CN103626972A - Copolymer containing siliconfluorene-benzobis(benzothiadiazole), preparation method thereof and applications thereof - Google Patents
Copolymer containing siliconfluorene-benzobis(benzothiadiazole), preparation method thereof and applications thereof Download PDFInfo
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- NAMXUDFFYGBCES-MSZQBOFLSA-N CC(C1)[C@H]1c1cc([N+]([O-])=O)cc2n[s]nc12 Chemical compound CC(C1)[C@H]1c1cc([N+]([O-])=O)cc2n[s]nc12 NAMXUDFFYGBCES-MSZQBOFLSA-N 0.000 description 1
- UXQMPBQRVICAFL-UHFFFAOYSA-N C[Si+]1c(cc(cc2)Br)c2-c(cc2)c1cc2Br Chemical compound C[Si+]1c(cc(cc2)Br)c2-c(cc2)c1cc2Br UXQMPBQRVICAFL-UHFFFAOYSA-N 0.000 description 1
- LYTBMLCMMFRBFS-UHFFFAOYSA-N Cc(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O Chemical compound Cc(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O LYTBMLCMMFRBFS-UHFFFAOYSA-N 0.000 description 1
- RAUWPNXIALNKQM-UHFFFAOYSA-N Nc(ccc([N+]([O-])=O)c1)c1N Chemical compound Nc(ccc([N+]([O-])=O)c1)c1N RAUWPNXIALNKQM-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the field of organic semiconductor materials, and discloses a copolymer containing siliconfluorene-benzobis(benzothiadiazole), a preparation method thereof and applications thereof. The copolymer has a general structure formula as follows, wherein R1, R2, R3 and R4 are the same or different C1-C20 alkyl; and n is an integer between 1 and 100. According to the copolymer, the benzobis(benzothiadiazole) is an excellent donor material. The benzobis(benzothiadiazole) has advantages of simple structure, symmetry, good electron delocalization performances, and the like, has a plane structure and is an excellent receptor material. The copolymer formed by the siliconfluorene and the benzobis(benzothiadiazole) can form a strong electron donor-receptor structure, thus facilitating reduction of the energy band gap of a material, thereby expanding the sunlight adsorption scope and increasing the photoelectric conversion rate.
Description
Technical field
The present invention relates to organic semiconductor material, relate in particular to multipolymer of a kind of siliceous fluorenes-benzo two (diazosulfide) and its preparation method and application.
Background technology
The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell, because complex manufacturing, cost are high, is restricted its application at present.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Multipolymer solar cell 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 copolymer and C
60between Photoinduced Electron transfer phenomena after, people drop into large quantity research aspect multipolymer solar cell, and have obtained development at full speed.At present the effciency of energy transfer of multipolymer solar cell is still low than silicon solar cell, one of reason be due to the carrier mobility of multipolymer than the mobility of inorganic monocrystal material low several orders of magnitude.The absorption spectrum of the conjugated copolymer photocell material using at present can not mate well with solar spectrum, is another major reason that causes energy transfer efficiency low.For further improving the performance of multipolymer solar cell, can adopt the utmost point narrow band gap multipolymer having compared with wide absorption spectrum to do to body and acceptor on the one hand, raising absorbs sun power, can adopt on the other hand annealing, add the materials such as tensio-active agent to be optimized device.
Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathodes such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.
Luxuriant and rich with fragrance by three six-rings one-tenth, all atoms are in same plane, there is good electronics cavity transmission ability, and the rigidity of molecule is conducive to improve the thermal stability of material, and luxuriant and rich with fragrance 9, easily modify for 10, can utilize easy method to introduce electron-donating group and electron-accepting group, regulate its confession/electrophilic performance.Therefore it has a wide range of applications in the photoelectric materials such as Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
Thiophene is five-membered ring structure, has moderate band gap, wider spectral response, preferably thermostability and film forming properties.Therefore, thiophene-based organic photoelectrical material is the up-and-coming material of a class, and the application in fields such as organic solar batteries has obtained broad research.。
Yet the multipolymer of siliceous fluorenes-benzo two (diazosulfide) does not still have document and patent report at present simultaneously, this has just limited greatly its range of application.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide the multipolymer of a kind of siliceous fluorenes-benzo two (diazosulfide)
Technical scheme of the present invention is as follows:
A multipolymer for siliceous fluorenes-benzo two (diazosulfide), this multipolymer has following general structure:
In formula: R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100.
