CN103833979B - And three thiophene-benzo two (selenole) multipolymer and its preparation method and application - Google Patents
And three thiophene-benzo two (selenole) multipolymer and its preparation method and application Download PDFInfo
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- CN103833979B CN103833979B CN201210491317.0A CN201210491317A CN103833979B CN 103833979 B CN103833979 B CN 103833979B CN 201210491317 A CN201210491317 A CN 201210491317A CN 103833979 B CN103833979 B CN 103833979B
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Abstract
A kind of also three thiophene-benzo two (selenole) multipolymer of the present invention, 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.Should and the carrier mobility of three thiophene-benzo two (selenole) multipolymer is higher, spectral response is wider.Further, the present invention also provides a kind of and the preparation method and application of three thiophene-benzo two (selenole) multipolymer.
Description
Technical field
The present invention relates to field of photovoltaic materials, particularly relate to a kind of also 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 of photovoltaic art always.Business-like silicon solar cell is high due to complex manufacturing, cost at present, makes it apply and is restricted.In order to reduce costs, expansive approach scope, 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 low in raw material price, quality are light, flexibility, simple, the available coating of production technique, printing such as to prepare at the advantage.Although people have dropped into large quantity research in polymer solar battery, and achieve 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 is the carrier mobility of polymkeric substance several orders of magnitude lower than the mobility of inorganic monocrystalline material.The spectral response of the conjugated polymers photocell material used at present is comparatively carried, and its absorption spectrum can not mate well with solar spectrum, is another major reason causing energy transfer efficiency low.
Therefore, the polymer photoelectric material that carrier mobility is high, spectral response is wide is most important for the performance improving 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.
Further, a kind of preparation method and application of also three thiophene-benzo two (selenole) multipolymer 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 preparation method of also 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, described chemical combination A and compd B are dissolved in solvent by 1.5:1 ~ 1:1.5 in molar ratio, add catalyzer, Stille coupled reaction is carried out 6 hours ~ 100 hours at 50 DEG C ~ 120 DEG C, obtain after separation and purification and three thiophene-benzo two (selenole) multipolymer, described and general molecular formula that is three thiophene-benzo two (selenole) multipolymer is:
Wherein, n is the integer between 1 ~ 100.
Wherein in an embodiment, described catalyzer is three (dibenzalacetone) two palladium, tetrakis triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride.
Wherein in an embodiment, the molar weight of described catalyzer is 0.05% ~ 20% of the molar weight of described compd B.
Wherein in an embodiment, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
Wherein in an embodiment, described compd A is adopted and is prepared with the following method:
There is provided Compound C and Compound D, 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 first mixed solution, instill catalyzer and alkali, at 130 DEG C, stirring reaction 4 hours, obtains described compd A after separation and purification; Wherein, the molar weight of described catalyzer is 10% of the molar weight of described Compound C, and 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.
Wherein in an embodiment, described Compound C is adopted and is prepared with the following method:
2-amino-5-N-methyl-p-nitroaniline and pyridine are dissolved in thionyl chloride, in 80 DEG C ~ 90 DEG C back flow reaction 24 hours, after separation and purification, obtain 5-nitro-2,1,3 diazosulfide;
Described 5-nitro-2,1,3 diazosulfide and Hydrogen bromide are carried out being mixed to get the first mixture, described first mixture is warming up to 127 DEG C of backflows, drip bromine to described first mixture and reflux 4 hours, separation and purification obtains 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide;
Described 4,7-bis-bromo-5-nitro-2,1,3 diazosulfides and copper powder are added in DMF, is heated to 120 DEG C of reactions 3 hours, obtains 4 after separation and purification, 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides;
By described 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides add in tetrahydrofuran (THF), then add tin chloride, be warming up to 100 DEG C, reflux 10 hours, obtains 4 after separation and purification, 4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides;
By described 4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfide adds in ethanol and obtains suspension, described suspension is cooled to 0 DEG C, then adds sodium borohydride, react 20 hours under room temperature, 4 are obtained after separation and purification, 4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine);
By described 4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine) be mixed to get the second mixture with ethanol, described second mixture is refluxed, drips the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution is filtered, obtain described Compound C.
