CN103772654A - Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof - Google Patents

Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof Download PDF

Info

Publication number
CN103772654A
CN103772654A CN201210406257.8A CN201210406257A CN103772654A CN 103772654 A CN103772654 A CN 103772654A CN 201210406257 A CN201210406257 A CN 201210406257A CN 103772654 A CN103772654 A CN 103772654A
Authority
CN
China
Prior art keywords
diazosulfide
reaction
bis
formula
benzo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201210406257.8A
Other languages
Chinese (zh)
Inventor
周明杰
管榕
黎乃元
黄佳乐
李满园
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201210406257.8A priority Critical patent/CN103772654A/en
Publication of CN103772654A publication Critical patent/CN103772654A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof. The copolymer containing anthryl-benzodi(benzothiadiazole) is a compound P represented by a general formula described in the specification. In the general formula, R1 and R2 are same or different C1-20 alkyl groups, R3 and R4 are H, C1-20 alkyl groups or C8 alkyloxy groups, and n is an integer in a range from 1 to 100. The copolymer includes a novel benzodi(benzothiadiazole) conjugate unit which can absorb spectrum to allow red shift to occur and has a high degree of matching with solar spectrum; the copolymer further includes a planar conjugate structure, so a high carrier migration rate and high energy conversion efficiency are obtained; the preparation method for the copolymer is simple and controllable; and the polymer has good application prospects in photoelectric material fields like polymer solar cells and organic electroluminescent devices.

Description

A kind of containing anthracene-benzo two (diazosulfide) multipolymer and preparation and application thereof
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing anthracene-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 due to complex manufacturing at present, and inorganic semiconductor material source is limited, expensive, poisonous, complicated process of preparation, and cost is high, and application is restricted.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.
At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.And the absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, it is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor, improve absorbing sunlight.
The conjugated polymers containing anthracene 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 anthracene-benzo two (diazosulfide) multipolymer, in this multipolymer, contain new benzo two (diazosulfide) conjugate unit, its absorption spectrum generation red shift, high with the matching degree of solar spectrum, be planar conjugate structure, carrier mobility speed is high simultaneously, and effciency of energy transfer is high.
The present invention also aims to provide preparation method and the application containing anthracene-benzo two (diazosulfide) multipolymer.
First aspect, the invention provides a kind of containing anthracene-benzo two (diazosulfide) multipolymer, for having the compound P of following general formula:
Figure BDA00002293098100021
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group, n is the integer between 1 ~ 100.
Contain new benzo two (diazosulfide) conjugate unit of the present invention containing in anthracene-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.
Meanwhile, contain anthryl group of the present invention containing in anthracene-benzo two (diazosulfide) copolymer structure, and anthracene and derivative thereof have good carrier transmission characteristics, and under its crystal room temperature, hole mobility can reach 3cm 2/ Vs, is the organic semiconductor material of a class excellence, and wide to the absorption region of sunlight, is beneficial to the matching that improves organic semiconductor material and sunlight, has good stability and good film-forming properties simultaneously, is widely used in field of photovoltaic materials.
New conjugate planes structure that what the present invention obtained on the basis of above two kinds of unit have containing anthracene-benzo two (diazosulfide) multipolymer, there is excellent sunlight matching, carrier mobility ability and configuration flexibility, have a extensive future.
Second aspect, the invention provides a kind of preparation method containing anthracene-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:
Figure BDA00002293098100031
In formula, R 1, R 2for identical or different C 1~ C 20alkyl, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group;
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 alkaline solution and catalyzer, at 50 ℃ ~ 120 ℃, carry out Suzuki coupling reaction 6 ~ 108 hours, obtain containing anthracene-benzo two (diazosulfide) multipolymer, described is the compound P with following general formula containing anthracene-benzo two (diazosulfide) multipolymer:
Figure BDA00002293098100041
Wherein, n is the integer between 1 ~ 100.
The reaction formula of described Suzuki coupling reaction is:
Figure BDA00002293098100042
Preferably, described 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, 0.05% ~ 20% of the mole dosage that the mole dosage of described catalyzer is compd B.More preferably, 0.05% ~ 3.56% of the mole dosage that the mole dosage of described catalyzer is compd B.
Preferably, described alkaline solution is Na 2cO 3the aqueous solution, Na 2cO 32 ~ 20 times of the amount of substance amount of substance that is compd A.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.
Preferably, the specific operation process of described Suzuki 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, and obtains containing anthracene-benzo two (diazosulfide) multipolymer.
