CN103833979A - Bitriselenophen-benzodi(benzoselendiazole) copolymer, preparation method and application thereof - Google Patents
Bitriselenophen-benzodi(benzoselendiazole) copolymer, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to bitriselenophen-benzodi(benzoselendiazole) copolymer. The general molecular formula of the copolymer is as shown in the specification, wherein R1, R2, R3 and R4 are alkyl groups from C1 to C20, and n is an integer between 1 and 100. The bitriselenophen-benzodi(benzoselendiazole) copolymer is high in carrier migration rate and wider in spectral response. The invention also provides a preparation method of the bitriselenophen-benzodi(benzoselendiazole) copolymer and application thereof.
Description
Technical field
The present invention relates to field of photovoltaic materials, particularly relate to a kind of and three thiophene-benzo two (selenole) multipolymer 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.
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.Although people have dropped into large quantity research aspect polymer solar battery, and obtain development at full speed, but at present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be polymkeric substance carrier mobility than the mobility of inorganic monocrystal material low several orders of magnitude.The spectral response of the conjugated polymers photocell material using at present is carried, and its absorption spectrum can not mate well with solar spectrum, is another major reason that causes energy transfer efficiency low.
Therefore the polymer photoelectric material that, carrier mobility is high, spectral response is wide is most important for the performance that improves polymer solar battery.
Summary of the invention
Based on this, be necessary to provide also three thiophene-benzo two (selenole) multipolymer that a kind of carrier mobility is higher, spectral response is wider.
A kind of preparation method and application of and three thiophene-benzo two (selenole) multipolymer further, are provided.
A kind of also three thiophene-benzo two (selenole) multipolymer, general molecular formula is:
Wherein, R
1, R
2, R
3and R
4for C
1~ C
20alkyl; N is the integer between 1 ~ 100.
A kind of also preparation method of three thiophene-benzo two (selenole) multipolymer, comprises the steps:
Improve compd A and compd B, wherein, the structural formula of described compd A is:
Wherein, R
1and R
2for C
1~ C
20alkyl;
The structural formula of described compd B is:
Wherein, R
3and R
4for C
1~ C
20alkyl; And
In atmosphere of inert gases, 1.5:1 ~ 1:1.5 is dissolved in described chemical combination A and compd B in solvent in molar ratio, add catalyzer, at 50 ℃ ~ 120 ℃, carry out Stille coupled reaction 6 hours ~ 100 hours, after separation and purification, obtain and three thiophene-benzo two (selenole) multipolymer, general molecular formula described and three thiophene-benzo two (selenole) multipolymer is:
Wherein, n is the integer between 1 ~ 100.
In an embodiment, described catalyzer is three (dibenzalacetone) two palladiums, tetrakis triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride therein.
Therein in an embodiment, 0.05% ~ 20% of the molar weight that the molar weight of described catalyzer is described compd B.
In an embodiment, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene therein.
In an embodiment, described compd A is adopted preparation with the following method therein:
Compound C and Compound D are provided, and the structural formula of described Compound C is:
The structural formula of described Compound D is:
Wherein, R
1and R
2for C
1~ C
20alkyl; And
In protection of inert gas atmosphere, described Compound C and Compound D are dissolved in the first solvent and obtain the first mixed solution, in described the first mixed solution, splash into catalyzer and alkali, at 130 ℃, stirring reaction 4 hours, obtains described compd A after separation and purification; Wherein, 10% of the molar weight that the molar weight of described catalyzer is described Compound C, the mol ratio of described alkali and described Compound D is 1: 1; The mol ratio of described Compound C and Compound D is 1:2.
In an embodiment, described Compound C is adopted preparation with the following method therein:
2-amino-5-N-methyl-p-nitroaniline and pyridine are dissolved in thionyl chloride, in 80 ℃ ~ 90 ℃ back flow reaction 24 hours, after separation and purification, obtain 5-nitro-2,1,3 diazosulfide;
By described 5-nitro-2,1,3 diazosulfide and Hydrogen bromide are mixed to get the first mixture, described the first mixture is warming up to 127 ℃ of backflows, drips bromine and reflux 4 hours to described the first mixture, separation and purification obtains 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide;
By described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide and copper powder add in DMF, are heated to 120 ℃ of reactions 3 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides;
By described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides add in tetrahydrofuran (THF), then add tin chloride, be warming up to 100 ℃, reflux 10 hours, obtains 4 after separation and purification, 4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-diazosulfide;
By described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3-diazosulfide adds and in ethanol, obtains suspension, described suspension is cooled to 0 ℃, then adds sodium borohydride, under room temperature, react 20 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine);
By described 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) be mixed to get the second mixture with ethanol, described the second mixture is refluxed, drip the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution is filtered, obtain described Compound C.
