CN103865042A - Copolymer containing dithienopyrrole and benzodi(benzoselenadiazole), and preparation method and application thereof - Google Patents
Copolymer containing dithienopyrrole and benzodi(benzoselenadiazole), and preparation method and application thereof Download PDFInfo
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- 0 C[C-]N=C(C(Br)=CC(*)=C1c2c(*)cc(*)c3c2N=S*3)C1=N Chemical compound C[C-]N=C(C(Br)=CC(*)=C1c2c(*)cc(*)c3c2N=S*3)C1=N 0.000 description 4
- ZJEOSNXCUDHDSF-UHFFFAOYSA-N [O-][N+](c(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O)=O Chemical compound [O-][N+](c(cc(c1n[s]nc11)Br)c1-c(c1n[s]nc1c(Br)c1)c1[N+]([O-])=O)=O ZJEOSNXCUDHDSF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a copolymer containing dithienopyrrole and benzodi(benzoselenadiazole), and the structural formula is shown in the specification. In the structural formula, n is an integer between 1 to 100, and R1, R2 and R3 are C1-C20 alkyl. The copolymer has the characteristics of wide light absorption scope, high carrier mobility, good solubility, good film forming property and the like, and is applicable to copolymer solar cell devices, organic electroluminescent devices, organic field effect transistors, organic optical storage and organic laser and the like. Additionally, the invention also provides a preparation method for the copolymer containing dithienopyrrole and benzodi(benzoselenadiazole), and the preparation method is mild in conditions, easy to control and high in product yield.
Description
Technical field
The present invention relates to solar cell material technical field, particularly relate to a kind of multipolymer containing two thiophene pyrroles and benzo two (selenole) unit and its preparation method and application.
Background technology
Utilize cheap material to prepare low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Although traditional silicon solar cell has higher usefulness, its complex manufacturing, cost are high, have limited it and have further applied.In order to reduce the production cost of solar cell, expand its range of application, people are finding novel solar cell material always.
Multipolymer solar cell because cost of material is cheap, quality is light, flexible, production technique simple, can large area flexible prepare etc., and advantage receives much concern.But the photoelectric transformation efficiency of multipolymer solar cell is more much lower than silicon solar cell, if multipolymer solar cell photoelectric efficiency of conversion can be brought up to the level that approaches commodity silicon solar cell, its market outlook will be very huge.
People drop into large quantity research aspect multipolymer solar cell, research shows that one of challenge that multipolymer solar cell will face future is exactly the copolymer material of synthesizing new, and copolymer material need to possess following characteristics: (a) good solubility, be conducive to solvent processing, realize suitability for industrialized production; (b) whole sunlight spectrum is had to wide and strong absorption; (c) high carrier mobility, is conducive to carrier transport.Wherein, how to widen the light abstraction width of copolymer material, make its light abstraction width farthest cover whole sunlight spectrum most important to the photoelectric transformation efficiency of raising multipolymer solar cell.
Summary of the invention
Based on this, be necessary the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit that provides a kind of light abstraction width wide.
A kind of multipolymer containing two thiophene pyrroles and benzo two (selenole) unit, has following structural formula:
Wherein, the integer that n is 1 ~ 100;
R
1, R
2and R
3for C
1~ C
20alkyl.
The above-mentioned multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit has lot of advantages, first, electron rich give body unit two thiophene pyrroles and electron deficiency be subject to body unit benzo two (selenole), form donor-receiver structure, there is the interaction of very strong " push away-La electronics ", improved on the one hand the stability of multipolymer; Reduce on the one hand the energy gap of multipolymer, can make its absorption band move to infrared and near infrared low energy wave band, widen the light abstraction width containing the multipolymer of two thiophene pyrroles and benzo two (selenole) unit, but also can improve the mobility of current carrier.Secondly, selenole unit has excellent reduction reversibility, and the radius of selenium atom in selenole unit is larger, can strengthen molecule between copolymer chain overlapping, be easy to form strong state of aggregation and make multipolymer there is higher carrier mobility; Selenole easily improves solvability and the molecular weight of multipolymer by introducing alkyl simultaneously, is conducive to film forming processing.And two thiophene pyrrole there are three five-membered ring structures, there is narrow band gap, strong conjugated nature, moderate band gap, wider spectral response, preferably thermostability and film forming properties.The characteristic such as therefore, the above-mentioned multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit has that light abstraction width is wide, carrier mobility is high, good stability, film forming properties are good.
A kind of preparation method of the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit, comprises the steps:
Compd A and compd B are provided, and the structural formula of compd A is:
The structural formula of compd B is:
Wherein, R
1, R
2and R
3for C
1~ C
20alkyl;
Under shielding gas atmosphere; under the condition that the ratio that is 1:1.5 ~ 1.5:1 according to mol ratio by compd A and compd B exists at catalyzer and organic solvent, carry out Stille coupled reaction; wherein; temperature of reaction is 50 ~ 120 DEG C; reaction times is 6 ~ 100 hours; after separation and purification, obtain having the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit of following structural formula
Wherein, the integer that n is 1 ~ 100.
