2), 4,9-bis-is bromo-6 in preparation, (B1), concrete operations are with the step in embodiment 1 (one) for 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e3,4-e] two (diazosulfides).
(3), poly-{ 4,8-bis-(5 '-hexadecyl-2 '-thienyl)-benzo [1,2-b:4,5-b'] two thiophene-benzo [1,2-b:4,5-b'], two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P3) is as follows:
Under nitrogen protection; compound A-13 (the 414.3mg that adds step () to prepare to round-bottomed flask; compound B-11 (the 219.9mg that 0.3mmol), prepared by step (two); 0.3mmol) with DME solvent 60mL; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh
3)
2cl
2(7.5mg, 0.01mmol), is heated to 90 ℃ of reactions 4.5 days.After reaction, 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 600mL 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, separate with neutral alumina chromatography column take sherwood oil as elutriant, organic solvent is removed in decompression, 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 { 4, 8-bis-(5 '-hexadecyl-2 '-thienyl)-benzo [1, 2-b:4, 5-b'] two thiophene-benzo [1, 2-b:4, 5-b'] two thiophene-6, 7-bis-(3, 7-dimethyl octyl group)-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P3), reaction formula is as follows:
To poly-{ 4,8-bis-(5 '-hexadecyl-2 '-thienyl)-benzo [1,2-b:4,5-b'] two thiophene-benzo [1,2-b:4,5-b'] two thiophene-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (P3) carry out GPC test, record number-average molecular weight Mn=116790, n=85, monodispersity coefficient is 2.0.
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, i.e. poly-{ 4,8-dimethyl-benzo [1,2-b:4,5-b '] two thiophene-6-methyl-7-propyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=1), be designated as copolymer p 4, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,8-dimethyl-2, the preparation method of 7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene (A4) is as follows:
Provide structural formula suc as formula the Compound C 3 shown in C3,4,8-dimethyl-2, the bromo-benzo of 7-bis-[1,2-b:4,5-b'] two thiophene;
In round-bottomed flask, add Compound C 3 (7.52g, 0.02mol) and 80mL THF, under nitrogen protection, be cooled to-78 ℃, drip the hexane solution 16.8mL (2.5M, 0.04mol) of n-Butyl Lithium, react 1 hour, add SnBu
3cl 11.2mL(0.04mol), then react after 1 hour and be warming up to room temperature, reaction 6h, stopped reaction.After adding water, with anhydrous diethyl ether extraction, get organic layer, add after anhydrous magnesium sulfate drying, take sherwood oil as elutriant, separate with neutral alumina chromatography column, after being dried, obtain 9g compd A 4, productive rate 56.2%, reaction formula is:
(2), 4, preparation method (B2) is as follows for the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfide):
Provide structural formula suc as formula the Compound D 2 shown in D2, i.e. 2 – hexins;
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides (6.8g, 10mmol), add Compound D 2(1.64g, 20mmol), 50mL DMF, passes into nitrogen gas stirring 20min, adds Bu
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 ℃, isothermal reaction 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, the ethyl acetate/normal hexane mixed solvent take volume ratio as 1:8 is elutriant, separates with silica gel column chromatography, obtain 2.6g 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) (B2), productive rate 60%, the reaction formula of above reaction process is:
Gained 4, the structured testing data of the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:
1HNMR（CDCl
3）δ（TMS，ppm）：8.32（d，2H），3.01（d，2H），2.63（s，3H?）,1.64（m，2H?），0.97（d，3H?）；
13CNMR（CDCl
3）δ（TMS，ppm）：134.0,131.7,130.4,129.8,124.9,123.6,130.0,30.3,25.0,16.6,13.7。
(3), poly-{ 4,8-dimethyl-benzo [1,2-b:4,5-b'], two thiophene-6-methyl-7-propyl group-benzo [2,1-e:3,4-e], two (diazosulfides) } preparation method (P4) is as follows:
Under nitrogen protection; compd A 4 (the 205mg that add step () to prepare to round-bottomed flask; 0.2mmol), step (two) compd B 2 (146.6mg, 0.3mmol) and the dioxane 40mL that prepare, then add Pd (PPh
3)
2cl
2(42mg, 0.060mmol), is heated to 50 ℃ of reaction 6h.After reaction, 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, take toluene as elutriant, separate with silica gel column chromatography, elutriant underpressure distillation is removed to organic solvent, 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 { 4, 8-dimethyl-benzo [1, 2-b:4, 5-b'] two thiophene-6-methyl-7-propyl group-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P4), reaction formula is as follows:
Poly-{ 4,8-dimethyl-benzo [1,2-b:4,5-b'], two thiophene-6-methyl-7-propyl group-benzo [2,1-e:3,4-e], two (diazosulfides) } (P4) are carried out to GPC test, record number-average molecular weight Mn=508, n=1.