In an embodiment, described compd B is adopted preparation with the following method therein:
Compd E is provided, and the structural formula of described compd E is:
Wherein, R
3and R
4for C
1~ C
20alkyl;
In atmosphere of inert gases, described compd E is dissolved in and in the second solvent, obtains the second mixed solution, at-78 ℃, in described the second mixed solution, add n-Butyl Lithium, and at-78 ℃, react 1 ~ 2 hour, then add tributyltin chloride, at-78 ℃, react 1 hour, then under room temperature, react 6 hours, after separation and purification, obtain described compd B; The mol ratio of wherein said compd E and described n-Butyl Lithium is 1:2, and the mol ratio of described compd E and described tributyltin chloride is 1:2.
Therein in an embodiment, the method of described separation and purification is specially: the reaction solution obtaining to Stille coupled reaction adds deionized water and toluene to extract, organic phase extraction being obtained with underpressure distillation concentrates, then the organic phase after described concentrating is splashed in dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina again, chloroform is removed in decompression, methyl alcohol sedimentation, suction filtration, gained solid extracts with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
Above-mentioned and three thiophene-benzo two (selenole) multipolymer polymer solar battery, organic electroluminescence device, organic field effect tube, organic light store and organic laser in application.
In above-mentioned and three thiophene-benzo two (selenole) multipolymer and three thiophene there are three five-membered ring structures, there is narrow band gap and strong conjugated nature, carrier mobility is high, benzo two (selenole) has the character of energy gap of outstanding adjusting material and wider spectral response, makes the carrier mobility of this and three thiophene-benzo two (selenole) multipolymer higher, spectral response is wider.
Accompanying drawing explanation
Fig. 1 is a preparation method's schema embodiment and three thiophene-benzo two (selenole) multipolymer;
Fig. 2 is the structural representation of the polymer solar cell device of embodiment 6;
Fig. 3 is the structural representation of embodiment 9 organic electroluminescence devices.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Also three thiophene-benzo two (selenole) multipolymer of one embodiment, its general molecular formula is:
Wherein, R
1, R
2, R
3and R
4for C
1~ C
20alkyl; N is the integer between 1 ~ 100.
R
1, R
2and R
3can be identical, also can be different.C
1~ C
20alkyl be straight chained alkyl or branched-chain alkyl.
Thiophene is five-membered ring structure, has moderate band gap, wider spectral response, good thermostability and film forming properties.And also three thiophene have three five-membered ring structures, there is narrow band gap and strong conjugated nature, carrier mobility is high.
Diazosulfide unit is a kind of good body unit that is subject to, and has good electronic transport property, can also regulate the energy gap of material simultaneously.Sulphur atom in selenole in the radius ratio diazosulfide of selenium atom is large, more can strengthen molecule between polymer chain overlapping, promotes the hopping process of electric charge.Thereby selenole has better electronic transport property than diazosulfide, and there is the character of energy gap of outstanding adjusting material and wider spectral response.The advantages such as benzo two (selenole) is a kind of very excellent donor material, and benzo two (selenole) has simple in structure, symmetrical, and electron delocalization performance is good, and be planar conjugate structure, carrier mobility is higher.
Above-mentioned and three thiophene-benzo two (selenole) multipolymer combines and the advantage of three thiophene and benzo two (selenole), polymkeric substance by compound three thiophene and benzo two (selenole) formation can form a kind of very strong donor-receiver structure, charge-transporting matter and the stability of material are conducive to improve on the one hand, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion, have advantages of that carrier mobility is higher, spectral response is wider.
Also three thiophene-benzo two (selenole) multipolymer is applied in solar cell, can improve the effciency of energy transfer of solar cell.And this multipolymer also can be widely used in, in organic electroluminescence device, Organic Light Emitting Diode, organic field effect tube, the storage of organic light and organic laser, being conducive to improve the performance of above-mentioned device.
And, and on three thiophene-benzo two (selenole) multipolymer and three thiophene and benzo two (selenole) are upper while introducing alkyl, also the solvability of three thiophene-benzo two (selenole) multipolymer is better, is conducive to film forming processing.
Refer to Fig. 1, a preparation method embodiment and three thiophene-benzo two (selenole) multipolymer, comprises the steps:
Step S110: compd A and compd B are provided.