In an embodiment, described catalyzer is Pd therein
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, 0.05% ~ 20% of the molar weight that the molar weight of described catalyzer is described compd B; Described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene;
The step of described separation and purification is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, methyl alcohol sedimentation, 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 the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit after purification.
In an embodiment, described compd A is adopted preparation with the following method therein:
Compound C is provided, and the structural formula of Compound C is:
Under shielding gas atmosphere; the ratio that is 1:2 according to mol ratio by Compound C and n-Butyl Lithium is reacted 1 ~ 2 hour in tetrahydrofuran (THF) under the condition of-78 DEG C; then add tributyltin chloride under the condition of-78 DEG C, to continue reaction 1 hour; then be warming up to room temperature; under room temperature, react 6 hours; obtain described compd A, wherein, the ratio of the mol ratio of tributyltin chloride and Compound C is 2:1.
In an embodiment, described compd B is adopted preparation with the following method therein:
Compound D and compd E are provided, and the structural formula of Compound D is:
The structural formula of compd E is:
Under shielding gas atmosphere, by Compound D, compd E and Bu
3n is that 1:2:1 ratio is at Pd (OAc) according to mol ratio
2with DMF exist condition under carry out ring closure reaction, obtain described compd B, wherein, temperature of reaction is 130 DEG C, the reaction times is 4 hours, Pd (OAc)
2the molar weight molar weight that is Compound D 10%.
In an embodiment, described Compound D is adopted preparation with the following method therein:
Compound F 17-hydroxy-corticosterone is provided, and the structural formula of compound F 17-hydroxy-corticosterone is:
Under shielding gas atmosphere, compound F 17-hydroxy-corticosterone is joined in ethanol, obtain mixed solution, under the condition refluxing, in described mixed solution, drip SeO
2the aqueous solution, and back flow reaction 2 hours, obtains described Compound D.
In an embodiment, described compound F 17-hydroxy-corticosterone is adopted preparation with the following method therein:
Compound G is provided, and the structural formula of compound G is:
Under shielding gas atmosphere, compound G is joined in ethanol, obtain suspension, then, at 0 DEG C, in described suspension, drip sodium borohydride, then stirring reaction 20 hours under room temperature, obtains described compound F 17-hydroxy-corticosterone.
In an embodiment, described compound G adopts preparation with the following method therein:
Compound H is provided, and the structural formula of compound H is:
Compound H, copper powder and DMF are mixed, are heated to 120 DEG C of reactions after 3 hours, be cooled to room temperature, add toluene, stir 30 minutes, obtain Compound I,
The structural formula of Compound I is:
By Compound I, tetrahydrofuran (THF) and SnCl
2mix, heating reflux reaction 10 hours, cooling after, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, rotary evaporation gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 DEG C, after dropwising, reacts 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, reacts 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, obtains described compound G.
In an embodiment, described compound H is adopted preparation with the following method therein:
Compound J is provided, and the structural formula of compound J is:
Compound J is mixed with thionyl chloride, stir and slowly drip pyridine, heating reflux reaction 24 hours, obtains compound K,
The structural formula of compound K is:
The Hydrogen bromide that is 40% with mass concentration by compound K mixes, and is warming up to after 127 DEG C, slowly drips bromine in 30 minutes, and then back flow reaction 4 hours, obtains described compound H.
The reaction conditions gentleness of the Stille reaction in above-mentioned preparation method, is easy to control, and the productive rate of product is high; The route of synthetic benzo two (selenole) is fairly simple, easily improves solvability and the molecular weight of multipolymer by introducing alkyl, is conducive to film forming processing; The characteristics such as the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit preparing has that light abstraction width is wide, carrier mobility is high, good stability, film forming properties are good can be applied in multipolymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
Brief description of the drawings
Fig. 1 is the preparation method's of the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit of an embodiment schema;
Fig. 2 is the structural representation of the multipolymer solar cell device of an embodiment;
Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment.
Embodiment
Below in conjunction with drawings and the specific embodiments, multipolymer containing two thiophene pyrroles and benzo two (selenole) unit and its preparation method and application is further detailed.
The copolymer structure formula containing two thiophene pyrroles and benzo two (selenole) unit of one embodiment is as follows:
Wherein, the integer that n is 1 ~ 100;
R
1, R
2and R
3for C
1~ C
20alkyl.
Benzo two (selenole) unit belongs to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, simple in structure, symmetrical, electron delocalization performance is good, there is two dimensional structure, be that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.And benzo two (selenole) unit also has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium.