Preferably, carry out after Suzuki coupling reaction, obtain containing anthracene-benzo two (diazosulfide) multipolymer by separating-purifying, the concrete operations of described separating-purifying are: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, separate with silica gel column chromatography, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain containing anthracene-benzo two (diazosulfide) multipolymer.
Described compd A is prepared in accordance with the following methods:
Provide structural formula suc as formula the Compound C shown in C, wherein, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group:
Figure BDA00002293098100051
After Compound C being mixed with tetrahydrofuran (THF) in inert atmosphere, be cooled to-78 ℃, add n-Butyl Lithium (n-BuLi), after reaction 2h, add 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-, under room temperature, reaction is spent the night, and obtains compd A, and reaction formula is:
Figure BDA00002293098100061
In embodiment below, for convenience of statement, Compound C is used respectively the expressions such as C1, C2, C3, and compd A is used respectively the expressions such as A1, A2, A3, and name is all as the criterion with the title in each embodiment.
Preferably, described inert atmosphere is nitrogen or argon gas.Described solvent is enough.
Preferably, the ratio of the amount of substance of Compound C and n-Butyl Lithium (n-BuLi) is 1:2,2-isopropoxy-4, and 4,5,5-tetramethyl--1,3,2-bis-is assorted, and oxygen pentaborane is 2:1 with the ratio of the amount of substance of Compound C.
The preparation method of described compd B comprises following operation steps:
I, by structural formula compound (1) 4-oil of mirbane-1 as the formula (1), 2-diamines reacts with thionyl chloride, obtains structural formula compound (2) 5-nitro-2 as the formula (2), 1,3 diazosulfide,
Reaction formula is:
Figure BDA00002293098100062
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.
II, structural formula compound (2) 5-nitro-2 as the formula (2), 1,3 diazosulfide generation bromination reaction, obtains the structural formula compound bromo-5-of (3) 4,7-bis-nitro-2 as the formula (3), 1,3 diazosulfide,
Reaction formula is:
Figure BDA00002293098100071
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.
III, the structural formula compound bromo-5-of (3) 4,7-bis-nitro-2 as the formula (3), 1,3 diazosulfide carries out linked reaction under the catalysis of copper powder, obtain structural formula compound (4) 4,4 '-bis-as the formula (4) bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide
Reaction formula is:
Figure BDA00002293098100072
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.
IV, structural formula compound (4) 4 as the formula (4), 4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides diazotization after being reduced into amino, react with potassiumiodide again, obtain structural formula compound (5) 4 as the formula (5), 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide
Reaction formula is:
Figure BDA00002293098100081
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.
V, provide suc as formula the Compound D shown in D, in formula, R 1, R 2for identical or different 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:
Figure BDA00002293098100083
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.
In embodiment below, for convenience of statement, compd B is used respectively B1, B2, and B3, B4 represents, Compound D is used respectively D1, D2, D3, D4 represents, name is all as the criterion with the title in each embodiment.
The third aspect, the invention provides a kind of application containing anthracene-benzo two (diazosulfide) multipolymer, is described containing the application of anthracene-benzo two (diazosulfide) multipolymer in polymer solar cell device and organic electroluminescence device.Described anthracene-benzo two (diazosulfide) multipolymer that contains is as described in first aspect present invention.
One provided by the invention, containing anthracene-benzo two (diazosulfide) multipolymer and preparation method thereof and application, has following beneficial effect:
Anthracene-benzo two (diazosulfide) multipolymer that contains of the present invention contains anthracene and new benzo two (diazosulfide) conjugate unit, its absorption spectrum generation red shift, high with the matching degree of solar spectrum, carrier mobility speed improves, ratio and charge collection efficiency that current carrier arrives electrode are high, and effciency of energy transfer is also improved.
There is no at present bibliographical information and related application openly containing anthracene-benzo two (diazosulfide) multipolymer, it is a kind of new photoelectric material, effciency of energy transfer is high, and can utilize Suzuki 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 of embodiment 6.
Fig. 2 is the structural representation of the organic electroluminescence device of embodiment 7.
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 anthracene-benzo two (diazosulfide) multipolymer, for thering is the copolymer p of following general formula:
Figure BDA00002293098100101
In formula, R 1, R 2for identical or different C 1~ C 20alkyl, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group, n is the integer between 1 ~ 100.