Wherein the structural formula of compd A is:
R
1and R
2for C
1~ C
20alkyl.R
1and R
2can be identical, also can be different.C
1~ C
20alkyl be straight chained alkyl or branched-chain alkyl.
Prepare compd A using Compound C and Compound D as reactant.Wherein, the structural formula of Compound C is:
The structural formula of Compound D is:
Wherein, R
1and R
2for C
1~ C
20alkyl.R
1and R
2can be identical, also can be different.C
1~ C
20alkyl be straight chained alkyl or branched-chain alkyl.
In protection of inert gas atmosphere, Compound C and Compound D are dissolved in the first solvent and obtain the first mixed solution, in the first mixed solution, splash into catalyzer and alkali, at 130 ℃, stirring reaction 4 hours, obtains compd A after separation and purification.There is ring closure reaction in Compound C and Compound D, generate compd A under catalyzer and alkali existence.
Wherein, 10% of the molar weight that the molar weight of catalyzer is Compound C, the mol ratio of alkali and Compound D is 1:1; The mol ratio of Compound C and Compound D is 1:2.
The first solvent is preferably dimethyl formamide (DMF).Alkali is preferably tri-n-butyl amine (Bu3N).Catalyzer is preferably acid chloride (Pd (OAc) 2).Being appreciated that catalyzer also can be other can catalytic cpd C and the catalyzer that reacts of Compound D.
The method of separation and purification is: after reaction solution is cooling, and washing, dichloromethane extraction, obtains organic layer, and anhydrous sodium sulfate drying filters, underpressure distillation, silica gel column chromatography separates, and obtains pure compd A.
Reaction formula is as follows:
Compound D is commercially available, and Compound C is adopted and prepared with the following method and obtain:
Be that 22.95g:2mL:100mL is dissolved in 2-amino-5-N-methyl-p-nitroaniline and pyridine in thionyl chloride by solid-to-liquid ratio, in 80 ℃ ~ 90 ℃ back flow reaction 24 hours, after separation and purification, obtain 5-nitro-2,1,3 diazosulfide.
The method of separation and purification is: after stopped reaction, reaction solution is heated to 80 ℃ and revolves and steam excessive thionyl chloride (SOCl
2), reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain pure 5-nitro-2,1,3 diazosulfide.
Reaction formula is as follows:
By 5-nitro-2,1,3 diazosulfide and Hydrogen bromide are mixed to get mixture, and mixture is warming up to 127 ℃ of backflows, in 30 minutes, drip bromine and reflux 4 hours to mixture, and separation and purification obtains the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide.Wherein, 5-nitro-2, the solid-to-liquid ratio of 1,3 diazosulfide, Hydrogen bromide and bromine is 10.35g:15ml:11.3ml.
The method of separation and purification is: by reaction solution heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for filter residue, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain pure 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide.
Reaction formula is as follows:
By bromo-4,7-bis-5-nitro-2,1,3 diazosulfide and copper powder add in DMF, are heated to 120 ℃ of reactions 3 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides.Wherein, the bromo-5-of 4,7-bis-nitro-2, the solid-to-liquid ratio of 1,3 diazosulfide, copper powder and DMF is 10.2g:9.5g:90mL.
The method of separation and purification is: reaction solution is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate, with saturated aqueous common salt and water washing, merges organic layer, anhydrous magnesium sulfate drying, filters, and revolves evaporate to dryness, dehydrated alcohol recrystallization, obtain pure 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide.
Reaction formula is as follows:
By 4,4 '-bis-is bromo-6, and 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides add in tetrahydrofuran (THF), then add tin chloride, are warming up to 100 ℃, reflux 10 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3-diazosulfide.Wherein, 4,4 '-bis-is bromo-6, and the solid-to-liquid ratio of 6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, tetrahydrofuran (THF) and tin chloride is 10.3g:300mL:40g.
Reaction formula is as follows:
By 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3-diazosulfide adds in ethanol and obtains suspension, and suspension is cooled to 0 ℃, then adds sodium borohydride, reacts 20 hours under room temperature, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine).Wherein, 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1, and the solid-to-liquid ratio of 3-diazosulfide, ethanol and sodium borohydride is: 6.80g:200mL:14g.
Reaction formula is as follows:
By 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) are mixed to get the second mixture with ethanol, and the second mixture is refluxed, and drip the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution are filtered, and obtain Compound C.