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, gather { 4,8-bis-(NSC 62789 base)-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=100), be designated as copolymer p 5, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,8-bis-(NSC 62789 base)-2, the preparation method of 7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene (A5) is as follows:
Provide structural formula suc as formula the Compound C 4 shown in C4,4,8-bis-(NSC 62789 base)-2, the bromo-benzo of 7-bis-[1,2-b:4,5-b'] two thiophene;
In round-bottomed flask, add Compound C 49.09g (0.01mol) and 80mL THF, under nitrogen protection, be cooled to-78 ℃, drip the hexane solution 8.4mL (2.5M, 0.02mol) of n-Butyl Lithium, react 1 hour, add SnBu
3cl 5.60mL(0.02mol), then react after 1 hour and be warming up to room temperature, reaction 6h, stopped reaction.After adding water, with anhydrous diethyl ether extraction, get organic layer, add after anhydrous magnesium sulfate drying, separate with neutral alumina chromatography column take sherwood oil as elutriant, after being dried, obtain 8.0g compound A-45, productive rate 60.2%, reaction formula is:
(2), 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) preparation method (B3) is as follows for octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfide):
Provide structural formula suc as formula the compound d3 shown in D3,2,6-dimethyl-9-30 alkynes;
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides (6.8g, 10mmol), add compound d3 (8.94g, 20mmol), 80mL DMF, passes into nitrogen gas stirring 20min, adds Bu
3n(1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 ℃, isothermal reaction 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, the ethyl acetate/normal hexane mixed solvent take volume ratio as 1:8 is elutriant, separates with silica gel column chromatography, obtain 5.0g compd B 3, productive rate 57.3%;
The reaction formula of above reaction process is as follows:
Gained 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) structured testing data (B3) are as follows:
1HNMR（CDCl
3）δ（TMS，ppm）：8.30（d，2H），3.01（m，4H），1.85(s,1H)，1.60-1.65(m,5H),1.25-1.34（m，40H），1.01-1.07（m，12H）；
13CNMR（CDCl
3）δ（TMS，ppm）：134.0，131.9，130.3，130.1，129.9，124.9，123.8，41.5,39.9,37.8，32.8，32.2，31.9，31.6，29.7，29.3，28.5,28.1，24.2，23.0，22.7，21.0，14.3。
(3), poly-{ 4,8-bis-(NSC 62789 base)-benzo [1,2-b:4,5-b'], two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P5) is as follows:
Under argon shield; compound A-45 (the 398.7mg that adds step () to prepare to round-bottomed flask; 0.3mmol), step (two) compd B 3 (174.6mg, 0.2mmol) and the tetrahydrofuran (THF) 40mL that prepare, then add Pd (PPh
3)
2cl
2(0.7mg, 0.001mmol), is heated to 120 ℃ of reaction 108h.After reaction, 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, take toluene as elutriant, separate with silica gel column chromatography, organic solvent is removed in decompression, 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 { 4, 8-bis-(NSC 62789 base)-benzo [1, 2-b:4, 5-b'] two thiophene-6-(3, 7-dimethyl) octyl group-7-NSC 62789 base-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P5), reaction formula is as follows:
To poly-{ 4,8-bis-(NSC 62789 base)-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (P5) carry out GPC test, record number-average molecular weight Mn=146200, n=100, monodispersity coefficient is 2.5.