Embodiment 1
A kind of containing anthracene-benzo two (diazosulfide) multipolymer, poly-{ anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=25), are designated as copolymer p 1, and structural formula is as follows:
Figure BDA00002293098100102
Preparation method comprises the following steps:
One, preparation 2,6-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (A1), comprises following operation steps:
Compound C 1 is provided, 9,10-dibromoanthracene;
Under nitrogen protection, adding Compound C 1 (10.08g in there-necked flask, 0.03mol) with 200mL tetrahydrofuran (THF), under-78 ℃ of conditions, slowly inject again the hexane solution (25.2mL of n-Butyl Lithium with syringe, 2.5M, 0.06mol), continue stirring reaction 2h, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane (13mL of 2-bis-, 0.06mol), under room temperature, stirring reaction spends the night, reaction solution after reaction is finished adds termination reaction in 60mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, with sherwood oil as elutriant, crude product is carried out to silica gel column chromatography separation, obtain 2, 6-bis-((4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-) anthracene (A1), productive rate 80%, reaction formula is:
Figure BDA00002293098100111
Two, 4,9-bis-is bromo-6, and preparation method (B1) is as follows for 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide):
I, prepare structural formula compound (2) 5-nitro-2 as the formula (2), 1,3 diazosulfide, reaction formula is:
In there-necked flask, add structural formula compound (1) 4-oil of mirbane-1 as the formula (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 structural formula compound (2) 5-nitro-2 as the formula (2), 1,3 diazosulfide 21.7g, productive rate 80%;
II, prepare the structural formula compound bromo-5-of (3) 4,7-bis-nitro-2 as the formula (3), 1,3 diazosulfide, reaction formula is as follows:
In there-necked flask, add structural formula compound (2) 5-nitro-2 as the formula (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 structural formula compound (3) 4 as the formula (3), the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide 10.2g, productive rate 50%;
III, to prepare structural formula compound (4) 4,4 '-bis-as the formula (4) bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, and reaction formula is as follows:
In there-necked flask, add structural formula compound (3) 4 as the formula (3), the bromo-5-of 7-bis-nitro-2, 1, 3 diazosulfide (10.2g, 30mmol), the copper powder of 9.5g, the N of 90mL, dinethylformamide (DMF), be heated to 120 ℃ of reactions after 3 hours, stopped reaction, be cooled to room temperature, add 90mL toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtain structural formula compound (4) 4 as the formula (4), 4 '-bis-bromo-6, 6 '-dinitrobenzene- Lian 2, 1, 3 diazosulfide 4.7g, productive rate 30.2%,
IV, prepare bromo-6,6 '-bis-iodo-2,1,3 diazosulfides of structural formula compound (5) 4,4 '-bis-as the formula (5), reaction formula is as follows:
In there-necked flask, add structural formula compound (4) 4 as the formula (4), 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfide (10.3g, 20mmol), add the tetrahydrofuran (THF) that 300mL is dry (THF), add 40g 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 hydrogenchloride 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 to steam and remove organic solvent, as elutriant, surplus materials silica gel column chromatography after revolving steaming is carried out to separating-purifying with sherwood oil, then carry out recrystallizing methanol, obtain 4.1g structural formula compound (5) 4 as the formula (5), 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide, productive rate is 30%.
V, provide Compound D 1,2,6,13,17-tetramethyl--9-octadecyne;
In there-necked flask, add structural formula compound (5) 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1 as the formula (5), 3 diazosulfides (3.4g, 5mmol), add Compound D 1(3.07g, 10mmol), 25mLDMF, 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, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters underpressure distillation, n-hexane/ethyl acetate mixed solvent take volume ratio as 8:1 is elutriant, carry out separating-purifying to distilling rear surplus materials with silica gel column chromatography, obtain 2.4g 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) are (B1), productive rate 70%, reaction formula is as follows:
The structured testing data of compound B-11 are as follows:
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。
Three, poly-{ anthracene-6,7-bis-(3,7-dimethyl) octyl group benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P1) comprises following operation steps:
Under nitrogen protection, in round-bottomed flask, add compd A 1 (86mg, 0.2mmol), compound B-11 (146.6mg, 0.2mmol) and glycol dimethyl ether 40mL, vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 2cl 2(5mg, 7.13 × 10 -3mmol), 2M Na 2cO 3solution 0.5mL (Na 2cO 3amount of substance be 1mmol), be heated to 90 ℃ reaction 72h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder dissolves with chloroform, with toluene as elutriant, carry out separating-purifying with silica gel column chromatography, 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, obtain poly-{ anthracene-6 of product, 7-bis-(3, 7-dimethyl) octyl group benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P1), reaction formula is as follows:
Figure BDA00002293098100151
Gained poly-{ anthracene-6,7-bis-(3,7-dimethyl) octyl group benzo [2,1-e:3,4-e] two (diazosulfides) } (P1) is carried out to gel chromatography (GPC) test, number-average molecular weight Mn=19475, n=25, monodispersity coefficient is 2.3.