Wherein, the solid-to-liquid ratio of 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine), ethanol and tin anhydride is: 3.12g:60mL:1.17g; In the tin anhydride aqueous solution, the concentration of tin anhydride is 53.2mg/mL.
Reaction formula is as follows:
The structural formula of compd B is:
Wherein, R
3and R
4for C
1~ C
20alkyl.
With compd E and tributyltin chloride (SnBu
3cl) prepare compd B as reactant.Wherein, the structural formula of compd E is:
Wherein, R
3and R
4for C
1~ C
20alkyl.C
1~ C
20alkyl be straight chained alkyl or branched-chain alkyl.
In atmosphere of inert gases, compd E is dissolved in the second solvent and obtains the second mixed solution, at-78 ℃, in the second mixed solution, add n-Butyl Lithium (CH
3(CH
2)
3li, is called for short n-BuLi), and at-78 ℃, react 1 ~ 2 hour, then add tributyltin chloride, at-78 ℃, react 1 hour, then under room temperature, react 6 hours, after separation and purification, obtain compd B.
The mol ratio of compd E and n-Butyl Lithium is 1:2, and the mol ratio of compd E and tributyltin chloride is 1:2.The second solvent is preferably tetrahydrofuran (THF) (THF).
The method of separation and purification is specially: add saturated sodium-chloride water solution termination reaction, then obtain organic layer with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, by filtrate collection and revolve and evaporate the second solvent and obtain crude product, finally crude product is carried out to neutral alumina column chromatography for separation and obtain pure compd B.
The reaction formula of preparing compd B is as follows:
Step S120: in atmosphere of inert gases, 1.5:1 ~ 1:1.5 is dissolved in chemical combination A and compd B in solvent in molar ratio, add catalyzer, at 50 ℃ ~ 120 ℃, carry out Stille coupled reaction 6 hours ~ 100 hours, after separation and purification, obtain and three thiophene-benzo two (selenole) multipolymer.
Solvent is tetrahydrofuran (THF) (THF), glycol dimethyl ether, ether, benzene or toluene.Solvent is enough, to guarantee that compd A, compd B and catalyzer fully dissolve.
Catalyzer is preferably 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), more preferably bi triphenyl phosphorus palladium chloride (Pd (PPh
3)
2cl
2).In other embodiments, also can adopt nickel catalyzator or copper catalyst.
The molar weight of catalyzer be preferably compd B molar weight 0.05% ~ 20%.
Compd A and compd B are take solvent as reaction medium, under catalyzer exists, at 50 ℃ ~ 120 ℃, carry out Stille coupled reaction 6 hours ~ 100 hours, obtain and three thiophene-benzo two (selenole) multipolymer after separation and purification, its general molecular formula is:
Wherein, n is the integer between 1 ~ 100.
Reaction formula is as follows:
The method of separation and purification is specially: obtain reaction solution to Stille coupled reaction and add deionized water and toluene to extract, organic phase extraction being obtained with underpressure distillation concentrates, then the organic phase after concentrated is splashed in dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina again, chloroform is removed in decompression, methyl alcohol sedimentation, suction filtration, gained solid extracts with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
The preparation method of above-mentioned and three thiophene-benzo two (selenole) multipolymer, technique is simple, to equipment require littlely, reaction conditions gentleness, is easy to control, and is easy to extensive preparation.
It is below specific embodiment
Embodiment 1
Preparation poly-{ 3,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }, structural formula is:
1, preparation Compound C-4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
(1) prepare compound 5-nitro-2,1,3 diazosulfide
In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, after heating, in 90 ℃ 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 product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
Reaction formula is as follows:
(2) prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide
In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide 15ml, be warming up to 127 ℃ of backflows, in 30min, slowly drip bromine 11.3ml the 4h that refluxes, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 10.2g, productive rate 50%.
Reaction formula is as follows:
(3) prepare compound 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides
In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g and the DMF of 90ml (DMF), be heated to 120 ℃ of reactions after 3 hours, stopped reaction, is 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, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.
Reaction formula is as follows:
(4) prepare compound 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-diazosulfide
In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran (THF) that 300ml is dry (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, obtains solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20ml(37.7mmol in 30 minutes), 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 potassiumiodide+100ml water) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
Reaction formula is as follows:
(5) prepare compound 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (6.80g, 0.01mol), adds the ethanol of 200ml, form suspension, 0 ℃ drips sodium borohydride (14g, 0.37mol), mixture stirring reaction 20 hours under room temperature, stopped reaction, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, obtain 5.49g product, productive rate 88%.