Wherein in an embodiment, described compd B is adopted and is prepared with the following method:
There is provided compd E, 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 the second solvent and obtains the second mixed solution, in described second mixed solution, n-Butyl Lithium is added at-78 DEG C, and react 1 ~ 2 hour at-78 DEG C, then tributyltin chloride is added, react 1 hour at-78 DEG C, then react 6 hours under room temperature, 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.
Wherein in an embodiment, the method of described separation and purification is specially: the reaction solution obtained to Stille coupled reaction adds deionized water and toluene extracts, concentrate extracting the organic phase obtained with underpressure distillation, then the organic phase after described concentrating is added dropwise in dehydrated alcohol and constantly stirs, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, again described pressed powder chloroform is dissolved, chromatography column is crossed again with neutral alumina, chloroform removed under pressure, methyl alcohol sedimentation, suction filtration, gained solid acetone apparatus,Soxhlet's extracts, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
Above-mentioned and three thiophene-benzo two (selenole) multipolymer stores and application in organic laser at polymer solar battery, organic electroluminescence device, organic field effect tube, organic light.
Above-mentioned and in 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 the energy gap of outstanding adjustment material and wider spectral response, such that the carrier mobility of this and three thiophene-benzo two (selenole) multipolymer is higher, spectral response is wider.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of also three thiophene-benzo two (selenole) multipolymer of an embodiment;
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 device.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by 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, preferably thermostability and film forming properties.And also three thiophene have three five-membered ring structures, have narrow band gap and strong conjugated nature, carrier mobility is high.
Diazosulfide unit a kind ofly excellent has good electronic transport property by body unit, can also regulate the energy gap of material simultaneously.In selenole selenium atom radius ratio diazosulfide in sulphur atom large, the molecule that more can strengthen between polymer chain is overlapping, promotes the hopping process of electric charge.Thus, selenole has better electronic transport property than diazosulfide, and has the character of the energy gap of outstanding adjustment material and wider spectral response.Benzo two (selenole) is a kind of very excellent donor material, the advantages such as it is simple, symmetrical that benzo two (selenole) has structure, and electron delocalization performance is good, and is planar conjugate structure, and carrier mobility is higher.
Above-mentioned and three thiophene-benzo two (selenole) multipolymer combines and the advantage of three thiophene and benzo two (selenole), a kind of very strong donor-receiver structure can be formed by the compound polymkeric substance that also three thiophene and benzo two (selenole) are formed, be conducive to the transferring charge character and the stability that improve material on the one hand, be conducive to the band gap reducing material on the other hand, thus expand sunlight absorption region, improve electricity conversion, there is the advantage that carrier mobility is higher, spectral response is wider.
Should also be applied in solar cell by three thiophene-benzo two (selenole) multipolymer, the effciency of energy transfer of solar cell can be improved.Further, 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 the performance improving above-mentioned device.
And, and on three thiophene-benzo two (selenole) multipolymer and three thiophene and benzo two (selenole) are upper when introducing alkyl, the solvability of being somebody's turn to do also three thiophene-benzo two (selenole) multipolymer is better, is conducive to film forming processing.
Refer to Fig. 1, the preparation method of also three thiophene-benzo two (selenole) multipolymer of an embodiment, 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.
Compd A is prepared as reactant using Compound C and Compound D.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, instill catalyzer and alkali, at 130 DEG C, 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 exist.
Wherein, the molar weight of catalyzer is 10% of the molar weight of Compound C, and the mol ratio of alkali and Compound D is 1:1; The mol ratio of Compound C and Compound D is 1:2.
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 the catalyzer that reacts of catalytic cpd C and Compound D.
The method of separation and purification is: after being cooled by reaction solution, washing, and dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, and silica gel column chromatography is separated, 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 2-amino-5-N-methyl-p-nitroaniline and pyridine are dissolved in thionyl chloride by 22.95g:2mL:100mL by solid-to-liquid ratio, in 80 DEG C ~ 90 DEG C 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 DEG C and revolves and steam excessive thionyl chloride (SOCl
2), reaction product is cooled to room temperature, in the large water gaging of impouring, stirs, filter, wash final vacuum drying, obtain pure 5-nitro-2,1,3 diazosulfide.