The present invention also provides the preparation method of the multipolymer of above-mentioned siliceous fluorenes-benzo two (diazosulfide), comprises the steps:
Under inert atmosphere, the structural formula that is 1:2 by mol ratio is
compd A and structural formula be
the first solvent of existing at the first catalyzer and alkaline solution of compd B in, at 100 ~ 150 ℃, carry out ring closure reaction 2 ~ 6 hours, make structural formula and be
compound C;
Under inert atmosphere, by structural formula, be
compound D be dissolved in tetrahydrofuran solvent, and be placed under-78 ℃ of conditions and add again n-Butyl Lithium, stirring reaction 1 ~ 2 hour; Add subsequently tributyltin chloride, continue reaction and rise to room temperature reaction 6 hours after 1 hour; Obtaining structural formula is
compd E; Wherein, the molar weight of described Compound D and n-Butyl Lithium is 1:2, and tributyltin chloride is identical with the molar weight of n-Butyl Lithium;
Under inert atmosphere, Compound C and compd E are added in the second solvent that the second catalyzer exists, at 50 ~ 120 ℃, carry out Stille coupling reaction 12 ~ 100 hours according to the ratio of mol ratio 1:1.5 ~ 1.5:1, make structural formula and be
the multipolymer of siliceous fluorenes-benzo two (diazosulfide);
In above-mentioned formula: R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100, and preferably n is the integer between 35-54;
In above-mentioned technique preparation, inert atmosphere, comprises the mixing atmosphere of nitrogen atmosphere, argon atmosphere or nitrogen and argon gas composition etc.
Described preparation method, wherein, described compd A is to adopt following steps to make: by structural formula, be
compound I add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is
compound F 17-hydroxy-corticosterone;
Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is
compound G;
Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be
compound H;
Compound H is added to SnCl
2in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes compd A.
Described preparation method, wherein, described the first catalyzer is palladium, the mole dosage of this first catalyzer is compd A 10%; Described alkaline solution is Bu
3n solution, alkali solute Bu in this alkaline solution
3the mole dosage of N is 1:1 with the ratio of the mole dosage of compd B; ; Described the first solvent is DMF.
Described preparation method, wherein, described the second catalyzer is tetrakis triphenylphosphine palladium, three (dibenzalacetone) two palladiums or two (triphenylphosphine) palladium chloride; The molar weight of this second catalyzer is 0.05 ~ 20% of Compound C molar weight; Described the second solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
The present invention also provides the application of above-mentioned multipolymer in organic solar batteries, organic electroluminescence device, organic field effect tube.
The multipolymer of siliceous fluorenes-benzo two provided by the invention (diazosulfide), benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, the multipolymer consisting of silicon fluorenes and benzo two (diazosulfide) can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion.
In the multipolymer preparation technology of siliceous fluorenes-benzo two provided by the invention (diazosulfide), the route of synthetic benzo two (diazosulfide) is fairly simple and ripe, easily by introducing alkyl, improve solvability and the molecular weight of product, be conducive to film forming processing; And Stille reaction is a kind of very ripe polyreaction, and productive rate is high, and mild condition, be easy to control.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic solar batteries that makes of embodiment 7;
Fig. 2 is the structural representation of the organic electroluminescence device that makes of embodiment 10.
Embodiment
The multipolymer of a kind of siliceous fluorenes-benzo two provided by the invention (diazosulfide), this multipolymer has following general structure:
In formula: R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100, and preferably n is the integer between 35-54.