Reaction formula is as follows:
(6) prepare compound 4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) (3.12g, 5mmol), add the ethanolic soln of 60ml, reflux, drip SeO2 (1.17g, 10.5mmol) the aqueous solution (hot water 22ml), reaction mixture refluxed 2 hours, stopped reaction, filters, obtain 3.48g product, productive rate 90%.
Reaction formula is as follows:
2, prepare compd A-4,9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (Compound C) (3.87g, 5mmol), 2,6,13,17-tetramethyl--9-octadecyne (Compound D) (3.07g, 10mmol) and 25ml DMF, pass into nitrogen gas stirring 20min, adds Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.48g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 60%.
Reaction formula is as follows:
3, compd B-3,5-dioctyl-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene also
Under the protection of nitrogen; in there-necked flask, add 3; 5-dioctyl-2; 6-dibromo also [3; 2-b:4; 5-b '] three thiophene (compd E) (5.79g; 0.01mol), add the tetrahydrofuran solvent of 60ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 2h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), at-78 ℃, react and after 1 hour, rise under room temperature stirring reaction 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, obtain organic layer, 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 product, productive rate 68%.
Reaction formula is as follows:
4, preparation poly-{ 3,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, add 3,5-dioctyl-2; 6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene (compd B) (199.8mg also; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (selenole) (compd A) (165.2mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh
3)
2cl
2(5mg, 7.1 × 10
-3mmol), be heated to 90 ℃ of 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 polymkeric substance/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, cross chromatography column with neutral alumina, 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 product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 57980, n=52, polymkeric substance monodispersity is 2.4.
Embodiment 2
Preparation poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }, structural formula is:
1, preparation Compound C-4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
Preparation method is with embodiment 1.
2, prepare compd A-4,9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (Compound C) (3.87g, 5mmol), 2,6,13,17-tetramethyl--9-octadecyne (Compound D) (3.07g, 10mmol) and 25ml DMF, pass into nitrogen gas stirring 20min, adds Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.48g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 60%.
Reaction formula is as follows:
3, prepare compd B-3,5-dimethyl-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene also
Under the protection of nitrogen; in there-necked flask, add 3; 5-dimethyl-2; 6-dibromo also [3; 2-b:4; 5-b '] three thiophene (compd E) (3.82g; 0.01mol), add the tetrahydrofuran solvent of 40ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), at-78 ℃, react and after 1 hour, be warming up under room temperature stirring reaction 6 hours.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 product, productive rate 60%.
Reaction formula is as follows:
4, preparation poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, add 3,5-dimethyl-2; 6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene (compd B) (160.4mg also; 0.2mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl) octyl group-benzo [2; 1-e:3,4-e] two (selenole) (compd A) (165.2mg, 0.2mmol) and tetrahydrofuran solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add Pd
2(dba)
3(5mg, 5.5 × 10
-3mmol), be heated to 90 ℃ of 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 polymkeric substance/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, cross chromatography column with neutral alumina, 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 product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 15623, n=17, polymkeric substance monodispersity is 2.5.
Reaction formula is as follows:
Embodiment 3
Preparation poly-{ 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) also }, structural formula is:
1, preparation Compound C-4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
Preparation method is with embodiment 1.
2, prepare compd A-4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (Compound C) (7.74g, 10mmol), (1.36g, 20mmol and 50ml DMF, pass into nitrogen gas stirring 20min to 2 – pentynes (Compound D), adds Bu
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 5.15g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.
Reaction formula is as follows:
3, prepare compd B-3,5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene also
Under the protection of nitrogen; in there-necked flask, add 3; 5-bis-(NSC 62789 base)-2; 6-dibromo also [3; 2-b:4; 5-b '] three thiophene (compd E) (9.15g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.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 product, productive rate 74%.
Reaction formula is as follows:
4, preparation poly-{ 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) also }
Under nitrogen protection, add 3,5-bis-(NSC 62789 base)-2; 6-bis-(tributyl tin) also [3; 2-b:4,5-b '] three thiophene (compd B) (267mg, 0.2mmol), 4; the bromo-6-methyl-7-of 9-bis-ethyl benzo [2; 1-e:3,4-e] two (selenole) (compd A) (117.6mg, 0.2mmol) and toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh
3)
4(9mg, 7.8 × 10
-3mmol), be heated to 90 ℃ of 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 polymkeric substance/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, cross chromatography column with neutral alumina, 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 product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 23066, n=19, polymkeric substance monodispersity is 2.3.