Reaction formula is as follows:
5-nitro-2,1,3 diazosulfide and Hydrogen bromide are carried out being mixed to get mixture, mixture is warming up to 127 DEG C of backflows, in 30 minutes, drip bromine to mixture and reflux 4 hours, separation and purification obtains 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide.Wherein, the solid-to-liquid ratio of 5-nitro-2,1,3 diazosulfide, Hydrogen bromide and bromine is 10.35g:15ml:11.3ml.
The method of separation and purification is: by reaction solution heat filtering, refilter after filtrate cooling, and filter residue is dry with a large amount of water washings, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain 4,7-bis-pure bromo-5-nitro-2,1,3 diazosulfides.
Reaction formula is as follows:
Bromo-for 4,7-bis-5-nitro-2,1,3 diazosulfide and copper powder are added in DMF, is heated to 120 DEG C of reactions 3 hours, obtains 4 after separation and purification, 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides.Wherein, the solid-to-liquid ratio of 4,7-bis-bromo-5-nitro-2,1,3 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, stirs 30 minutes, filter, filtrate saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolves evaporate to dryness, dehydrated alcohol recrystallization, obtain pure 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides.
Reaction formula is as follows:
By 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides add in tetrahydrofuran (THF), then add tin chloride, are warming up to 100 DEG C, and reflux 10 hours, obtains 4 after separation and purification, 4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides.Wherein, 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, the solid-to-liquid ratio of 3 diazosulfides, tetrahydrofuran (THF) and tin chloride is 10.3g:300mL:40g.
Reaction formula is as follows:
By 4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfide adds in ethanol and obtains suspension, suspension is cooled to 0 DEG C, then adds sodium borohydride, reacts 20 hours under room temperature, 4 are obtained, 4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine) after separation and purification.Wherein, the solid-to-liquid ratio of 4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides, ethanol and sodium borohydride is: 6.80g:200mL:14g.
Reaction formula is as follows:
4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine) and ethanol are mixed to get the second mixture, the second mixture is refluxed, drip the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution is filtered, obtain Compound C.
Wherein, 4,4 '-two bromo-6, the solid-to-liquid ratio of 6 '-two iodo-di-(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) compd B is prepared 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 DEG C, in the second mixed solution, add n-Butyl Lithium (CH
3(CH
2)
3li, is called for short n-BuLi), and react 1 ~ 2 hour at-78 DEG C, then add tributyltin chloride, react 1 hour at-78 DEG C, then react 6 hours under room temperature, 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.Second solvent is preferably tetrahydrofuran (THF) (THF).
The method of separation and purification is specially: add saturated sodium-chloride water solution termination reaction, then organic layer is obtained with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates the second solvent and obtain crude product, finally crude product is carried out neutral alumina column chromatography for separation and obtain pure compd B.
The reaction formula preparing compd B is as follows:
Step S120: in atmosphere of inert gases, chemical combination A and compd B are dissolved in solvent by 1.5:1 ~ 1:1.5 in molar ratio, add catalyzer, at 50 DEG C ~ 120 DEG C, carry out Stille coupled reaction 6 hours ~ 100 hours, obtain after separation and purification and three thiophene-benzo two (selenole) multipolymer.
Solvent is tetrahydrofuran (THF) (THF), glycol dimethyl ether, ether, benzene or toluene.Solvent is enough, to ensure 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), be more preferably bi triphenyl phosphorus palladium chloride (Pd (PPh
3)
2cl
2).In other embodiments, also nickel catalyzator or copper catalyst can be adopted.
The molar weight of catalyzer is preferably 0.05% ~ 20% of the molar weight of compd B.