The present invention also provides the preparation method of the multipolymer of above-mentioned siliceous fluorenes-benzo two (diazosulfide), comprises the steps:
S1, prepare structural formula and be
compd A (being 5-nitro-2,1,3 diazosulfide):
1, by structural formula, be
compound I (4-oil of mirbane-1,2-diamines) add in thionyl chloride, stir and (structural formula is toward thionyl chloride
) (structural formula is middle dropping pyridine
molecular formula is C
5h
5n), back flow reaction at 85 ℃, stopped reaction, makes structural formula and is
compound F 17-hydroxy-corticosterone (being 5-nitro-2,1,3 diazosulfide); Reaction formula is as follows:
Preferably compound F 17-hydroxy-corticosterone is carried out to purification process:
Reaction solution is heated to 80 ℃ to be revolved and steams excessive SOCl
2after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain
2, compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, 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, obtaining structural formula is
the i.e. bromo-5-of 4,7-bis-nitro-2 of compound G(, 1,3 diazosulfide); Reaction formula is as follows:
3, compound G is added in DMF (DMF) solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be
compound H (4,4 '-bis-is bromo-6, and 6 '-dinitrobenzene-Lian 2,1,3 diazosulfides); Reaction formula is as follows:
Preferably to 4,4 '-bis-is bromo-6, and 6 '-dinitrobenzene-Lian 2,1, and 3 diazosulfides carry out purification process:
Stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains 4 of purifying, 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides.
4, compound H is added to SnCl
2in tetrahydrofuran (THF) (THF) solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolve and steam gained organic layer, obtain solid crude product, be put in there-necked flask, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 ℃, and it is yellow that solution is, after dropwising, react 30 minutes.Then the solution after reaction after reaction being stopped is added dropwise in potassiumiodide (KI) solution, vigorous stirring, and reaction 12h, makes compd A (i.e. 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides); Reaction formula is as follows:
Under S2, inert atmosphere, the above-mentioned compd A making and the structural formula that by mol ratio, are 1:2 are
the first solvent of existing at the first catalyzer and alkaline solution of compd B (acetylene compound) in, at 100 ~ 150 ℃, carry out ring closure reaction 2 ~ 6 hours, make structural formula and be
compound C (4,9-bis-is bromo-6,7-dialkyl group-benzo [2,1-e:3,4-e] two (diazosulfides)); Reaction formula is as follows:
Under S3, inert atmosphere, by structural formula, be
compound D (9,9-dialkyl group-2,7-dibromo silicon fluorenes) be dissolved in tetrahydrofuran (THF) (THF) solvent, and be placed under-78 ℃ of conditions and add again n-Butyl Lithium (n-BuLi), stirring reaction 1 ~ 2 hour; Add subsequently tributyltin chloride (SnBu
3cl), continue reaction and rise to room temperature reaction 6 hours after 1 hour, then by neutral alumina column layer, the structural formula that obtains purifying is
compd E (9,9-dialkyl group-2,7-bis-(tributyl tin) silicon fluorenes); Wherein, the molar weight of described Compound D and n-Butyl Lithium is 1:2, and tributyltin chloride is identical with the molar weight of n-Butyl Lithium; Reaction formula is as follows:
Under S4, inert atmosphere, the above-mentioned Compound C making and compd E are added in the second solvent that the second catalyzer exists, at 50 ~ 120 ℃, carry out Stille coupling reaction 12 ~ 100 hours according to the ratio of mol ratio 1:1.5 ~ 1.5:1, make structural formula and be
the multipolymer of siliceous fluorenes-benzo two (diazosulfide); Reaction formula is as follows:
Above-mentioned various in, R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100, and preferably n is the integer between 35-54;
In above-mentioned technique preparation, inert atmosphere, comprises the mixing atmosphere of nitrogen atmosphere, argon atmosphere or nitrogen and argon gas composition etc.;
Preferably, during described Stille coupling reaction, its temperature of reaction is 70 ~ 100 ℃, and the reaction times is 24 ~ 72 hours.