Thiophene is five-membered ring structure, has moderate band gap, wider spectral response, preferably thermostability and film forming properties.Thiophene has formed σ *-π * conjugation, makes the minimum not occupied orbital (lowest unocccupied molecular orbital, LUMO) of thiophene molecule lower, has good electron affinity and electronic mobility simultaneously.In the structure of two thiophene pyrroles, having three five-membered ring structures, have narrow band gap and strong conjugated nature, is a kind of good in body unit, at present in the photoelectric material such as widespread use and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
The above-mentioned multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit has lot of advantages, first, electron rich give body unit two thiophene pyrroles and electron deficiency be subject to body unit benzo two (selenole), form donor-receiver structure, there is the interaction of very strong " push away-La electronics ", improved on the one hand the stability of multipolymer; Reduce on the one hand the energy gap of multipolymer, can make its absorption band move to infrared and near infrared low energy wave band, widen the light abstraction width containing the multipolymer of two thiophene pyrroles and benzo two (selenole) unit, but also can improve the mobility of current carrier.Secondly, selenole unit has excellent reduction reversibility, and the radius of selenium atom in selenole unit is larger, can strengthen molecule between copolymer chain overlapping, be easy to form strong state of aggregation and make multipolymer there is higher carrier mobility; Selenole easily improves solvability and the molecular weight of multipolymer by introducing alkyl simultaneously, is conducive to film forming processing.And two thiophene pyrrole there are three five-membered ring structures, there is narrow band gap, strong conjugated nature, moderate band gap, wider spectral response, preferably thermostability and film forming properties.The characteristic such as therefore, the above-mentioned multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit has that light abstraction width is wide, carrier mobility is high, good stability, film forming properties are good.
In addition, present embodiment also provides a kind of preparation method of the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit, as shown in Figure 1, comprises the steps:
Step S110, provides compd A and compd B.The structural formula of compd A is:
The structural formula of compd B is:
Wherein, R
1, R
2and R
3for C
1~ C
20alkyl.
Step S120; under shielding gas atmosphere; under the condition that the ratio that is 1:1.5 ~ 1.5:1 according to mol ratio by compd A and compd B exists at catalyzer and organic solvent, carry out Stille coupled reaction; wherein; temperature of reaction is 50 ~ 120 DEG C; reaction times is 6 ~ 100 hours, obtains having the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit of following structural formula after separation and purification
Wherein, the integer that n is 1 ~ 100.
In the present embodiment, shielding gas atmosphere comprises nitrogen, argon gas etc.
Catalyzer is organic palladium, as Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, be preferably Pd (PPh
3)
2cl
2.Be appreciated that catalyzer also can be organic palladium and organophosphorus ligand (as, P (o-Tol)
3or tricyclohexyl phosphine) mixture, as, that mol ratio 1:2 ~ 1:20 is Pd
2(dba)
3with P (o-Tol)
3mixture.
The consumption of catalyzer be compd B molar weight 0.05% ~ 20%.
Organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene, and the amount of solvent is enough.
In the present embodiment, the purification procedures in step S120 is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of organic phase by the method for underpressure distillation, again organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, methyl alcohol sedimentation, 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 the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit after purification.
In step S110, compd A can be adopted preparation with the following method:
Step S111, provides Compound C, and the structural formula of Compound C is:
Wherein, R
3for C
1~ C
20alkyl.
Step S112, under shielding gas atmosphere, the ratio that is 1:2 according to mol ratio by Compound C and n-Butyl Lithium is reacted 1 ~ 2 hour in tetrahydrofuran (THF) under the condition of-78 DEG C, then adds tributyltin chloride (SnBu
3cl) under the condition of-78 DEG C, continue reaction 1 hour, be then warming up to room temperature, under room temperature, react 6 hours, obtain compd A, wherein, SnBu
3the ratio of the mol ratio of Cl and Compound C is 2:1.
The reaction process of this step is as follows:
In step S110, compd B can be adopted preparation with the following method:
Step S211, provides Compound D and compd E, and the structural formula of Compound D is:
The structural formula of compd E is:
Wherein, R
1and R
2for C
1~ C
20alkyl.
Step S212, under shielding gas atmosphere, by Compound D, compd E and Bu
3n is that 1:2:1 ratio is at Pd (OAc) according to mol ratio
2with DMF exist condition under carry out ring closure reaction, obtain compd B, wherein, temperature of reaction is 130 DEG C, the reaction times is 4 hours, Pd (OAc)
2the molar weight molar weight that is Compound D 10%.
The reaction process of this step is as follows:
In step S211, Compound D can be adopted preparation with the following method:
Step S221, provides compound F 17-hydroxy-corticosterone, and the structural formula of compound F 17-hydroxy-corticosterone is:
Step S222, under shielding gas atmosphere, joins compound F 17-hydroxy-corticosterone in ethanol, obtains mixed solution, under the condition refluxing, drips SeO in mixed solution
2the aqueous solution, and back flow reaction 2 hours, obtains Compound D.