Embodiment 2
A kind of containing anthracene-benzo two (diazosulfide) multipolymer, poly-{ 2,6-, bis-positive decyl anthracene-6,7-dioctyl-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=60), are designated as copolymer p 2, and structural formula is as follows:
Preparation method comprises the following steps:
One, 2, positive decyl-9 of 6-bis-, the preparation method of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (A2) comprises the following steps:
Compound C 2 is provided, 2, positive decyl-9 of 6-bis-, 10-dibromoanthracene;
Under nitrogen protection, adding Compound C 2 (12.34g in there-necked flask, 0.02mol) with 200mL tetrahydrofuran (THF), under-78 ℃ of conditions, slowly inject again the hexane solution (16.8mL of n-Butyl Lithium with syringe, 2.5M, 0.04mol), continue stirring reaction 2h, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane (8.6mL of 2-bis-, 0.04mol), under room temperature, stir and spend the night, reaction solution after reaction is finished adds termination reaction in 60mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, using sherwood oil as elutriant, crude product is carried out to silica gel column chromatography separating-purifying, obtain 2, positive decyl-9 of 6-bis-, 10-bis-(4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-) anthracene (A2), productive rate 85%, reaction formula is:
Figure BDA00002293098100162
Two, 4,9-bis-is bromo-6, and 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) preparation (B1) is with embodiment 1 step 2.
Three, poly-{ 2,6-didecyl anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P2) comprises the following steps:
Under nitrogen protection, add compd A 2 (177.8mg, 0.25mmol), compound B-11 (183.3mg, 0.25mmol) and tetrahydrofuran (THF) 50mL to round-bottomed flask, vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 4(5mg, 4.33 × 10 -3mmol), 2M Na 2cO 3solution 1.25mL (Na 2cO 3amount of substance be 2.5mmol), be heated to 90 ℃ reaction 72h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 6mL left and right, splashed in 500mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, using toluene as elutriant, carry out separating-purifying 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 { 2, 6-didecyl anthracene-6, 7-bis-(3, 7-dimethyl) octyl group-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P2), reaction formula is as follows:
To poly-{ 2,6-didecyl anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (P2) carry out gel chromatography (GPC) test, number-average molecular weight Mn=61800, n=60, polymkeric substance monodispersity coefficient is 1.8.
Embodiment 3
A kind of containing anthracene-benzo two (diazosulfide) multipolymer, i.e. poly-{ 2,6-, bis-octyloxy anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (n=50), be designated as copolymer p 3, structural formula is as follows:
Figure BDA00002293098100181
Preparation method comprises the following steps:
One, 2,6-bis-octyloxy-9, the preparation method of 10-bis-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (A3) comprises the following steps:
Compound C 3 is provided, 2,6-bis-octyloxy-9,10-dibromoanthracene;
Under nitrogen protection, adding Compound C 3 (5.92g in there-necked flask, 0.01mol) with 200mL tetrahydrofuran (THF), under-78 ℃ of conditions, slowly inject again the hexane solution (8.4mL of n-Butyl Lithium with syringe, 2.5M, 0.02mol), continue stirring reaction 2h, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane (4.3mL of 2-bis-, 0.02mol), under room temperature, stir and spend the night, reaction solution after reaction is finished adds termination reaction in 60mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, using sherwood oil as elutriant, crude product is carried out to separating-purifying with silica gel column chromatography, obtain 2, 6-bis-octyloxy-9, 10-bis-(4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-) anthracene (A3), productive rate 88%, reaction formula is:
Two, 4,9-bis-is bromo-6, and 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) preparation (B1) is with embodiment 1 step 2.
Three, poly-{ 2,6-, bis-octyloxy anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P3) comprises following operation steps:
Under argon shield, add compound A-13 (206mg, 0.3mmol), compound B-11 (219.9mg, 0.3mmol) and toluene 60mL to round-bottomed flask, vacuumize deoxygenation and be filled with nitrogen, then add 5mgPd 2(dba) 3(5.46 × 10 -3mmol), 2M Na 2cO 3solution 1.5mL (Na 2cO 3amount of substance be 3mmol), be heated to 90 ℃ reaction 72h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 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, using toluene as elutriant, carry out silica gel column chromatography separation, 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 { 2, 6-bis-octyloxy anthracene-6, 7-bis-(3, 7-dimethyl) octyl group-benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P3), reaction formula is as follows:
Figure BDA00002293098100201
To poly-{ 2,6-, bis-octyloxy anthracene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (P3) carry out gel chromatography (GPC) test, number-average molecular weight Mn=50250, n=50, polymkeric substance monodispersity coefficient is 2.2.