In above-mentioned preparation method, also need the multipolymer of siliceous fluorenes-benzo two (diazosulfide) that step S4 is made to carry out purification process:
After S5, Stille coupling reaction stop, adjusting the pH value to 8.0 of reaction solution with sodium hydroxide solution, then anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtains solid crude product; Follow in the hydrochloric acid that solid crude product is added, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 ℃, and it is yellow that solution is, and after dropwising, reacts 30 minutes; Follow again, reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, with anhydrous diethyl ether extraction, organic layer washing, anhydrous magnesium sulfate drying, filters, and revolves evaporate to dryness filtrate, separated with silica gel column chromatography, then carry out recrystallizing methanol, obtain the multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of purifying.
In above-mentioned preparation method, preferably the first catalyzer is palladium (Pd (OAc)
2), the mole dosage of this first catalyzer is compd A 10%; Described the second catalyzer is tetrakis triphenylphosphine palladium (Pd (PPh
3)
4), three (dibenzalacetone) two palladium (Pd
2(dba)
3) or two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2).The molar weight of this second catalyzer is 0.05 ~ 20% of Compound C molar weight.
In above-mentioned preparation method, preferred bases solution is Bu
3n solution, alkali solute Bu in this alkaline solution
3the mole dosage of N is 1:1 with the ratio of the mole dosage of compd B.
In above-mentioned preparation method, preferably described the first solvent is DMF (DMF); Described the second solvent is tetrahydrofuran (THF) (THF), glycol dimethyl ether, ether, benzene or toluene.
The present invention also provides the application of above-mentioned multipolymer in multipolymer solar cell, organic electroluminescence device.
The multipolymer of siliceous fluorenes-benzo two provided by the invention (diazosulfide), benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, the multipolymer consisting of silicon fluorenes and benzo two (diazosulfide) can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion.
In the multipolymer preparation technology of siliceous fluorenes-benzo two provided by the invention (diazosulfide), the route of synthetic benzo two (diazosulfide) is fairly simple and ripe, easily by introducing alkyl, improve solvability and the molecular weight of product, be conducive to film forming processing; And Stille reaction is a kind of very ripe polyreaction, and productive rate is high, and mild condition, be easy to control.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-dioctyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }, its structural formula is as follows:
Preparation technology's flow process is as follows:
One, 4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
1, compound 5-nitro-2, the preparation of 1,3 diazosulfide
In there-necked flask, add 4-oil of mirbane-1,2-diamines (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, and after heating, in 85 ℃ of back flow reaction 24h, stopped reaction, is heated to 80 ℃ and revolves and steam excessive SOCl
2after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain purified product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%;
2, compound 4, the bromo-5-of 7-bis-nitro-2, the preparation of 1,3 diazosulfide
In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide (HBr) 15ml, be warming up to 127 ℃ of backflows, slowly drips bromine (Br in 30min
2) 11.3ml the 4h that refluxes, heat filtering, refilters after filtrate is cooling, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, again with Gossypol recrystallized from chloroform once, obtain purified product 10.2g, productive rate: 50%3,4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1, the preparation of 3 diazosulfides
In there-necked flask, add 4, the bromo-5-of 7-bis-nitro-2, 1, 3 diazosulfide (10.2g, 30mmol), the copper powder of 9.5g (Cu), 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 purified product 4, 4 '-bis-bromo-6, 6 '-dinitrobenzene-Lian 2, 1, 3 diazosulfide 4.7g, productive rate 30.2%,
4,4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian 2,1, and 3 diazosulfides (10.3g, 20mmol) add the tetrahydrofuran (THF) that 300ml is dry (THF), add 40g 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 (HCl) of 58ml (21.7mmol), agitation and dropping Sodium Nitrite (NaNO in 30 minutes
2) solution 20ml(37.7mmol), temperature is controlled at below 5 ℃, and it is yellow that solution is, and after dropwising, reacts 30 minutes.Then the solution after reaction being stopped is added dropwise in potassiumiodide (KI) solution (62g potassiumiodide+100ml water), 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, separated with silica gel column chromatography, then carry out recrystallizing methanol, obtain 4.1g purified product 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
Two, compound 4, and 9-bis-is bromo-6, the preparation of 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), add 2,6,13,17-tetramethyl--9-octadecyne (3.07g, 10mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 25ml DMF, pass into nitrogen gas stirring 20min, add Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, and ring closure reaction 2h is carried out in heating, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography is separated, obtains 2.4g purified product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 70%.