Compd A and compd B take solvent as reaction medium, in the presence of a catalyst, at 50 DEG C ~ 120 DEG C, carry out Stille coupled reaction 6 hours ~ 100 hours, obtain after separation and purification and three thiophene-benzo two (selenole) multipolymer, 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 extracts, concentrate extracting the organic phase obtained with underpressure distillation, then the organic phase after concentrated is added dropwise in dehydrated alcohol and constantly stirs, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, again pressed powder chloroform is dissolved, chromatography column is crossed again with neutral alumina, chloroform removed under pressure, methyl alcohol sedimentation, suction filtration, gained solid acetone apparatus,Soxhlet's extracts, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
Above-mentioned and the preparation method of three thiophene-benzo two (selenole) multipolymer, technique is simple, little to the requirement of equipment, and reaction conditions is gentle, is easy to control, 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-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) also }, structural formula is:
1, Compound C-4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
(1) compound 5-nitro-2,1,3 diazosulfide is prepared
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, in 90 DEG C of back flow reaction 24h after heating, stopped reaction, is heated to 80 DEG C and revolves and steam excessive SOCl
2after, reaction product is cooled to room temperature, in the large water gaging of impouring, stirs, filter, wash final vacuum drying, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
Reaction formula is as follows:
(2) compound 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide is prepared
5-nitro-2,1,3 diazosulfide (10.35g is added in there-necked flask, 60mmol) and the Hydrogen bromide 15ml of 40%, be warming up to 127 DEG C of backflows, slowly drip bromine 11.3ml in 30min and the 4h that refluxes, heat filtering, refilter after filtrate cooling, solid is dry with a large amount of water washings, 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) compound 4 is prepared, 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides
The bromo-5-nitro-2,1 of 4,7-bis-is added in there-necked flask, the copper powder of 3 diazosulfides (10.2g, 30mmol), 9.5g and the DMF (DMF) of 90ml, be heated to 120 DEG C of reactions after 3 hours, stopped reaction, is cooled to room temperature, add 90ml toluene, stir 30 minutes, filter, filtrate saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.
Reaction formula is as follows:
(4) compound 4 is prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides
In there-necked flask, add 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide (10.3g, 20mmol), adds the tetrahydrofuran (THF) (THF) of 300ml drying, adds 40gSnCl
2(200mmol), 100 DEG C are warming up to, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extracts, and revolves and steams gained organic layer, obtain 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 controls below 5 DEG C, solution, in yellow, after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (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 is washed, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, be separated with silica gel column chromatography, then carry out recrystallizing methanol, obtain 4.1g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, productive rate is 30%.
Reaction formula is as follows:
(5) compound 4 is prepared, 4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine)
In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides (6.80g, 0.01mol), add the ethanol of 200ml, form suspension, 0 DEG C drips sodium borohydride (14g, 0.37mol), mixture stirring reaction 20 hours under room temperature, stopped reaction, extracts with anhydrous diethyl ether, organic layer is washed, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, obtain 5.49g product, productive rate 88%.
Reaction formula is as follows:
(6) compound 4 is prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine) (3.12g, 5mmol), add the ethanolic soln of 60ml, backflow, 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, compd A-4 are prepared, bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3, the 4-e] two (selenole) of 9-bis-
4 are added, 4 '-two bromo-6,6 '-two iodo-2,1 in there-necked flask, 3 selenoles (Compound C) (3.87g, 5mmol), 2,6,13,17-tetramethyl--9-octadecyne (Compound D) (3.07g, 10mmol) and 25mlDMF, passes into nitrogen gas stirring 20min, adds Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, and obtains 2.48g product 4,9-bis-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) [3,2-b:4,5-b '] three thiophene
Under the protection of nitrogen; 3 are added in there-necked flask; 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 DEG C of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react at-78 DEG C and rise to stirred at ambient temperature after 1 hour and react 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, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out 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-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) also }
Under nitrogen protection, 3,5-dioctyl-2 is added; 6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (compd B) (199.8mg; 0.2mmol), 4,9-bis-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 adding Pd (PPh
3)
2cl
2(5mg, 7.1 × 10
-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 57980, n=52, and polymkeric substance monodispersity is 2.4.
Embodiment 2
Preparation poly-{ 3,5-dimethyl is [3,2-b:4,5-b '] three thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) also }, structural formula is:
1, Compound C-4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
Preparation method is with embodiment 1.