Embodiment 4
A kind of containing anthracene-benzo two (diazosulfide) multipolymer, poly-{ 2,6-bis-(NSC 62789 base) anthracene-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 4, structural formula is as follows:
Figure BDA00002293098100202
Preparation method comprises the following steps:
One, 2,6-bis-(NSC 62789 base)-9,10-bis-(preparation method of (4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (A4) comprises the following steps:
Compound C 4 is provided, 2,6-bis-(NSC 62789 base)-9,10-dibromoanthracene;
Under nitrogen protection, adding Compound C 4 (8.97g in there-necked flask, 0.01mol) with 100mL tetrahydrofuran (THF), under-78 ℃ of conditions, slowly inject again the hexane solution (8.4mL of n-Butyl Lithium with syringe, 2.5M, 0.02mol), continue stirring reaction 2h, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane (4.3mL of 2-bis-, 0.02mol), under room temperature, stir and spend the night, reaction solution after reaction is finished adds termination reaction in 60mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, with sherwood oil as elutriant, crude product is carried out to silica gel column chromatography separation, obtain 2, 6-bis-(NSC 62789 base)-9, 10-bis-((4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-) anthracene (A4), productive rate 90%, reaction formula is as follows:
Figure BDA00002293098100211
Two, 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfide) preparation method (B2) comprises the following steps:
Prepare bromo-6,6 '-bis-iodo-2,1,3 diazosulfides of structural formula compound (5) 4,4 '-bis-as the formula (5) according to the operation of the I ~ IV of embodiment 1 step 2;
Provide Compound D 2, i.e. 2,6 – dimethyl-9-30 alkynes;
In there-necked flask, add structural formula compound (5) 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1 as the formula (5), 3 diazosulfides (6.8g, 10mmol), Compound D 2(8.94g, 20mmol), with 80mL DMF, pass into nitrogen gas stirring 20min, add Bu 3n (1.814g, 20mmol) and Pd (OAc) 2(230mg, 1.0mmol), be warming up to 130 ℃, isothermal reaction 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, the n-hexane/ethyl acetate mixed solvent take volume ratio as 8:1 is elutriant, carry out separating-purifying to distilling rear surplus materials with silica gel column chromatography, obtain 5.0g product, 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) (B2), productive rate 57.3%;
Reaction formula is as follows:
The structured testing data of compd B 2 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；
Three, poly-{ 2,6-bis-(NSC 62789 base) anthracene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides) } preparation method (P4) comprises the following steps:
Under nitrogen protection, in round-bottomed flask, add compd A 4 (297.3mg, 0.3mmol), compd B 2 (146.6mg, 0.2mmol) and benzene 40mL, vacuumize deoxygenation and be filled with nitrogen, then add 46.16mgPd (PPh 3) 4(0.04mmol), the Na of 2M 2cO 3solution 3mL (Na 2cO 3amount of substance be 6mmol), be heated to 120 ℃ reaction 108h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder dissolves with chloroform, take toluene as elutriant, carry out separating-purifying with silica gel column chromatography, 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, obtain product poly-{ 2, 6-bis-(NSC 62789 base) anthracene-6-(3, 7-dimethyl) octyl group-7-NSC 62789 base benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P4), reaction formula is as follows:
Figure BDA00002293098100231
By gained poly-{ 2,6-bis-(NSC 62789 base) anthracene-6-(3,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides) } (P4) carry out gel chromatography (GPC) test, number-average molecular weight Mn=104800, n=100, polymkeric substance monodispersity coefficient is 3.5.