Three, 9,9-dioctyl-2, the preparation of 7-bis-(tributyl tin) silicon fluorenes
Under the protection of nitrogen, in there-necked flask, add 9,9-dioctyl-2; 7-dibromo silicon fluorenes (8.48g; 0.015mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, with syringe, slowly inject n-Butyl Lithium (12.6mL again; 2.5M; 0.03mol), continue stirring reaction 2h, under-78 ℃ of conditions, with syringe, inject tributyltin chloride (8.4mL; 0.03mol), low-temp reaction rises to room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain purified product 9,9-dioctyl-2,7-bis-(tributyl tin) silicon fluorenes, productive rate 75%.
Four, the preparation of poly-{ 9,9-dioctyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }
Under nitrogen protection, add 9,9-dioctyl-2; 7-bis-(tributyl tin) silicon fluorenes (197mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mgPd (PPh
3)
2cl
2, be heated to 80 ℃ and carry out Stille coupling reaction 60h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, take out and spend the night, obtain purified product poly-{ 9,9-dioctyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }.
Multipolymer after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 48384, n=48, multipolymer monodispersity is 2.2.
Embodiment 2
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-didecyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }, its structural formula is as follows:
Preparation technology's flow process is as follows:
One, 4, this step 1 of the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides is identical with the step 1 in embodiment 1.
Two, the preparation of poly-{ 9,9-didecyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }
This step 2 is identical with the step 2 of implementing in 1.
Three, 9,9-didecyl-2, the preparation of 7-bis-(tributyl tin) silicon fluorenes
Under the protection of argon gas, in there-necked flask, add 9,9-didecyl-2; 7-dibromo silicon fluorenes (6.21g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, with syringe, slowly inject n-Butyl Lithium (8.4mL again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, with syringe, inject tributyltin chloride (5.6mL; 0.02mol), low-temp reaction rises to room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain purified product 9,9-didecyl-2,7-bis-(tributyl tin) silicon fluorenes, productive rate 60%.
Four, the preparation of poly-{ 9,9-didecyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }
Under argon shield, add 9,9-didecyl-2; 7-bis-(tributyl tin) silicon fluorenes (208.2mg; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with argon gas, then add 5mgPd (PPh
3)
2cl
2, be heated to 120 ℃ and carry out Stille coupling reaction 6h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains purified product poly-{ 9,9-didecyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }.
Multipolymer after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 57402, n=54, multipolymer monodispersity is 2.2.
Embodiment 3
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-, bis-NSC 62789 base silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) }, its structural formula is as follows:
Preparation technology's flow process is as follows:
One, 4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step 1 is identical with the step 1 in embodiment 1.
Two,, 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) preparation of octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), (synthetic method is with reference to Chem.Commun. to add 2,6 – dimethyl-9-30 alkynes (4.47g, 10mmol), 2011,47,8850-8852), 25ml DMF, pass into nitrogen gas stirring 20min, add Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 100 ℃, and ring closure reaction 6h is carried out in heating, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography is separated, obtains 2.7g purified product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 62%.
Three, 9,9-bis-NSC 62789 base-2, the preparation of 7-bis-(tributyl tin) silicon fluorenes
Under the protection of nitrogen and argon gas gas mixture, in there-necked flask, add 9,9-, bis-NSC 62789 base-2; 7-dibromo silicon fluorenes (9.01g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, with syringe, slowly inject n-Butyl Lithium (8.4mL again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 ℃ of conditions, with syringe, inject tributyltin chloride (5.6mL; 0.02mol), low-temp reaction rises to room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain purified product 9,9-bis-NSC 62789 base-2,7-bis-(tributyl tin) silicon fluorenes, productive rate 68%.