The reaction process of this step is as follows:
In step S221, compound F 17-hydroxy-corticosterone can be adopted preparation with the following method:
Step S231, provides compound G, and the structural formula of compound G is:
Step S232, under shielding gas atmosphere, joins compound G in ethanol, obtains suspension, then, at 0 DEG C, in suspension, drips sodium borohydride, and then stirring reaction 20 hours under room temperature, obtains compound F 17-hydroxy-corticosterone.
The reaction process of this step is as follows:
In step S231, compound G can adopt preparation with the following method:
Step S241, provides compound H, and the structural formula of compound H is:
Step S242, mixes compound H, copper powder and DMF, is heated to 120 DEG C of reactions after 3 hours, is cooled to room temperature, adds toluene, stirs 30 minutes, obtains Compound I, and the structural formula of Compound I is:
The reaction process of this step is as follows:
Step S243, by Compound I, tetrahydrofuran (THF) and SnCl
2mix, heating reflux reaction 10 hours, cooling after, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, rotary evaporation gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 DEG C, after dropwising, reacts 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, reacts 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, obtains compound G.
The reaction process of this step is as follows:
In step S241, compound H can be adopted preparation with the following method:
Step S251, provides compound J, and the structural formula of compound J is:
Step S252, mixes compound J with thionyl chloride, stir and slowly drip pyridine, and heating reflux reaction 24 hours, obtains compound K, and the structural formula of compound K is:
The reaction process of this step is as follows:
Step S253, the Hydrogen bromide that is 40% with mass concentration by compound K mixes, and is warming up to after 127 DEG C, slowly drips bromine in 30 minutes, and then back flow reaction 4 hours, obtains compound H.
The reaction process of this step is as follows:
The reaction conditions gentleness of the Stille reaction in above-mentioned preparation method, is easy to control, and the productive rate of product is high; The route of synthetic benzo two (selenole) is fairly simple, easily improves solvability and the molecular weight of multipolymer by introducing alkyl, is conducive to film forming processing; The characteristics such as the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit preparing has that light abstraction width is wide, carrier mobility is high, good stability, film forming properties are good can be applied in multipolymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
Multipolymer containing two thiophene pyrroles and benzo two (selenole) unit and its preparation method and application is described below in conjunction with specific embodiment.
Embodiment 1
P1: poly-{ 4-dodecyl two thieno-s [3,2-b:4,5-b '] pyrroles-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }, have following structural formula:
The preparation process of above-mentioned copolymer p 1 is as follows:
Step 1, prepare compound 5-nitro-2,1,3 diazosulfide
In there-necked flask, add 0.15mol 2-amino-5-N-methyl-p-nitroaniline and 100mL thionyl chloride, and in there-necked flask, slowly drip 2mL pyridine, then heating reflux reaction 24 hours under the condition stirring; Reaction solution is heated to 80 DEG C of rotations and steams after excessive thionyl chloride, will be cooled in the large water gaging of reaction product impouring of room temperature and stir; Filter, obtain solid matter, and solid matter after vacuum-drying washing, product 5-nitro-2 obtained, 1,3 diazosulfide 21.7g, productive rate 80%.
Step 2, prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide
In there-necked flask, add 60mmol 5-nitro-2, the Hydrogen bromide that 1,3 diazosulfide and 15mL mass concentration are 40%, obtains mixed solution; Mixed solution is warming up to after 127 DEG C, in 30 minutes, slowly drips 11.3mL bromine, then back flow reaction 4 hours; Heat filtering reaction solution refilters after cooling the filtrate obtaining, and obtains solid matter, with a large amount of water washing solid matter dry, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide 10.2g, productive rate is 50%.
Step 3, preparation 4,4 '-bis-are bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides
In there-necked flask, add 30mmol 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide, 9.5g copper powder and 90mL DMF (DMF), obtain mixed solution; Mixed solution is heated to 120 DEG C, and at 120 DEG C, reacts 3 hours; Add 90mL toluene to being cooled in the reaction solution of room temperature, and stir 30 minutes; Then filter, the filtrate obtaining with saturated aqueous common salt and water washing respectively, and merge organic layer; Anhydrous magnesium sulfate drying organic layer; Filter, collect filtrate; By the method for rotary evaporation, the solvent in filtrate is removed, obtained solid matter; Solid matter dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfide 4.7g, and productive rate is 30.2%.
Step 4, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
In there-necked flask, add 20mmol 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides, tetrahydrofuran (THF) (THF) and 200mmol SnCl that 300mL is dry
2, obtain mixed solution; Mixed solution is heated to 100 DEG C, and heating reflux reaction 10 hours; After question response liquid cooling but, with sodium hydroxide solution adjust pH to 8.0; Then with anhydrous diethyl ether extraction, rotary evaporation gained organic layer, obtains solid crude product; The solid crude product obtaining is put in there-necked flask, adds the hydrochloric acid (21.7mmol) of 58mL, and in 30 minutes agitation and dropping 20mL sodium nitrite solution (37.7mmol), temperature is controlled at below 5 DEG C, it is yellow that solution is; After dropwising, react 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide and 100mL water), vigorous stirring, reacts 12 hours; After reaction stops, with sodium hydroxide solution adjust pH to 7.0; Then extract with anhydrous diethyl ether, and collected organic layer; Organic layer is after washing, with anhydrous magnesium sulfate drying; Filter, collect filtrate; By the method for rotary evaporation, the solvent in filtrate is removed, obtained crude product; Crude product is carried out to silica gel column chromatography separation, and the material recrystallizing methanol that separation is obtained, obtains 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide 4.1g, and productive rate is 30%.