Embodiment 5
A kind of containing anthracene-benzo two (diazosulfide) multipolymer, poly-{ 2,6-dimethylanthracene-6-methyl-7-propyl group-benzo [2,1-e:3,4-e], two (diazosulfides) } (n=1), are designated as copolymer p 5, and structural formula is as follows:
Figure BDA00002293098100241
Preparation method comprises the following steps:
One, 2,6-dimethyl-9,10-bis-(preparation method of (4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) anthracene (A5) comprises the following steps:
Compound D 5 is provided, 2,6-dimethyl-9,10-dibromoanthracene;
Under nitrogen protection, adding Compound D 5 (3.64g in there-necked flask, 0.01mol) with 100mL tetrahydrofuran (THF), under-78 ℃ of conditions, slowly inject again the hexane solution (8.4mL of n-Butyl Lithium with syringe, 2.5M, 0.02mol), continue stirring reaction 2h, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane (4.3mL of 2-bis-, 0.02mol), under room temperature, stir and spend the night, reaction solution after reaction is finished adds termination reaction in 60mL saturated sodium-chloride water solution, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate anhydrous diethyl ether, obtain crude product, using sherwood oil as elutriant, crude product is carried out to silica gel column chromatography separation, obtain 4 "-methyl-4, 4 '-bis-((4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-) anthracene (A5), productive rate 82%, reaction formula is:
Figure BDA00002293098100242
Two, 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfide) is preparation method (B3) comprise the following steps:
Prepare bromo-6,6 '-bis-iodo-2,1,3 diazosulfides of structural formula compound (5) 4,4 '-bis-as the formula (5) according to the operation of embodiment 1 step I ~ IV;
Provide compound d3, i.e. 2-hexin;
Then in there-necked flask, add structural formula compound (5) 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1 as the formula (5), 3 diazosulfides (6.8g, 10mmol), compound d3 (1.64g, 20mmol) and 50mLDMF, pass into nitrogen gas stirring 20min, add 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 n-hexane/ethyl acetate mixed solvent take volume ratio as 8:1 is elutriant, carries out separating-purifying 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) (B3), productive rate is 60%, reaction formula is:
Figure BDA00002293098100251
The bromo-6-methyl-7-of 4,9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) structured testing data (B3) 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。
Three, poly-{ 2,6-dimethylanthracene-6-methyl-7-propyl group benzo [2,1-e:3,4-e], two (diazosulfides) } preparation method (P5) comprises the following steps:
Under argon shield, in round-bottomed flask, add compound A-45 (91.6mg, 0.2mmol), compd B 3 (152.4mg, 0.3mmol) and tetrahydrofuran (THF) 40mL, vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh 3) 4(0.17mg, 1.5 × 10 -4mmol), 2M Na 2cO 3solution 0.2mL (Na 2cO 3amount of substance be 0.4mmol), be heated to 50 ℃ reaction 6h.
After reaction finishes, in round-bottomed flask, add deionized water and toluene to extract, get organic phase, underpressure distillation is to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder dissolves with chloroform, take toluene as elutriant, carry out separating-purifying with silica gel column chromatography, 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, obtain product poly-{ 2, 6-dimethylanthracene-6-methyl-7-propyl group benzo [2, 1-e:3, 4-e] two (diazosulfides) } (P5), reaction formula is as follows:
Figure BDA00002293098100261
Gained poly-{ 2,6-dimethylanthracene-6-methyl-7-propyl group benzo [2,1-e:3,4-e], two (diazosulfides) } (P5) is carried out to gel chromatography (GPC) and test, number-average molecular weight Mn=583, n=1.
Embodiment 6
What prepare take the embodiment of the present invention is active coating containing anthracene-benzo two (diazosulfide) multipolymer, prepare polymer solar cell device, its structure comprises 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 tin indium oxide (ITO), is that square resistance is the tin indium oxide of 10 Ω/mouths; The material of middle supplementary layer 3 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material (PEDOT:PSS, commodity are called CLEVIOS P VPAl 4083); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor(ED) be the embodiment of the present invention prepare containing anthracene-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 ito glass thickness is 1.1mm, after ultrasonic cleaning, with oxygen plasma (oxygen-Plasma) processing; Then on ito glass, apply PEDOT:PSS, supplementary layer 3 in the middle of obtaining, thickness is 120nm; That prepared by the 10mg embodiment of the present invention is dissolved in 0.4mL dimethylbenzene and obtains solution containing anthracene-benzo two (diazosulfide) multipolymer again, be dissolved in 8mg PCBM the solution blending that 0.4mL chlorobenzene obtains, in the middle of being spun on, on supplementary layer, thickness is 110nm, obtains active coating 4; Be 2 × 10 at pressure -3under the vacuum condition of Pa, evaporation metal aluminium obtains 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 anthracene-benzo two (diazosulfide) multipolymer, can device suitably be improved or be modified.
That prepares using embodiment 1,2 and 3 respectively prepares polymer solar cell device containing anthracene-benzo two (diazosulfide) copolymer p 1, P2, P3 as the material of active coating, obtain device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, obtain the performance data of device in table 1.
Table 1 is prepared as active coating containing anthracene-benzo two (diazosulfide) multipolymer take of the present invention
The performance data of polymer solar cell device
Figure BDA00002293098100281
As seen from the data in Table 1, be 0.97 ~ 1.35 with the energy conversion efficiency of the polymer solar cell device of preparing as active coating containing anthracene-benzo two (diazosulfide) multipolymer of the present invention.Show that anthracene-benzo two (diazosulfide) multipolymer that contains of the present invention is owing to containing anthracene and 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 current carrier and arrive ratio and the charge collection efficiency of electrode, thereby improve effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.