Four, the preparation of poly-{ 9,9-, bis-NSC 62789 base silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) }
Under nitrogen and the protection of argon gas gas mixture; add 9,9-NSC 62789 base-2,7-bis-(tributyl tin) silicon fluorenes (264.2mg; 0.2mmol), 4; the bromo-6-of 9-bis-(3,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3; 4-e] two (diazosulfide) (173.6mg; 0.2mmol), with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen and argon gas gas mixture, then add 5mg Pd (PPh
3)
2cl
2, be heated to 100 ℃ and carry out Stille coupling reaction 24h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, take out and spend the night, obtain purified product poly-{ 9,9-, bis-NSC 62789 base silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) }.
Multipolymer after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 148500, n=100, multipolymer monodispersity is 2.9.
Embodiment 4
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-dimethyl-silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }, its structural formula is as follows:
n=40
Preparation technology's flow process is as follows:
One, 4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step 1 is identical with the step 1 in embodiment 1.
Two, 4, the preparation of the bromo-6-of 9-bis-(3,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides)
This step 2 is identical with the step 2 in embodiment 3.
Three, 9,9-dimethyl-2, the preparation of 7-bis-(tributyl tin) silicon fluorenes
Under the protection of nitrogen, in there-necked flask, add 9,9-dimethyl-2; 7-dibromo silicon fluorenes (7.36g; 0.02mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, with syringe, slowly inject n-Butyl Lithium (16.8mL again; 2.5M; 0.04mol), continue stirring reaction 1.5h, under-78 ℃ of conditions, with syringe, inject tributyltin chloride (11.2mL; 0.04mol), low-temp reaction rises to room temperature reaction 6 hours after 1 hour.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina column chromatography for separation, obtain purified product 9,9-dimethyl-2,7-bis-(tributyl tin) silicon fluorenes, productive rate 70%.
Four, the preparation of poly-{ 9,9-dimethyl-silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection; add 9,9-dimethyl-2,7-bis-(tributyl tin) silicon fluorenes (157.6mg; 0.2mmol), 4; the bromo-6-of 9-bis-(3,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3; 4-e] two (diazosulfide) (173.6mg; 0.2mmol), with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2cl
2, be heated to 70 ℃ and carry out Stille coupling reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, take out and spend the night, obtain purified product poly-{ 9,9-dimethyl-silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e], two (diazosulfides) }.
Multipolymer (P3) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 38080, n=40, multipolymer monodispersity is 2.1.
Embodiment 5
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-dimethyl-silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }, its structural formula is as follows:
Preparation technology's flow process is as follows:
One, 4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step 1 is identical with the step 1 in embodiment 1.
Two, 4, the preparation of the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] (diazosulfide)
This step 2 is identical with the step 2 in embodiment 4.
Three, 4, the preparation of the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (6.8g, 10mmol), add 2 – pentyne (1.36g, 20mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 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 ℃, ring closure reaction 2h is carried out in heating, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, obtain 2.6g purified product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 52.6%.
Four, the preparation of poly-{ 9,9-dimethyl-silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection; add 9; 9-dimethyl-2,7-bis-(tributyl tin) silicon fluorenes (157.6mg, 0.2mmol), 4; the bromo-6-methyl-7-of 9-bis-ethyl benzo [2; 1-e:3,4-e] two (diazosulfide) (148.2mg, 0.3mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 0.11mg Pd (PPh
3)
2cl
2, be heated to 50 ℃ and carry out Stille coupling reaction 100h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 100ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, take out and spend the night, obtain purified product poly-{ 9,9-dimethyl-silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }.
Multipolymer after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 573, n=1,
Embodiment 6
The multipolymer of the siliceous fluorenes-benzo two (diazosulfide) of the present embodiment, i.e. poly-{ 9,9-dioctyl silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }, its structural formula is as follows:
Preparation technology's flow process is as follows:
One, 4, the preparation of 4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step 1 is identical with the step 1 in embodiment 1.
Two, 4, this step 2 of preparation of the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (diazosulfides) is identical with the step 2 of embodiment 5.