Step 5, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine)
In there-necked flask, add 0.01mol 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides and 200ml ethanol, form suspension; Then, at 0 DEG C, in suspension, drip 0.37mol sodium borohydride, then stirring reaction 20 hours under room temperature; With anhydrous diethyl ether extractive reaction liquid, and collected organic layer; Organic layer is after washing, with anhydrous magnesium sulfate drying; Filter, collect filtrate; By the method for rotary evaporation, the solvent in filtrate is removed, obtained product 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) 5.49g, productive rate 88%.
Step 6, preparation 4,4 '-bis-are bromo-6,6 '-bis-iodo-2,1,3-selenole
In there-necked flask, add 5mmol 4,4 '-bis-bromo-6,6 '-bis-iodo-di-s (1,2-phenylenediamine) and 60ml ethanol, obtain mixed solution; Under the condition refluxing, in mixed solution, drip 22ml containing 10.5mmol SeO
2hydrothermal solution, then back flow reaction 2 hours; Question response liquid cooled and filtered, obtains product 4, and 4 '-bis-is bromo-6,6 '-bis-iodo-2,1,3-selenole 3.48g, productive rate 90%.
4,9-bis-is bromo-6 for step 7, preparation, 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 5mmol 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles, 10mmol2, (synthetic method is with reference to Chem.Commun. for 6,13,17-tetramethyl--9-octadecyne, 2011,47,8850-8852) and 25ml DMF, mixed solution obtained; Under the condition stirring, in mixed solution, pass into nitrogen 20min, then add 10mmol Bu
3n and 0.5mmol Pd (OAc)
2, be warming up to 130 DEG C, and at 130 DEG C, react 4 hours; After question response liquid cooling but, wash with water, dichloromethane extraction, obtains organic layer; Anhydrous sodium sulfate drying organic layer; Filter, collect filtrate; By the method for underpressure distillation, the solvent in filtrate is removed, obtained crude product; Crude product is carried out to silica gel column chromatography separation, obtain product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenole) 2.48g, productive rate 60%.
Step 8, preparation 4-dodecyl-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles
Under the protection of nitrogen, in there-necked flask, add 0.01mol 4-dodecyl-2,6-dibromo two thieno-s [3,2-b:4,5-b '] pyrroles and 51ml tetrahydrofuran solvent, obtain mixed solution; Under-78 DEG C of conditions, slowly in mixed solution, inject 8.6mL n-Butyl Lithium (0.02mol) with syringe, and stirring reaction 2 hours; Then under-78 DEG C of conditions, inject 5.6mL tributyltin chloride (0.02mol) again with syringe in mixed solution, stirring reaction is warming up to after 1 hour under room temperature and continues stirring reaction 6 hours; Add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, obtain organic layer; Anhydrous sodium sulfate drying organic layer, removes desolventizing by filtrate collection rotary evaporation after filtering, and obtains crude product; Crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 65%.
Step 9, preparation poly-{ 4-dodecyl two thieno-s [3,2-b:4,5-b '] pyrroles-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, in reaction flask, add 0.2mmol 4-dodecyl-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles, 0.2mmol 4,9-bis-bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) and 40ml tetrahydrofuran solvent, obtain mixed solution; Vacuumize and remove the oxygen in mixed solution and be filled with nitrogen; Then add 7.1 × 10
-3mmol Pd (PPh
3)
2cl
2, and be heated to 90 DEG C 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 multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, 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.
Copolymer p 1 after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 50016, n=48, multipolymer monodispersity is 2.2.
Embodiment 2
P2: poly-{ 4-methyl two thieno-s [3,2-b:4,5-b '] pyrroles-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }, have following structural formula:
The preparation process of above-mentioned copolymer p 2 is as follows:
Step 1-7 is with the step 1-7 of embodiment 1.
Step 8, preparation 4-methyl-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles
Under the protection of nitrogen, in there-necked flask, add 0.01mol 4-methyl-2,6-dibromo two thieno-s [3,2-b:4,5-b '] pyrroles and 40ml tetrahydrofuran solvent, obtain mixed solution; Under-78 DEG C of conditions, slowly in mixed solution, inject 8.6mL n-Butyl Lithium (0.02mol) with syringe, continue stirring reaction 1.5 hours; Then under-78 DEG C of conditions, inject 5.6mL tributyltin chloride (0.02mol) again with syringe in mixed solution, stirring reaction is warming up to after 1 hour under room temperature and continues stirring reaction 6 hours; Add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, obtain organic layer, anhydrous sodium sulfate drying organic layer, removes desolventizing by filtrate collection rotary evaporation after filtering, and obtains crude product; Crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 60%.