Embodiment 4
Preparation poly-{ 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6-(3 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) }, structural formula is:
1, preparation Compound C-4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
Preparation method is with embodiment 1.
2, prepare compd A-4, the bromo-6-(2 of 9-bis-, 7-dimethyl) 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 selenoles (Compound C) (3.87g, 5mmol), 2,6 – dimethyl-9-30 alkynes (Compound D) (4.47g, 10mmol) and 30mlDMF, pass into nitrogen gas stirring 20min, add Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.7g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 62%.
Reaction formula is as follows:
3, prepare compd B-3,5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene also
Under the protection of nitrogen; in there-necked flask, add 3; 5-bis-(NSC 62789 base)-2; 6-dibromo also [3; 2-b:4; 5-b '] three thiophene (compd E) (9.15g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.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 product, productive rate 74%.
Reaction formula is as follows:
4, gather 3,5-bis-(NSC 62789 base) is [3,2-b:4,5-b '] three thiophene-6-(3 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles)
Under nitrogen protection, add 3, 5-bis-(NSC 62789 base)-2, 6-bis-(tributyl tin) also [3, 2-b:4, 5-b '] three thiophene (compd B) (267mg, 0.2mmol) (400.5mg, 0.3mmol), 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2, 1-e:3, 4-e] two (selenole) (compd A) (193.4mg, 0.2mmol) with glycol dinitrate ether solvents 40ml, vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh3) 2Cl2 (28.04mg, 0.04mmol), be heated to 120 ℃ of 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 polymkeric substance/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, cross chromatography column with neutral alumina, 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 product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 159200, n=100, polymkeric substance monodispersity is 5.1
Reaction formula is as follows:
Embodiment 5
Preparation poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) also }, structural formula is:
1, preparation Compound C-4,4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole
Preparation method is with embodiment 1.
2, prepare compd A-4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles (Compound C) (7.74g, 10mmol), (1.36g, 20mmol and 50ml DMF, pass into nitrogen gas stirring 20min to 2 – pentynes (Compound D), adds Bu
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 5.15g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.
Reaction formula is as follows:
3, prepare compd B-3,5-dimethyl-2,6-bis-(tributyl tin) is [3,2-b:4,5-b '] three thiophene also
Under the protection of nitrogen; in there-necked flask, add 3; 5-dimethyl-2; 6-dibromo also [3; 2-b:4; 5-b '] three thiophene (compd E) (3.82g; 0.01mol), add the tetrahydrofuran solvent of 40ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 ℃ of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.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 product, productive rate 60%.
Reaction formula is as follows:
4, preparation poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) also }
Under nitrogen protection, add 3,5-dimethyl-2; 6-bis-(tributyl tin) also [3; 2-b:4,5-b '] three thiophene (compd B) (160.4mg, 0.2mmol), 4; the bromo-6-methyl-7-of 9-bis-ethyl benzo [2; 1-e:3,4-e] two (selenole) (compd A) (176.4mg, 0.3mmol) and benzene solvent 40ml; vacuumize deoxygenation and be filled with nitrogen, then add Pd (PPh
3)
2cl
2(1.05mg, 1.5 × 10
-4mmol) be heated to 50 ℃ of 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 polymkeric substance/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, cross chromatography column with neutral alumina, 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 product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 681, n=1
Reaction formula is as follows:
Embodiment 6
Polymer solar cell device
Refer to Fig. 2, solar cell device comprises auxiliary 13 layers of substrate 11, anode 12, the centre, active coating 14 and the negative electrode 15 that stack gradually, and the representation of this device is substrate/anode/middle supplementary layer/active coating/negative electrode.Wherein, substrate 11 adopts substrate of glass; Anode 12 is that square resistance is the indium tin oxide films (ITO) of 10 Ω/mouths; The material of middle supplementary layer 13 is PEDOT:PSS matrix material, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid); The material of active coating 14 comprises electron donor material and electron acceptor material, adopt poly-{ 3 of embodiment 1,5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } as electron donor material, electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); Negative electrode 15 is aluminium.
Wherein, substrate 11 is substrate of glass, chooses ito glass (with the ito glass substrate of anode 12, can buy) when making, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then in ito glass substrate, apply PEDOT:PSS and form middle supplementary layer 13, thickness is 120nm; That prepared by 10mg embodiment 1 gathers { 3 again, 5-dioctyl is [3,2-b:4,5-b '] three thiophene-6 also, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } be dissolved in 0.4ml dimethylbenzene, be dissolved in 8mg PCBM the solution blending that 0.4ml chlorobenzene obtains and obtain mixture, this mixture is spun on PEDOT:PSS rete, and thickness is about 150nm, obtains active coating 14; At vacuum condition (2 × 10
-3pa) lower evaporation metal aluminium forms negative electrode 15 on active coating, and thickness is 120nm, obtains polymer solar cell device.Above-mentioned preparation process is all carried out in the glove box that nitrogen inert atmosphere is provided.