2, compd A-4 are prepared, bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3, the 4-e] two (selenole) of 9-bis-
4 are added, 4 '-two bromo-6,6 '-two iodo-2,1 in there-necked flask, 3 selenoles (Compound C) (3.87g, 5mmol), 2,6,13,17-tetramethyl--9-octadecyne (Compound D) (3.07g, 10mmol) and 25mlDMF, passes into nitrogen gas stirring 20min, adds Bu
3n (0.907g, 10mmol) and Pd (OAc)
2(115mg, 0.5mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, and obtains 2.48g product 4,9-bis-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 are prepared, 5-dimethyl-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene
Under the protection of nitrogen; 3 are added in there-necked flask; 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 DEG C of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react at-78 DEG C and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out 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-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) also }
Under nitrogen protection, 3,5-dimethyl-2 is added; 6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene (compd B) (160.4mg; 0.2mmol), 4,9-bis-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 adding Pd
2(dba)
3(5mg, 5.5 × 10
-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 15623, n=17, and polymkeric substance monodispersity is 2.5.
Reaction formula is as follows:
Embodiment 3
Preparation poly-{ 3,5-bis-(NSC 62789 base) [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }, structural formula is:
1, Compound C-4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
Preparation method is with embodiment 1.
2, compd A-4 are prepared, the bromo-6-methyl of 9-bis--7-ethyl benzo [2,1-e:3,4-e] two (selenole)
In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles (Compound C) (7.74g, 10mmol), (1.36g, 20mmol and 50mlDMF pass into nitrogen gas stirring 20min, add Bu 2 – pentynes (Compound D)
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, obtain 5.15g product 4,9-bis-bromo-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.
Reaction formula is as follows:
3, compd B-3 are prepared, 5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene
Under the protection of nitrogen; 3 are added in there-necked flask; 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 DEG C of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out 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) [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }
Under nitrogen protection, 3,5-bis-(NSC 62789 base)-2 is added; 6-bis-(tributyl tin) [3; 2-b:4,5-b '] three thiophene (compd B) (267mg, 0.2mmol), 4; the bromo-6-methyl of 9-bis--7-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 adding Pd (PPh
3)
4(9mg, 7.8 × 10
-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 23066, n=19, and polymkeric substance monodispersity is 2.3.
Embodiment 4
Preparation poly-{ 3,5-bis-(NSC 62789 base) [3,2-b:4,5-b '] three thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenole) }, structural formula is:
1, Compound C-4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
Preparation method is with embodiment 1.
2, compd A-4 are prepared, bromo-6-(2, the 7-dimethyl of 9-bis-) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfide)
4 are added, 4 '-two bromo-6,6 '-two iodo-2,1 in there-necked flask, 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 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, and obtains 2.7g product 4,9-bis-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, compd B-3 are prepared, 5-bis-(NSC 62789 base)-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene
Under the protection of nitrogen; 3 are added in there-necked flask; 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 DEG C of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productive rate 74%.
Reaction formula is as follows:
4, poly-{ 3,5-bis-(NSC 62789 base) [3,2-b:4,5-b '] three thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenole) }
Under nitrogen protection, add 3, 5-bis-(NSC 62789 base)-2, 6-bis-(tributyl tin) [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 Pd (PPh3) 2Cl2 (28.04mg is added, 0.04mmol), be heated to 120 DEG C of reaction 100h.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 159200, n=100, and 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 (selenole) also }, structural formula is:
1, Compound C-4 are prepared, 4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
Preparation method is with embodiment 1.
2, compd A-4 are prepared, the bromo-6-methyl of 9-bis--7-ethyl benzo [2,1-e:3,4-e] two (selenole)
In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles (Compound C) (7.74g, 10mmol), (1.36g, 20mmol and 50mlDMF pass into nitrogen gas stirring 20min, add Bu 2 – pentynes (Compound D)
3n (1.814g, 20mmol) and Pd (OAc)
2(230mg, 1.0mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, obtain 5.15g product 4,9-bis-bromo-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.