Step 9, preparation poly-{ 4-methyl two thieno-s [3,2-b:4,5-b '] pyrroles-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, in reaction flask, add 0.2mmol 4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene is coughed up also [2,1-b; 3,4-b '] two thiophene, 0.2mmol 4,9-bis-is bromo-6, and 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) and 40ml tetrahydrofuran solvent, obtain mixed solution; Vacuumize and remove the oxygen in mixed solution and be filled with nitrogen, then add 5.5 × 10
-3mmol Pd
2(dba)
3, and be heated to 90 DEG C 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 multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, 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.
Copolymer p 2 after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 16872, n=19, multipolymer monodispersity is 2.5.
Embodiment 3
P3: poly-{ 4-NSC 62789 base two thieno-s [3,2-b:4,5-b '] pyrroles-6-methyl-7-ethyl benzos [2,1-e:3,4-e] two (selenoles) }, have following structural formula:
The preparation process of above-mentioned copolymer p 3 is as follows:
Step 1-6 is with the step 1-6 of embodiment 1.
Step 7, preparation 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles)
In there-necked flask, add 10mmol 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles, 20mmol2-pentyne (synthetic method with reference to Chem.Commun., 2011,47,8850-8852) and 50ml DMF, obtain mixed solution; Under the condition stirring, in mixed solution, pass into nitrogen 20min, then add 20mmol Bu
3n and 1.0mmol Pd (OAc)
2, be warming up to 130 DEG C, and at 130 DEG C, react 4 hours; After question response liquid cooling but, wash with water, dichloromethane extraction, obtains organic layer; Anhydrous sodium sulfate drying organic layer; Filter, collect filtrate; By the method for underpressure distillation, the solvent in filtrate is removed, obtained crude product; Crude product is carried out to silica gel column chromatography separation, obtain product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (selenole) 5.15g, productive rate 65%.
Step 8, preparation 4-NSC 62789 base-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles
Under the protection of nitrogen, in there-necked flask, add 0.01mol 4-NSC 62789 base-2,6-dibromo two thieno-s [3,2-b:4,5-b '] pyrroles and 70ml tetrahydrofuran solvent, obtain mixed solution; Under-78 DEG C of conditions, slowly in mixed solution, inject 8.6mL n-Butyl Lithium (0.02mol) with syringe, and stirring reaction 1 hour; Then under-78 DEG C of conditions, inject 5.6mL tributyltin chloride (0.02mol) again with syringe in mixed solution, stirring reaction is warming up to after 1 hour under room temperature and continues stirring reaction 6 hours; Add 30ml saturated sodium-chloride water solution termination reaction, with anhydrous diethyl ether extraction, obtain organic layer; Anhydrous sodium sulfate drying organic layer, removes desolventizing by filtrate collection rotary evaporation after filtering, and obtains crude product; Crude product is carried out to neutral alumina column chromatography for separation, obtain product, productive rate 70%.
Step 9, preparation poly-{ 4-NSC 62789 base two thieno-s [3,2-b:4,5-b '] pyrroles-6-methyl-7-ethyl benzos [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, in reaction flask, add 0.2mmol 4-NSC 62789 base-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles, 0.2mmol 4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) and 40ml toluene solvant, obtain mixed solution; Vacuumize and remove the oxygen in mixed solution and be filled with nitrogen; Then add 7.8 × 10
-3mmol Pd (PPh
3)
4, and be heated to 90 DEG C 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 multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, 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.
Multipolymer (P3) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 18320, n=20, multipolymer monodispersity is 2.7.
Embodiment 4
P4: poly-4-NSC 62789 base two thieno-s [3,2-b:4,5-b '] pyrroles-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) }, there is following structural formula:
The preparation process of above-mentioned copolymer p 4 is as follows:
Step 1-6 is with the step 1-6 in embodiment 1.
Step 7, the bromo-6-(2 of preparation 4,9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides)
In there-necked flask, add 5mmol 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 selenoles, 10mmol2, and 6-dimethyl-9-30 alkynes (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852) and 30mlDMF, mixed solution obtained; Under the condition stirring, in mixed solution, pass into nitrogen 20min, then add 10mmol Bu
3n and 0.5mmol Pd (OAc)
2, be warming up to 130 DEG C, and at 130 DEG C, react 4 hours; After question response liquid cooling but, wash with water, dichloromethane extraction, obtains organic layer; Anhydrous sodium sulfate drying organic layer; Filter, collect filtrate; By the method for underpressure distillation, the solvent in filtrate is removed, obtained crude product; Crude product is carried out to silica gel column chromatography separation, obtains product 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfide) 2.7g, productive rate 62%.