Embodiment 7
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, the preparation method of each layer is undertaken by spin coating method.Wherein, on glass substrate 1, deposit the tin indium oxide that square resistance is 10 Ω/mouths (ITO) (150nm), as transparent anode 2, it is CLEVIOS P VP Al4083 that anode buffer layer 3 adopts PEDOT:PSS(trade name) preparation, thickness is 30nm, the material of luminescent layer 4 is copolymer p 1 prepared by the embodiment of the present invention 1, thickness is 90nm, the material of buffer layer 5 is lithium fluoride (LiF), thickness is 1.5nm, the material of negative electrode 6 is metallic aluminium (Al), and thickness is 150nm, and 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 2400Sourcemeter), 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 14.0cd/A, and high-high brightness is 1250cd/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 make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. containing anthracene-benzo two (diazosulfide) multipolymer, it is characterized in that, described is the compound P with following general formula containing anthracene-benzo two (diazosulfide) multipolymer:
Figure FDA00002293098000011
In formula, R 1, R 2for C 1~ C 20alkyl, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group, n is the integer between 1 ~ 100.
2. containing a preparation method for anthracene-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:
Figure FDA00002293098000012
In formula, R 1, R 2for identical or different C 1~ C 20alkyl, R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group;
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 alkaline solution and catalyzer, at 50 ℃ ~ 120 ℃, carry out Suzuki coupling reaction 6 ~ 108 hours, obtain containing anthracene-benzo two (diazosulfide) multipolymer, described is the compound P with following general formula containing anthracene-benzo two (diazosulfide) multipolymer:
Figure FDA00002293098000021
Wherein, n is the integer between 1 ~ 100.
3. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that, the preparation method of described compd A comprises following operation steps:
Provide structural formula suc as formula the Compound C shown in C, wherein R 3, R 4for H, C 1~ C 20alkyl or C 8alkoxyl group:
Figure FDA00002293098000022
After Compound C being mixed with tetrahydrofuran (THF) in inert atmosphere, be cooled to-78 ℃, add n-Butyl Lithium, Compound C: the ratio of the amount of substance of n-Butyl Lithium is 1:2, after reaction 2h, add 2-isopropoxy-4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-, 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-bis-is assorted, and oxygen pentaborane is 2:1 with the ratio of the amount of substance of Compound C, under room temperature, reaction is spent the night, and obtains compd A, and reaction formula is:
Figure FDA00002293098000031
4. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that, the preparation method of described compd B comprises following operation steps:
I, by structural formula compound (1) 4-oil of mirbane-1 as the formula (1), 2-diamines reacts with thionyl chloride, obtains structural formula compound (2) 5-nitro-2 as the formula (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;
II, structural formula compound (2) 5-nitro-2 as the formula (2), 1,3 diazosulfide generation bromination reaction, obtains the structural formula compound bromo-5-of (3) 4,7-bis-nitro-2 as the formula (3), 1,3 diazosulfide,
Reaction formula is:
Figure FDA00002293098000033
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;
III, the structural formula compound bromo-5-of (3) 4,7-bis-nitro-2 as the formula (3), 1,3 diazosulfide carries out linked reaction under the catalysis of copper powder, obtain structural formula compound (4) 4,4 '-bis-as the formula (4) bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide
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;
IV, structural formula compound (4) 4 as the formula (4), 4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian 2,1, nitro in 3 diazosulfides diazotization after being reduced into amino, react with potassiumiodide again, obtain structural formula compound (5) 4 as the formula (5), 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide
Reaction formula is:
Figure FDA00002293098000042
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;
V, provide suc as formula the Compound D shown in D, in formula, R 1, R 2for identical or different C 1~ C 20alkyl:
Figure FDA00002293098000051
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:
Figure FDA00002293098000052
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.
5. the preparation method containing anthracene-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.
6. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that 0.05% ~ 20% of the mole dosage that the mole dosage of described catalyzer is compd B.
7. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 6, is characterized in that 0.05% ~ 3.56% of the mole dosage that the mole dosage of described catalyzer is compd B.
8. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 2, is characterized in that, described alkaline solution is Na 2cO 3the aqueous solution, Na in the aqueous solution 2cO 32 ~ 20 times of the amount of substance amount of substance that is compd A.