Embodiment 6
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, gather { 4,8-bis-(dihexyl) oxygen base-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=50), be designated as copolymer p 6, general formula is as follows:
Preparation method comprises the following steps:
(1), preparation 4,9-bis-bromo-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) (B3), concrete operations are with step (two) in embodiment 5.
(2), poly-{ 4,8-bis-(dihexyl) oxygen base-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P6) is as follows:
Provide structural formula suc as formula the compd A 6 shown in A6,4,8-(dihexyl) oxygen base-2,7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene, buy from Shenzhen Rui Xun photoelectric material Science and Technology Ltd.;
Under nitrogen protection, the compd B 3 (174.6mg, 0.2mmol) and the toluene 40mL that add compd A 6 (193.8mg, 0.2mmol), step () to prepare to round-bottomed flask, then add Pd (PPh
3)
4(5mg, 0.004mmol), is heated to 90 ℃ of reaction 72h.After reaction, 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, take toluene as elutriant, separate with silica gel column chromatography, organic solvent is removed in decompression, 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 { 4, 8-bis-(dihexyl) oxygen base-benzo [1, 2-b:4, 5-b'] two thiophene-6-(3, 7-dimethyl) octyl group-7-NSC 62789 base-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P6), reaction formula is as follows:
To poly-{ 4,8-bis-(dihexyl) oxygen base-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (P6) carry out GPC test, record number-average molecular weight Mn=55050, n=50, monodispersity coefficient is 2.1.
Embodiment 7
A kind of containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, gather { 4,8-bis-(n-hexadecane oxygen base)-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=60), be designated as copolymer p 7, general formula is as follows:
Preparation method comprises the following steps:
(1), 4,8-bis-(n-hexadecane oxygen base)-2, the preparation method of 7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene (A7) is as follows:
Provide structural formula suc as formula the Compound C 5 shown in C5,4,8-bis-(n-hexadecane oxygen base)-2, the bromo-benzo of 7-bis-[1,2-b:4,5-b'] two thiophene;
In round-bottomed flask, add Compound C 58.29g (0.01mol) and 80mL THF, under nitrogen protection, be cooled to-78 ℃, drip the hexane solution 8.4mL (2.5M, 0.02mol) of n-Butyl Lithium, react 1 hour, add SnBu
3cl 5.60mL(0.02mol), then react after 1 hour and be warming up to room temperature, reaction 6h, stopped reaction.After adding water, extract with anhydrous diethyl ether, get organic layer, add after anhydrous magnesium sulfate drying, carry out column chromatography for separation take sherwood oil as elutriant with neutral alumina chromatography column, after being dried, obtain 7.0g compd A 74,8-bis-(n-hexadecane oxygen base)-2,7-bis-(tributyl tinbase)-benzo [1,2-b:4,5-b'] two thiophene, productive rate 56.0%, reaction formula is as follows:
(2), preparation 4,9-bis-bromo-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) (B3), concrete operations are with the step in embodiment 5 (two).
(3), poly-{ 4,8-bis-(n-hexadecane oxygen base)-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P7) is as follows:
Under nitrogen protection, add compd A 7 (249.8mg, 0.2mmol) prepared by step (), compd B 3 (174.6mg, 0.2mmol) and tetrahydrofuran solvent 40mL prepared by step (two) to round-bottomed flask, then add Pd
2(dba)
3(5mg, 0.005mmol), is heated to 90 ℃ of reaction 72h.After reaction, to adding deionized water in round-bottomed flask and toluene extracts, get organic phase, underpressure distillation is to 5mL left and right, splash in 450mL dehydrated alcohol and constantly stir, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, take toluene as elutriant, separate with silica gel column chromatography, organic solvent is removed in decompression, 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 { 4, 8-bis-(n-hexadecane oxygen base)-benzo [1, 2-b:4, 5-b'] two thiophene-6-(3, 7-dimethyl) octyl group-7-NSC 62789 base-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P7), reaction formula is as follows:
To poly-{ 4,8-bis-(n-hexadecane oxygen base)-benzo [1,2-b:4,5-b'] two thiophene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (P7) carry out GPC test, record number-average molecular weight Mn=82920, n=60, monodispersity coefficient is 2.4.