Embodiment 7
Polymer solar cell device
In the present embodiment, the structure of polymer solar cell device is identical with embodiment 6, except the electron donor material of active coating 14 adopts poly-{ 3 of embodiment 2,5-dimethyl also [3,2-b:4,5-b '] three thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } outside, all the other are identical with embodiment 6.
Embodiment 8
In the present embodiment, the structure of polymer solar cell device is identical with embodiment 6, except the electron donor material of active coating 14 adopts poly-{ 3 of embodiment 3,5-bis-(NSC 62789 base) also [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) } outside, all the other are identical with embodiment 6.
Adopt Keithley236 current/voltage source-measuring system performance of the polymer solar cell device of test implementation example 6 ~ 8 respectively, test result is in table 1.
The performance data of the polymer solar cell device of table 1 embodiment 6 ~ 8
As seen from the data in Table 1, the energy conversion efficiency of the polymer solar cell device of preparing as the electron donor material of active coating with embodiment 6 ~ 8 multipolymers is 0.89 ~ 1.60, show that also three thiophene-benzo two (selenole) multipolymer of embodiment 6 ~ 8 is owing to containing new benzo two (selenole) 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 improve effciency of energy transfer.
Embodiment 9
Organic electroluminescence device
Refer to Fig. 3, the structure of organic electroluminescence device is: substrate 21/ anode 22/ luminescent layer 23/ buffer layer 24/ negative electrode 25, substrate 21 is glass substrate, deposits the tin indium oxide that one deck square resistance is 20 Ω/mouths (ITO) as anode 22 on glass substrate, and the thickness of anode 22 is 150nm; Adopt poly-{ also [3, the 2-b:4 of 3,5-dioctyl of embodiment 1,5-b '] three thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } as the material of luminescent layer 23, the thickness of luminescent layer 23 is 80nm; On luminescent layer 23, vacuum evaporation lithium fluoride (LiF) forms buffer layer 24, and the thickness of buffer layer 24 is 1.5nm; Evaporation metal Al forms negative electrode 25 on buffer layer, obtains organic electroluminescence device, and the thickness of negative electrode 25 is 150nm.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley2400Sourcemeter), 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 13.5cd/A, and high-high brightness is 1155cd/m
2.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. and three thiophene-benzo two (selenole) multipolymer, it is characterized in that, general molecular formula is:
Wherein, R
1, R
2, R
3and R
4for C
1~ C
20alkyl; N is the integer between 1 ~ 100.
2. and the preparation method of three thiophene-benzo two (selenole) multipolymer, it is characterized in that, comprise the steps:
Improve compd A and compd B, wherein, the structural formula of described compd A is:
Wherein, R
1and R
2for C
1~ C
20alkyl;
The structural formula of described compd B is:
Wherein, R
3and R
4for C
1~ C
20alkyl; And
In atmosphere of inert gases, 1.5:1 ~ 1:1.5 is dissolved in described chemical combination A and compd B in solvent in molar ratio, add catalyzer, at 50 ℃ ~ 120 ℃, carry out Stille coupled reaction 6 hours ~ 100 hours, after separation and purification, obtain and three thiophene-benzo two (selenole) multipolymer, general molecular formula described and three thiophene-benzo two (selenole) multipolymer is:
Wherein, n is the integer between 1 ~ 100.
3. the preparation method of according to claim 2 and three thiophene-benzo two (selenole) multipolymer, it is characterized in that, described catalyzer is three (dibenzalacetone) two palladiums, tetrakis triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride.
4. according to preparation method described in claim 2 or 3 and three thiophene-benzo two (selenole) multipolymer, it is characterized in that 0.05% ~ 20% of the molar weight that the molar weight of described catalyzer is described compd B.