Reaction formula is as follows:
3, compd B-3 are prepared, 5-dimethyl-2,6-bis-(tributyl tin) [3,2-b:4,5-b '] three thiophene
Under the protection of nitrogen; 3 are added in there-necked flask; 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 DEG C of conditions, slowly inject n-Butyl Lithium (8.6mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 1.5h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out 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 (selenole) also }
Under nitrogen protection, 3,5-dimethyl-2 is added; 6-bis-(tributyl tin) [3; 2-b:4,5-b '] three thiophene (compd B) (160.4mg, 0.2mmol), 4; the bromo-6-methyl of 9-bis--7-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 adding Pd (PPh
3)
2cl
2(1.05mg, 1.5 × 10
-4mmol) 50 DEG C of reaction 6h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Polymkeric substance after purifying is carried out 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 comprise stack gradually substrate 11, anode 12, middle auxiliary 13 layers, active coating 14 and negative electrode 15, the representation of this device is substrate/anode/middle supplementary layer/active coating/negative electrode.Wherein, substrate 11 adopts substrate of glass; The indium tin oxide films (ITO) of anode 12 to be square resistances be 10 Ω/mouth; 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 (selenole) } 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, and choose ito glass (with the ito glass substrate of anode 12, can buy) during making, thickness is 1.1mm, after ultrasonic cleaning, processes with oxygen-Plasma; Then in ito glass substrate, apply PEDOT:PSS form middle supplementary layer 13, thickness is 120nm; Again prepared by 10mg embodiment 1 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 (selenole) } be dissolved in 0.4ml dimethylbenzene, be dissolved in 8mgPCBM the solution blending that 0.4ml chlorobenzene obtains and obtain mixture, be spun on PEDOT:PSS rete by this mixture, thickness is about 150nm, obtains active coating 14; At vacuum condition (2 × 10
-3pa) evaporation metal aluminium under, active coating is formed negative electrode 15, and thickness is 120nm, obtains polymer solar cell device.Above-mentioned preparation process is all carried out in the glove box providing nitrogen inert atmosphere.
Embodiment 7
Polymer solar cell device
In the present embodiment, the structure of polymer solar cell device is identical with embodiment 6, electron donor material except 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) } outward, 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, electron donor material except active coating 14 adopts poly-{ 3 of embodiment 3,5-bis-(NSC 62789 base) [3,2-b:4,5-b '] three thiophene-6-methyl-7-ethyl benzos [2,1-e:3,4-e] two (selenoles) } outward, all the other are identical with embodiment 6.
Adopt the performance of the polymer solar cell device of Keithley236 current/voltage source-measuring system difference testing example 6 ~ 8, 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 prepared as the electron donor material of active coating with embodiment 6 ~ 8 multipolymer is 0.89 ~ 1.60, show embodiment 6 ~ 8 and three thiophene-benzo two (selenole) multipolymer due 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, ratio and charge collection efficiency that current carrier arrives electrode can be improved, thus 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, deposit on the glass substrate one deck square resistance be the tin indium oxide (ITO) of 20 Ω/mouth as anode 22, the thickness of anode 22 is 150nm; Adopt poly-{ 3,5-dioctyl also [3, the 2-b:4 of embodiment 1,5-b '] three thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzos [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 the buffer layer, obtains organic electroluminescence device, and the thickness of negative electrode 25 is 150nm.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 13.5cd/A, and high-high brightness is 1155cd/m
2.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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:
There is provided 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, described chemical combination A and compd B are dissolved in solvent by 1.5:1 ~ 1:1.5 in molar ratio, add catalyzer, Stille coupled reaction is carried out 6 hours ~ 100 hours at 50 DEG C ~ 120 DEG C, obtain after separation and purification and three thiophene-benzo two (selenole) multipolymer, described and general molecular formula that is three thiophene-benzo two (selenole) multipolymer is:
Wherein, n is the integer between 1 ~ 100.
3. the according to claim 2 and preparation method of three thiophene-benzo two (selenole) multipolymer, it is characterized in that, described catalyzer is three (dibenzalacetone) two palladium, tetrakis triphenylphosphine palladium or bi triphenyl phosphorus palladium chloride.
4. the preparation method of also three thiophene-benzo two (selenole) multipolymer according to Claims 2 or 3, it is characterized in that, the molar weight of described catalyzer is 0.05% ~ 20% of the molar weight of described compd B.