Embodiment 8
What prepare take the embodiment of the present invention is active coating containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, prepare polymer solar cell device, its structure comprises the substrate of glass stacking gradually, comprise the substrate of glass 1 stacking gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, see Fig. 1.Wherein, anode 2 is ITO, that square resistance is the tin indium oxide of 10 Ω/mouths, the material of middle supplementary layer 3 is poly-(3,4-Ethylenedioxy Thiophene) and polystyrolsulfon acid matrix material, with PEDOT:PSS(commodity CLEVIOS P VP Al 4083 by name) preparation, active coating 4 comprises electron donor material and electron acceptor material, electron donor material be the embodiment of the present invention prepare containing benzene 1,4-Dithiapentalene-benzo 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, is chosen ito glass when making,, 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 preparing, thickness is 120nm; That prepared by the 10mg embodiment of the present invention is dissolved in 0.4mL dimethylbenzene and obtains solution containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer again, be dissolved in 8mg PCBM the solution blending that 0.4mL chlorobenzene obtains, be spun on middle supplementary layer, thickness is 120nm, obtains active coating 4; At vacuum condition (2 × 10
-3pa) lower evaporation metal aluminum is for negative electrode 5, and thickness is 120nm, obtains polymer solar cell device.Contain the present invention and be not limited to the present embodiment containing preparation method and the structure of the polymer solar cell device of benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, can device suitably be improved or be modified.
Prepare polymer solar cell device using benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer that contains of embodiment 1,2 and 3 preparations as the material of active coating respectively, obtain device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, obtain the performance data of device in table 1.
Table 1 is take the performance data of the polymer solar cell device prepared as active coating containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer
As seen from the data in Table 1, be 1.46 ~ 1.99 with the energy conversion efficiency of the polymer solar cell device of preparing as active coating containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer of the present invention.Show prepared by the present invention containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer owing to containing new benzo two (diazosulfide) conjugate unit, 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, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.
Embodiment 9
The copolymer p 1 of preparing take embodiment 1 is luminescent layer, be prepared with organic electroluminescence devices, its structure comprises 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, on glass substrate 1, deposit the tin indium oxide that square resistance is 10 Ω/mouths (ITO) (thickness is 150nm), as transparent anode 2, the material of anode buffer layer 3 is poly-(3, 4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) matrix material, adopt PEDOT:PSS(commodity CLEVIOS P VPAl 4083 by name) preparation, 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), the structure of practical devices is not limited to this.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 11.0cd/A, and high-high brightness is 1120cd/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. containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, it is characterized in that, for thering is the compound P of following general formula:
In formula, R
1, R
2for C
1~ C
20alkyl, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r ' is C
16alkyl, n is the integer between 1 ~ 100.
2. containing a preparation method for benzene 1,4-Dithiapentalene-benzo 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:
In formula, R
1, R
2for C
1~ C
20alkyl, R
3, R
4for C
1~ C
20alkyl, C
6~ C
16alkoxyl group or thiophene derivant group, the structural formula of described thiophene derivant group is
r ' is C
16alkyl;
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 ℃ ~ 120 ℃, carry out Stille coupling reaction 6 ~ 108 hours, after separation and purification, obtain containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer, described is the compound P with following general formula containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer:
In formula, n is the integer between 1 ~ 100.
3. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that, the preparation method of described compd B comprises following operation steps:
(1) 4-oil of mirbane-1,2-diamines reacts with thionyl chloride and pyridine, and separate and obtain 5-nitro-2,1,3 diazosulfide, reaction formula is:
Described 4-oil of mirbane-1,2-diamines: the molecular volume of thionyl chloride is than being 1.5:1mol/mL, and the volume ratio of described thionyl chloride and pyridine is 50:1, and the temperature of described reaction is 80 ~ 90 ℃, 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 ℃, and the reaction times is 4h;
(3) by bromo-4,7-bis-5-nitro-2, there is linked reaction in 1,3 diazosulfide under copper powder catalysis, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, reaction formula is:
Described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide: the mol ratio of copper powder is 0.2:1, described temperature of reaction is 120 ℃, the reaction times is 3 hours;
(4) 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides, after tindichloride is reduced to amino, carries out diazotization reaction with Sodium Nitrite under the condition existing, then react with potassiumiodide at hydrochloric acid, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, reaction formula is:
Described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides: the mol ratio of tindichloride is 1: 10, the temperature of described reduction reaction is 100 ℃, 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 ℃, 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 Compound D, wherein, R
1, R
2for C
1~ C
20alkyl:
In solvent dimethylformamide and under oxygen free condition, there is ring closure reaction in 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides and Compound D, obtain compd B under the catalysis of tributylamine and palladium, and reaction formula is:
Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides: the mol ratio of Compound D is 1:2, and the temperature of described reaction is 130 ℃, and the time is 4h, Compound D: tributylamine: the mol ratio of palladium is 20:20:1.
4. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 2, it is characterized in that, described catalyzer is three (dibenzalacetone) two palladiums, tetrakis triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride.
5. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that 0.5% ~ 20% of the mole dosage that the mole dosage of described catalyzer is compd B.
6. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 5, is characterized in that, the mole dosage of described catalyzer is compd B 2% ~ 3.5%.
7. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that, described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, dioxane or toluene.
8. the preparation method containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer as claimed in claim 2, it is characterized in that, being operating as of described separation and purification: after reaction finishes, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, splash in dehydrated alcohol, separate out precipitation, suction filtration, dry, obtain pressed powder, after pressed powder being dissolved with chloroform, take toluene or sherwood oil as elutriant, carry out column chromatography for separation with neutral alumina chromatography column or silica gel column chromatography, after the underpressure distillation of gained chromatographic solution, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
9. the application containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer according to claim 1, it is characterized in that, be describedly applied to and prepare polymer solar cell device or organic electroluminescence device containing benzene 1,4-Dithiapentalene-benzo two (diazosulfide) multipolymer.
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| CN111205307A (en) * | 2020-02-27 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Thienobenzothiadiazoledione organic compound, and preparation method and application thereof |
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| CN105367759A (en) * | 2015-12-23 | 2016-03-02 | 宁波优而雅电器有限公司 | Conjugated polymer for photovoltaic device, and preparation method and application of conjugated polymer |
| CN105418898A (en) * | 2015-12-23 | 2016-03-23 | 宁波优而雅电器有限公司 | Conjugate polymer used for photo-electric devices and preparation method thereof |
| CN105418899A (en) * | 2015-12-24 | 2016-03-23 | 杨荣 | Preparation method and application of conjugate polymer used in organic semiconductor |
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| WO2018014163A1 (en) * | 2016-07-18 | 2018-01-25 | South University Of Science And Technology Of China | Donor-acceptor polymer with 4-alkoxyl thiophene as conjugated side chain and composition having the same |
| CN111205307A (en) * | 2020-02-27 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Thienobenzothiadiazoledione organic compound, and preparation method and application thereof |
| CN111205307B (en) * | 2020-02-27 | 2022-11-04 | 中国科学院宁波材料技术与工程研究所 | Thienobenzothiadiazoledione organic compound, and preparation method and application thereof |
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