Three, 9,9-dioctyl-2, the preparation of 7-bis-(tributyl tin) silicon fluorenes
This step 2 is identical with the step 2 of embodiment 1.
Four, the preparation of poly-{ 9,9-dioctyl silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }
Under nitrogen protection; add 9; 9-dioctyl-2,7-bis-(tributyl tin) silicon fluorenes (295.5mg, 0.3mmol), 4; the bromo-6-methyl-7-of 9-bis-ethyl benzo [2; 1-e:3,4-e] two (diazosulfide) (98.8mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 28.04mg Pd (PPh
3)
2cl
2, be heated to 90 ℃ and carry out Stille coupling reaction 36h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 100ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, with neutral alumina, cross chromatography column, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, take out and spend the night, obtain purified product poly-{ 9,9-dioctyl silicon fluorenes-6-methyl-7-ethyl-benzo [2,1-e:3,4-e], two (diazosulfides) }.
Multipolymer after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 26915, n=35, multipolymer monodispersity is 2.3.
Embodiment 7
The present embodiment is organic solar batteries, and its structure as shown in Figure 1, comprises the substrate of glass 11, anode layer 12, middle supplementary layer 13, active coating 14 and the cathode layer 15 that stack gradually.Wherein, the material of anode layer is ITO, is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and middle supplementary layer adopts poly-(3,4-Ethylenedioxy Thiophene) (be called for short PEDOT): polystyrolsulfon acid (being called for short PSS) matrix material, is expressed as PEDOT:PSS; Active coating comprises electron donor material and electron acceptor material, electron donor material be embodiment 1 make poly-{ 9,9-dioctyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (with P1, representing), electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); Cathode layer is aluminium, and this device architecture can briefly be described as: glass/ITO/PEDOT:PSS/P1/Al.
Wherein, substrate of glass, as bottom, is chosen ito glass (with anode ITO layer, can buy) during making, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma, processes; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 120nm; Again the P1 of 10mg is dissolved in to 0.4ml dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4ml chlorobenzene obtains, be spun on PEDOT:PSS rete, thickness is about 120nm, obtains active coating; At vacuum condition (2 * 10
-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains organic solar batteries.Accompanying drawing 1, represents that this multipolymer produces photoelectric current as the organic solar batteries of active coating under illumination effect, realizes opto-electronic conversion.
Embodiment 8 and 9, is organic solar batteries, the electron donor material in its luminescent layer be embodiment 2 and 3 make poly-{ 9,9-didecyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) } (with P2, representing) and poly-{ 9,9-bis-NSC 62789 base silicon fluorenes-6-(3,7-dimethyl) octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) } (with P3, representing), other are identical with embodiment 7.
Embodiment 7,8 and 9 all preparation process are all carried out in the glove box of nitrogen inert atmosphere is provided.
The organic solar batteries that embodiment 7,8 and 9 is prepared, the material of its active coating adopts respectively the multipolymer (adopting respectively P1, P2, P3 to replace) of embodiment 1,2 and 3 preparations.The electrical property of organic solar batteries, I-E characteristic, is obtained by Keithley236 current/voltage source-measuring system and test component test, in Table 1.
Table 1
As seen from the data in Table 1, the energy conversion efficiency of the organic solar batteries that the multipolymer making with the present invention is prepared as active coating is 1.39 ~ 1.71, by silicon fluorenes and the synthetic multipolymer of diazosulfide monomer, its effciency of energy transfer is for being 1.6%, these show that siliceous fluorenes-benzo two of the present invention (diazosulfide) multipolymer is owing to containing new benzo two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and pass through the improvement of device architecture or modification, can obtain higher effciency of energy transfer.