5. the according to claim 2 and preparation method of three thiophene-benzo two (selenole) multipolymer, it is characterized in that, described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene.
6. the according to claim 2 and preparation method of three thiophene-benzo two (selenole) multipolymer, is characterized in that, described compd A is adopted and prepared with the following method:
There is provided Compound C and Compound D, 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 first mixed solution, instill catalyzer and alkali, at 130 DEG C, stirring reaction 4 hours, obtains described compd A after separation and purification; Wherein, the molar weight of described catalyzer is 10% of the molar weight of described Compound C, and 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 according to claim 6 and preparation method of three thiophene-benzo two (selenole) multipolymer, is characterized in that, described Compound C is adopted and prepared with the following method:
2-amino-5-N-methyl-p-nitroaniline and pyridine are dissolved in thionyl chloride, in 80 DEG C ~ 90 DEG C back flow reaction 24 hours, after separation and purification, obtain 5-nitro-2,1,3-diazosulfide;
Described 5-nitro-2,1,3-diazosulfide and Hydrogen bromide are carried out being mixed to get the first mixture, described first mixture is warming up to 127 DEG C of backflows, drip bromine to described first mixture and reflux 4 hours, separation and purification obtains 4,7-bis-bromo-5-nitro-2,1,3-diazosulfide;
Described 4,7-bis-bromo-5-nitro-2,1,3-diazosulfides and copper powder are added in DMF, is heated to 120 DEG C of reactions 3 hours, obtains 4 after separation and purification, 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3-diazosulfide;
By described 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3-diazosulfide adds in tetrahydrofuran (THF), then adds tin chloride, be warming up to 100 DEG C, reflux 10 hours, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extracts, and revolves and steams gained organic layer, obtain solid crude product, described solid crude product is put in there-necked flask;
Hydrochloric acid is added in described solid crude product, agitation and dropping sodium nitrite solution in 30 minutes, temperature controls below 5 DEG C, solution is in yellow, after dropwising, react 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, reaction 12h, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extract with anhydrous diethyl ether, organic layer is washed, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness filtrate, be separated with silica gel column chromatography, then recrystallizing methanol is carried out, obtain 4, 4 '-two bromo-6, 6 '-two iodo-2, 1, 3-diazosulfide,
By described 4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfide adds in ethanol and obtains suspension, described suspension is cooled to 0 DEG C, then adds sodium borohydride, react 20 hours under room temperature, 4 are obtained after separation and purification, 4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine);
By described 4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine) be mixed to get the second mixture with ethanol, described second mixture is refluxed, drips the tin anhydride aqueous solution, reflux and after 2 hours, reaction solution is filtered, obtain described Compound C.
8. the according to claim 2 and preparation method of three thiophene-benzo two (selenole) multipolymer, is characterized in that, described compd B is adopted and prepared with the following method:
There is provided compd E, 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 the second solvent and obtains the second mixed solution, in described second mixed solution, n-Butyl Lithium is added at-78 DEG C, and react 1 ~ 2 hour at-78 DEG C, then tributyltin chloride is added, react 1 hour at-78 DEG C, then react 6 hours under room temperature, 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 according to claim 2 and preparation method of three thiophene-benzo two (selenole) multipolymer, it is characterized in that, the method of described separation and purification is specially: the reaction solution obtained to Stille coupled reaction adds deionized water and toluene extracts, concentrate extracting the organic phase obtained with underpressure distillation, then the organic phase after described concentrating is added dropwise in dehydrated alcohol and constantly stirs, solid precipitation is had to separate out, suction filtration, pressed powder is obtained after oven dry, again described pressed powder chloroform is dissolved, after neutral alumina chromatography column, chloroform removed under pressure, methyl alcohol sedimentation, suction filtration, gained solid acetone apparatus,Soxhlet's extracts, methyl alcohol sedimentation, suction filtration obtains pure also three thiophene-benzo two (selenole) multipolymer.
10. the application of also three thiophene-benzo two (selenole) multipolymer as claimed in claim 1 in polymer solar battery, organic electroluminescence device, organic field effect tube, the storage of organic light and organic laser.
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| 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 |
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