9. the preparation method containing anthracene-benzo two (diazosulfide) multipolymer as claimed in claim 2, it is characterized in that, carry out after Suzuki coupling reaction, obtain containing anthracene-benzo two (diazosulfide) multipolymer by separating-purifying, the concrete operations of described separating-purifying are: after reaction, in reaction solution, add deionized water and toluene to extract, get organic phase, after underpressure distillation, add in dehydrated alcohol, separate out precipitation, suction filtration, after oven dry, obtain pressed powder, after pressed powder being dissolved with chloroform, separate with silica gel column chromatography, after chromatographic solution underpressure distillation, use methyl alcohol sedimentation, suction filtration, gained solid extracts in apparatus,Soxhlet's with acetone three days, use again methyl alcohol sedimentation, suction filtration, vacuum filtration spends the night, obtain containing anthracene-benzo two (diazosulfide) multipolymer.
10. according to claim 1 containing the application of anthracene-benzo two (diazosulfide) multipolymer in polymer solar battery and organic electroluminescence device.
CN201210406257.8A 2012-10-23 2012-10-23 Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof Pending CN103772654A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210406257.8A CN103772654A (en) 2012-10-23 2012-10-23 Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210406257.8A CN103772654A (en) 2012-10-23 2012-10-23 Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof

Publications (1)

Publication Number Publication Date
CN103772654A true CN103772654A (en) 2014-05-07

Family

ID=50565458

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210406257.8A Pending CN103772654A (en) 2012-10-23 2012-10-23 Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN103772654A (en)

Similar Documents

Publication Publication Date Title
CN103772656A (en) Benzodithiophene-benzodi(benzothiadiazole) containing copolymer, preparation and application thereof
CN103772657A (en) Fluorene-benzodi(benzothiadiazole) containing copolymer, preparation method and application thereof
CN103772655A (en) Triphenylamine-benzodi(benzothiadiazole) containing copolymer, preparation and application thereof
CN103833979A (en) Bitriselenophen-benzodi(benzoselendiazole) copolymer, preparation method and application thereof
CN103833976B (en) A kind of thionaphthene-thiophene that contains is coughed up and two (diazosulfide) multipolymer and Synthesis and applications thereof
CN103833981A (en) Benzo[3,4-b]dithiophene-benzo-di(benzoselenadiazole) copolymer as well as preparation method and application thereof
CN103626972A (en) Copolymer containing siliconfluorene-benzobis(benzothiadiazole), preparation method thereof and applications thereof
CN103772654A (en) Copolymer containing anthryl-benzodi(benzothiadiazole) and preparation and application thereof
CN103772652A (en) Copolymer containing [3,4-b]dithiophene-benzobis(benzothiadiazole), preparation method and applications thereof
CN103833978B (en) Contain also [3,4-b] two thiophene-thiophene to cough up and two (diazosulfide) multipolymer and Synthesis and applications thereof
CN103833975B (en) A kind of 1,4-Dithiapentalene-thiophene that contains is coughed up and two (diazosulfide) multipolymer and Synthesis and applications thereof
CN103833974B (en) A kind of also two selenophens-thiophene that contains is coughed up and two (diazosulfide) multipolymer and Synthesis and applications thereof
CN103833977B (en) A kind of benzene 1,4-Dithiapentalene-thiophene that contains is coughed up and two (diazosulfide) multipolymer and preparation and application thereof
CN103833985A (en) [3,2-b]bi-thiofuran-benzo-2(benzo-selenium diazole) combined copolymer as well as preparation method and application thereof
CN103833983B (en) And [3,2-b] two selenophens-benzo two (selenole) multipolymer and its preparation method and application
CN103804653A (en) Seleno[3,2-b]thiophene-benzodi(benzothiadiazole) containing copolymer as well as preparation method and application thereof
CN103833967A (en) 1,8-carbazole-silolodi(benzothiadiazole)-containing copolymer, preparation method and application thereof
CN103626970A (en) Copolymer containing dithiophenepyrrole-benzobis(benzothiadiazole), preparation method thereof and applications thereof
CN103936963A (en) Copolymer containing cyclopentadiene bithiophene-benzobis(benzothiadiazole), preparation method and applications thereof
CN103833964A (en) Fluorene-silole di (benzo thiadiazole) copolymer and its preparation method and application
CN103833965A (en) Triphenylamine-silole di (benzo thiadiazole) copolymer and its preparation method and application
CN103772650A (en) Copolymer containing [3,2-b]dithiophene-benzobis(benzothiadiazole), preparation method and applications thereof
CN103833963A (en) Selenophen bithiophene-silole di (benzo thiadiazole) copolymer and its preparation and application
CN103833966A (en) Silole di thiophene-silole di (benzo thiadiazole) copolymer and its preparation method and application
CN104072734A (en) Selenophene bithiophene-benzodi(benzoselenadiazole) copolymer material as well as preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140507