5. the preparation method of according to claim 2 and three thiophene-benzo two (selenole) multipolymer, is characterized in that, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
6. the preparation method of according to claim 2 and three thiophene-benzo two (selenole) multipolymer, is characterized in that, described compd A is adopted preparation with the following method:
Compound C and Compound D are provided, and the structural formula of described Compound C is:
The structural formula of described Compound D is:
Wherein, R
1and R
2for C
1~ C
20alkyl; And
In protection of inert gas atmosphere, described Compound C and Compound D are dissolved in the first solvent and obtain the first mixed solution, in described the first mixed solution, splash into catalyzer and alkali, at 130 ℃, stirring reaction 4 hours, obtains described compd A after separation and purification; Wherein, 10% of the molar weight that the molar weight of described catalyzer is described Compound C, the mol ratio of described alkali and described Compound D is 1:1; The mol ratio of described Compound C and Compound D is 1:2.
7. the preparation method of according to claim 6 and three thiophene-benzo two (selenole) multipolymer, is characterized in that, described Compound C is adopted preparation with the following method:
2-amino-5-N-methyl-p-nitroaniline and pyridine are dissolved in thionyl chloride, in 80 ℃ ~ 90 ℃ back flow reaction 24 hours, after separation and purification, obtain 5-nitro-2,1,3 diazosulfide;
By described 5-nitro-2,1,3 diazosulfide and Hydrogen bromide are mixed to get the first mixture, described the first mixture is warming up to 127 ℃ of backflows, drips bromine and reflux 4 hours to described the first mixture, separation and purification obtains 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide;
By described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide and copper powder add in DMF, are heated to 120 ℃ of reactions 3 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides;
By described 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides add in tetrahydrofuran (THF), then add tin chloride, be warming up to 100 ℃, reflux 10 hours, obtains 4 after separation and purification, 4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-diazosulfide;
By described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3-diazosulfide adds and in ethanol, obtains suspension, described suspension is cooled to 0 ℃, then adds sodium borohydride, under room temperature, react 20 hours, after separation and purification, obtain 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine);
By described 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) be mixed to get the second mixture with ethanol, described the second mixture is refluxed, drip the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution is filtered, obtain described Compound C.
8. the preparation method of according to claim 2 and three thiophene-benzo two (selenole) multipolymer, is characterized in that, described compd B is adopted preparation with the following method:
Compd E is provided, and the structural formula of described compd E is:
Wherein, R
3and R
4for C
1~ C
20alkyl;
In atmosphere of inert gases, described compd E is dissolved in and in the second solvent, obtains the second mixed solution, at-78 ℃, in described the second mixed solution, add n-Butyl Lithium, and at-78 ℃, react 1 ~ 2 hour, then add tributyltin chloride, at-78 ℃, react 1 hour, then under room temperature, react 6 hours, after separation and purification, obtain described compd B; The mol ratio of wherein said compd E and described n-Butyl Lithium is 1:2, and the mol ratio of described compd E and described tributyltin chloride is 1:2.
9. the preparation method of according to claim 2 and three thiophene-benzo two (selenole) multipolymer, it is characterized in that, the method of described separation and purification is specially: the reaction solution obtaining to Stille coupled reaction adds deionized water and toluene to extract, organic phase extraction being obtained with underpressure distillation concentrates, then the organic phase after described concentrating is splashed in dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina again, chloroform is removed in decompression, methyl alcohol sedimentation, suction filtration, gained solid extracts with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
10. the as claimed in claim 1 and application of three thiophene-benzo two (selenole) multipolymer in polymer solar battery, organic electroluminescence device, organic field effect tube, the storage of organic light and organic laser.
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| CN105418899A (en) * | 2015-12-24 | 2016-03-23 | 杨荣 | Preparation method and application of conjugate polymer used in organic semiconductor |
| 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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| CN1731901A (en) * | 2005-05-31 | 2006-02-08 | 华南理工大学 | Organic / macromolecule top emission light-emitting device and its application |
| CN102159618A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from benzobis(silolothiophene) and their use as organic semiconductors |
| CN102746492A (en) * | 2012-06-25 | 2012-10-24 | 南京邮电大学 | Conjugated backbone doped fold-line water-soluble poly(aryleneethynylene) and preparation method thereof |
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| CN1731901A (en) * | 2005-05-31 | 2006-02-08 | 华南理工大学 | Organic / macromolecule top emission light-emitting device and its application |
| CN102159618A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from benzobis(silolothiophene) and their use as organic semiconductors |
| CN102746492A (en) * | 2012-06-25 | 2012-10-24 | 南京邮电大学 | Conjugated backbone doped fold-line water-soluble poly(aryleneethynylene) and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105418899A (en) * | 2015-12-24 | 2016-03-23 | 杨荣 | Preparation method and application of conjugate polymer used in organic semiconductor |
| 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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