Embodiment 10
The present embodiment is organic electroluminescence device, and the multipolymer of preparing with embodiment 1 (gathers { 9,9-dioctyl silicon fluorenes-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides) }, adopt P1 to represent) and for luminescent layer, be prepared with organic electroluminescence devices, as shown in Figure 2, comprise the glass substrate 21 stacking gradually, transparent anode 22, luminescent layer 23, cathode buffer layer 24, negative electrode 25.Wherein, transparent anode is that square resistance is the tin indium oxide (ITO) (thickness 150nm) of 10-20 Ω/mouth, buffer layer adopts PEDOT:PSS (thickness 30nm), luminescent layer is the copolymer p 1(thickness 80nm of embodiment 1 preparation), buffer layer is LiF (thickness 1.5nm), and negative electrode is metal A l (thickness 150nm); Wherein, PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid), PEDOT:PSS represent PEDOT and PSS compound.
The structure of this organic electroluminescence devices is: ITO/PEDOT:PSS/P1/LiF/Al.
By Keithley source measuring system (Keithley 2400 Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, 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 11.5cd/A, and high-high brightness is 1110cd/m
2.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a multipolymer for siliceous fluorenes-benzo two (diazosulfide), is characterized in that, this multipolymer has following general structure:
In formula: R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100.
2. multipolymer according to claim 1, is characterized in that, n is the integer between 35-54.
3. a preparation method for the multipolymer of siliceous fluorenes-benzo two (diazosulfide), is characterized in that, comprises the steps:
Under inert atmosphere, the structural formula that is 1:2 by mol ratio is
compd A and structural formula be
the first solvent of existing at the first catalyzer and alkaline solution of compd B in, at 100 ~ 150 ℃, carry out ring closure reaction 2 ~ 6 hours, make structural formula and be
compound C;
Under inert atmosphere, by structural formula, be
compound D be dissolved in tetrahydrofuran solvent, and be placed under-78 ℃ of conditions and add again n-Butyl Lithium, stirring reaction 1 ~ 2 hour; Add subsequently tributyltin chloride, continue reaction and rise to room temperature reaction 6 hours after 1 hour; Obtaining structural formula is
compd E; Wherein, the molar weight of described Compound D and n-Butyl Lithium is 1:2, and tributyltin chloride is identical with the molar weight of n-Butyl Lithium;
Under inert atmosphere, Compound C and compd E are added in the second solvent that the second catalyzer exists, at 50 ~ 120 ℃ to Stille coupling reaction 6 ~ 100 hours according to the ratio of 1: 1.5 ~ 1.5:1 of mol ratio, make structural formula and be
the multipolymer of siliceous fluorenes-benzo two (diazosulfide);
In above-mentioned formula: R
1, R
2, R
3, R
4be respectively identical or not identical C
1~ C
20alkyl; N is the integer between 1-100.
4. preparation method according to claim 3, is characterized in that, n is the integer between 35-54.
5. preparation method according to claim 3, is characterized in that, described compd A is to adopt following steps to make:
By structural formula, be
compound I add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is
compound F 17-hydroxy-corticosterone;
Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is
compound G;
Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be
compound H;
Compound H is added to SnCl
2in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes compd A.
6. preparation method according to claim 3, is characterized in that, described the first catalyzer is palladium, and the mole dosage of this first catalyzer is compd A 10%; Described alkaline solution is Bu
3n solution, alkali solute Bu in this alkaline solution
3the mole dosage of N is 1:1 with the ratio of the mole dosage of compd B; Described the first solvent is DMF.
7. preparation method according to claim 3, is characterized in that, described the second catalyzer is tetrakis triphenylphosphine palladium, three (dibenzalacetone) two palladiums or two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2); The molar weight of this second catalyzer is 0.05 ~ 20% of Compound C molar weight; Described the second solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
8. preparation method according to claim 3, is characterized in that, during Stille coupling reaction, temperature of reaction is 70 ~ 100 ℃, and the reaction times is 24 ~ 72 hours.
9. the application of multipolymer claimed in claim 1 in multipolymer solar cell, organic electroluminescence device.
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|---|---|---|---|---|
| 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 |
| CN108409682A (en) * | 2018-03-15 | 2018-08-17 | 华东师范大学 | A kind of chirality diazole and binaphthol derivative and its synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN108409682A (en) * | 2018-03-15 | 2018-08-17 | 华东师范大学 | A kind of chirality diazole and binaphthol derivative and its synthetic method |
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Application publication date: 20140312 |