Step 8 is with the step 8 in embodiment 3.
Step 9, preparation poly-{ 4-NSC 62789 base two thieno-s [3,2-b:4,5-b '] pyrroles-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, in reaction flask, add 0.3mmol 4-NSC 62789 base-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles, 0.2mmol 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (selenoles) and 40ml glycol dinitrate ether solvents, obtain mixed solution; Vacuumize and remove in mixed solution oxygen and be filled with nitrogen, then add 0.04mmol Pd (PPh
3)
2cl
2, and be heated to 120 DEG C 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 multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, 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.
Copolymer p 4 after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 129800, n=100, multipolymer monodispersity is 5.8.
Implement 5
P5: poly-{ 4-methyl two thieno-s [3,2-b:4,5-b '] pyrroles-6-methyl-7-ethyl benzos [2,1-e:3,4-e] two (selenoles) }, have following structural formula:
The preparation process of above-mentioned copolymer p 5 is as follows:
Step 1-6 is with the step 1-6 in embodiment 1.
Step 7 is with the step 7 in embodiment 3.
Step 8 is with the step 8 in embodiment 2.
Step 9, preparation poly-{ 4-methyl two thieno-s [3,2-b:4,5-b '] pyrroles-6-methyl-7-ethyl benzos [2,1-e:3,4-e] two (selenoles) }
Under nitrogen protection, in reaction flask, add 0.2mmol 4-methyl-2,6-bis-(tributyl tin)-bis-thieno-[3,2-b:4,5-b '] pyrroles (154.2mg), 0.3mmol 4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (selenoles) and 40ml solvent benzol, obtain mixed solution; Vacuumize and remove in mixed solution oxygen and be filled with nitrogen, then add 1.5 × 10
-4mmol Pd (PPh
3)
2cl
2, and be heated to 50 DEG C of reactions 6 hours; After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by multipolymer/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, 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.
Copolymer p 5 after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 650, n=1.
Embodiment 6
The multipolymer of preparing taking the embodiment of the present invention is active coating, prepares multipolymer solar cell device.Its structure as shown in Figure 2, comprises the substrate of glass 210 stacking gradually, anode 220, middle supplementary layer 230, active coating 240 and negative electrode 250.Wherein, anode 220 is ITO, is preferably the tin indium oxide that square resistance is 10 Ω/ (ITO), and middle supplementary layer 230 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, is called for short PEDOT:PSS; Active coating 240 comprises electron donor material and electron acceptor material, and electron donor material is multipolymer prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); Negative electrode 250 is aluminium, and this device architecture can briefly be described as glass/ITO/PEDOT:PSS/ active coating/Al.
The preparation method of above-mentioned multipolymer solar cell device is summarized as follows: using substrate of glass as bottom, choose ito glass (with anode ITO layer, can buy) when making, thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 110nm; The multipolymer of again being prepared by the 10mg embodiment of the present invention is dissolved in 0.4mL dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4mL chlorobenzene obtains, and is spun on PEDOT:PSS rete, and thickness is about 150nm, obtains active coating; At vacuum condition (2 × 10
-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains multipolymer solar cell device.Preparation method and the structure of the multipolymer solar cell device that contains multipolymer of the present invention are not limited to the present embodiment, can device suitably be improved or be modified.
Prepared multipolymer solar cell device using the multipolymer (P1, P2 and P3) of embodiment 1,2 and 3 preparations as active layer material respectively, obtained device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.
By the I-E characteristic of Keithley236 current/voltage source-measuring system and test component, obtain the performance data of device in table 1.
Table 1
As seen from the data in Table 1, the energy conversion efficiency of the multipolymer solar cell that the multipolymer making with the present invention is prepared as active coating is 0.90% ~ 1.38%, show that the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit of the present invention can mate preferably with solar spectrum, and the carrier mobility containing the multipolymer of two thiophene pyrroles and benzo two (selenole) unit is higher, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.
Embodiment 7
To the preparation containing the organic electroluminescence device of multipolymer of the present invention, its structure as shown in Figure 3:
The copolymer p 1 of preparing taking embodiment 1 is luminescent layer, is prepared with organic electroluminescence devices, and its structure as shown in Figure 3, comprises the glass substrate 310 stacking gradually, transparent anode 320, anode buffer layer 330, luminescent layer 340, cathode buffer layer 350 and negative electrode 360.Wherein, it is the tin indium oxide (ITO) that 10 Ω/, thickness are 150nm that transparent anode 320 is preferably square resistance, and it is the PEDOT:PSS preparation of 30nm that anode buffer layer 330 adopts thickness; Copolymer p 1 prepared by the embodiment 1 that luminescent layer 340 is 100nm for thickness, the LiF that cathode buffer layer 350 is 1.5nm for thickness, the metal A l that negative electrode 360 is 150nm for thickness, the structure of device is: glass/ITO/PEDOT:PSS/ copolymer p 1/LiF/Al, but the structure of practical devices is not limited to this.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 14.5cd/A, and high-high brightness is 1188cd/m
2.The above results shows, multipolymer prepared by embodiment 1 can improve luminance efficiency and high-high brightness as the luminescent layer of organic electroluminescence device.
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. containing a multipolymer for two thiophene pyrroles and benzo two (selenole) unit, there is following structural formula:
Wherein, the integer that n is 1 ~ 100;
R
1, R
2and R
3for C
1~ C
20alkyl.
2. a preparation method who contains the multipolymer of two thiophene pyrroles and benzo two (selenole) unit, comprises the steps:
Compd A and compd B are provided, and the structural formula of compd A is:
The structural formula of compd B is:
Wherein, R
1, R
2and R
3for C
1~ C
20alkyl;
Under shielding gas atmosphere; under the condition that the ratio that is 1:1.5 ~ 1.5:1 according to mol ratio by compd A and compd B exists at catalyzer and organic solvent, carry out Stille coupled reaction; wherein; temperature of reaction is 50 ~ 120 DEG C; reaction times is 6 ~ 100 hours, obtains having the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit of following structural formula after separation and purification:
Wherein, the integer that n is 1 ~ 100.
3. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 2, is characterized in that, described catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, 0.05% ~ 20% of the molar weight that the molar weight of described catalyzer is described compd B; Described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene;
The step of described separation and purification is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, use methyl alcohol sedimentation, 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 the multipolymer containing two thiophene pyrroles and benzo two (selenole) unit after purification.
4. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 2, is characterized in that, described compd A is adopted preparation with the following method:
Compound C is provided, and the structural formula of Compound C is:
Under shielding gas atmosphere; the ratio that is 1:2 according to mol ratio by Compound C and n-Butyl Lithium is reacted 1 ~ 2 hour in tetrahydrofuran (THF) under the condition of-78 DEG C; then add tributyltin chloride under the condition of-78 DEG C, to continue reaction 1 hour; then be warming up to room temperature; under room temperature, react 6 hours; obtain described compd A, wherein, the ratio of the mol ratio of tributyltin chloride and Compound C is 2:1.
5. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 2, is characterized in that, described compd B is adopted preparation with the following method:
Compound D and compd E are provided, and the structural formula of Compound D is:
The structural formula of compd E is:
Under shielding gas atmosphere, by Compound D, compd E and Bu
3n is that 1:2:1 ratio is at catalyst P d (OAc) according to mol ratio
2with solvent DMF exist condition under carry out ring closure reaction, obtain described compd B, wherein, temperature of reaction is 130 DEG C, the reaction times is 4 hours, Pd (OAc)
2the molar weight molar weight that is Compound D 10%.
6. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 5, is characterized in that, described Compound D is adopted preparation with the following method:
Compound F 17-hydroxy-corticosterone is provided, and the structural formula of compound F 17-hydroxy-corticosterone is:
Under shielding gas atmosphere, compound F 17-hydroxy-corticosterone is joined in ethanol, obtain mixed solution, under the condition refluxing, in described mixed solution, drip SeO
2the aqueous solution, and back flow reaction 2 hours, obtains described Compound D.
7. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 6, is characterized in that, described compound F 17-hydroxy-corticosterone is adopted preparation with the following method:
Compound G is provided, and the structural formula of compound G is:
Under shielding gas atmosphere, compound G is joined in ethanol, obtain suspension, then, at 0 DEG C, in described suspension, drip sodium borohydride, then stirring reaction 20 hours under room temperature, obtains described compound F 17-hydroxy-corticosterone.
8. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 7, is characterized in that, described compound G adopts preparation with the following method:
Compound H is provided, and the structural formula of compound H is:
Compound H, copper powder and DMF are mixed, be heated to 120 DEG C of reactions after 3 hours, be cooled to room temperature, add toluene, stir 30 minutes, obtain Compound I, the structural formula of Compound I is:
By Compound I, tetrahydrofuran (THF) and SnCl
2mix, heating reflux reaction 10 hours, cooling after, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, rotary evaporation gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 DEG C, after dropwising, reacts 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, reacts 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, obtains described compound G.
9. the preparation method of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 8, is characterized in that, described compound H is adopted preparation with the following method:
Compound J is provided, and the structural formula of compound J is:
Compound J is mixed with thionyl chloride, stir and slowly drip pyridine, heating reflux reaction 24 hours, obtains compound K, and the structural formula of compound K is:
Compound K is mixed with Hydrogen bromide, be warming up to after 127 DEG C, slowly drip bromine in 30 minutes, then back flow reaction 4 hours, obtains described compound H.
10. the application of the multipolymer that contains two thiophene pyrroles and benzo two (selenole) unit as claimed in claim 1 in multipolymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
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